Crystal landscape in the orcinol:4,4′-bi­pyridine system: synthon modularity, polymorphism and transferability of multipole charge density parameters

Polymorphism in the orcinol:4,4′-bipyridine cocrystal system is analyzed in terms of a robust convergent modular phenol⋯pyridine supramolecular synthon. Employing the Synthon Based Fragments Approach (SBFA) to transfer the multipole charge density parameters, it is demonstrated that the crystal landscape can be quantified in terms of intermolecular interaction energies in the five crystal forms so far isolated in this complex system. There are five crystal forms. The first has an open, divergent O—H⋯N based structure with alternating orcinol and bipyridine molecules. The other four polymorphs have different three-dimensional packing but all of them are similar at an interaction level, and are based on a modular O—H⋯N mediated supramolecular synthon that consists of two orcinol and two bipyridine molecules in a closed, convergent structure. The SBFA method, which depends on the modularity of synthons, provides good agreement between experiment and theory because it takes into account the supramolecular contribution to charge density. The existence of five crystal forms in this system shows that polymorphism in cocrystals need not be considered to be an unusual phenomenon. Studies of the crystal landscape could lead to an understanding of the kinetic pathways that control the crystallization processes, in other words the valleys in the landscape. These pathways are traditionally not considered in exercises pertaining to computational crystal structure prediction, which rather monitors the thermodynamics of the various stable forms in the system, in other words the peaks in the landscape.

1. Introduction

Crystal engineering is concerned with the development of logical design strategies based on the concept of the supramolecular synthon (Desiraju, 1995) and the execution of such strategies to obtain entire families of related crystal forms of a series of chemically similar molecules. The purpose of obtaining these engineered structures is to achieve physical and chemical properties of interest and utility (Desiraju, 1989; Desiraju et al., 2011). At a more fundamental level, crystal engineering may be reduced to elucidating the mechanism of crystallization (Weissbuch et al., 2003; Erdemir et al., 2009). Given any molecular structure, what is the crystal structure that would be obtained? If this question could be answered fully, the essential problem of crystal engineering would be solved because any pre-desired crystal structure could then be obtained at will. However, it is not likely that such an answer will be available anytime soon. The issues involved in the aggregation of molecules into clusters, larger ensembles and finally the events that lead up to nucleation and beyond are still way too complex to be addressed experimentally or computationally, in any general sense. Crystallography provides images of the `final' outcomes of the crystallization event, but the constraints of long-range periodicity that are implicit for any species that gives a three-dimensional diffraction pattern hardly reveal the multiplicity and variety of chemical events that have taken place before the crystal is obtained. Perhaps there is still some justification in Ruzicka's dismissal of solids as chemical cemeteries (Dunitz et al., 1988).

Still, and even within the limits imposed by diffraction-based crystallography, one might explore a small portion of the structural panorama that just precedes the `final' crystal because there are several higher energy crystal forms that may be isolated and characterized with crystallography that provide a hint about the mechanism of crystallization, at least in the later stages (Davey et al., 2006; Kulkarni et al., 2012; Hunter et al., 2012; Davey et al., 2013). These forms could include polymorphs with higher values of Z′, various solvates, kinetically labile species and other metastable and higher energy forms of the compound in question (Mukherjee et al., 2011; Braun et al., 2012). Taken collectively, one might envisage these forms as constituting a kind of landscape that profiles the structural and energetic changes that take place during the late stages of crystallization of an organic compound (Gavezzotti, 2003; Blagden & Davey, 2003; Price, 2008). Some of us have shown recently, using the example of fluoro-substitution in benzoic acids, that subtle chemical variation of a molecular scaffold permits the exploration of structural space that would otherwise be experimentally inaccessible (Dubey et al., 2012).

The formation of two-component molecular crystals, or cocrystals (Desiraju, 2003; Dunitz, 2003), is a well researched aspect of modern crystal engineering (Herbstein, 2005; Bond, 2007; Stahly, 2009; Wouters et al., 2011), although the phenomenon itself has been known since the isolation of quinhydrone more than 150 years ago (Wöhler, 1844). An interesting aspect of recent research on cocrystals, and indeed this was hinted at more than a decade ago when cocrystals came into the foreground, is that they may be less prone to form polymorphs than single-component crystals (Vishweshwar et al., 2005). This type of thinking possibly arose from the idea that cocrystal formation is only possible if very specific interactions between the two components are optimized and as such, these substances are less likely to form multiple crystal forms. Of course, such a contention can hardly be proved or disproved because it is, in Zaworotko's words, like `proving the negative' (Almarsson & Zaworotko, 2004). However, there has always been an interest in this matter. Recently, one of us co-authored a report on two polymorphs of the 2:3 cocrystal of orcinol (5-methylresorcinol) and 4,4′-bipyridine, I and II (Tothadi et al., 2011). Subsequently, the present group of authors were able to isolate two more polymorphs, III and IV, and one 1:1 cocrystal, V, which might be termed pseudopolymorphs. Noting that it was quite unusual to obtain five crystal forms in a cocrystal system, a systematic investigation of these forms was initiated, in the context of the structural landscape. In the course of this study, it was noted that the five forms are related through some basic supramolecular synthons and this confers a certain element of modularity (Desiraju, 2010; MacGillivray et al., 2000) in these crystal structures. We have previously shown that the modularity of the supramolecular synthon is responsible for the successful transferability of charge density derived multipole parameters for structural fragments, thus creating a possibility for the derivation of charge density maps for new compounds, in effect opening up an opportunity for the large scale application of charge density maps as a general structural tool in crystal engineering. We termed this methodology the Supramolecular Synthon Based Fragments Approach (SBFA) (Hathwar, Thakur, Row et al., 2011). We also showed that the SBFA method is applicable not only to single-component crystal structures but also to two-component crystals, or cocrystals (Hathwar, Thakur, Dubey et al., 2011). The SBFA approach is applied here to the crystal forms in the present study, in other words to polymorphs of cocrystals. The purpose of the transferability was to quantify the various intermolecular interactions present in the different polymorphic forms of the crystal landscape of the multi-component system. In effect, the utility of transferability of multipole parameters among the robust synthons in the various polymorphic modifications in cocrystals is demonstrated. The link between charge density distribution associated with transferable synthons and the possible aggregation pathways indicated in the landscape offers a unique possibility to quantify intermolecular interaction energies associated with kinetically stable polymorphic forms.

2. Experimental

2.1. Materials

Orcinol was purchased from Sigma Aldrich and 4,4′-bipyridine from Alfa Aesar and used without further purification. For the crystallization of all compounds, several stoichiometric ratios such as 1:1, 1:2, 2:1 and 2:3 were tried along with various crystallization methods such as solvent evaporation, sublimation and use of anti-solvent. After a week, good quality single crystals, which were suitable for the single-crystal diffraction experiments, were obtained. The ratio of the two compounds obtained in the crystal is not necessarily the ratio in which they are taken for the crystallization. Table 1 gives salient details of the cocrystals investigated in this study. Despite several attempts, it was not possible to obtain cocrystal I again. It may be noted that form III is obtained via sublimation, a technique that is not generally customary for multi-component crystals.

Table 1
Crystallographic details of forms II through to V

	II	III	IV	V
CCDC No.	944960	944963	944961	944962
Stoichiometric ratio (taken)	2:3	1:2	1:2	2:1
Stoichiometric ratio (in the crystal)	2:3	2:3	6:9	4:4
Method of crystallization	Solvent evaporation	Melt sublimation	From polymorph III at around 150 K	Solvent evaporation
Solvent	CH3NO2	–	–	CH3NO2
Crystal color	Light yellow	Colorless	Colorless	Yellow
Melting point (K)	453.2	453.4	–	448.9
Molecular formula	C7H8O2·C15H12N3	C7H8O2·C15H12N3	C21H24O6·C45H36N10	C28H32O8·C40H32N8
Formula weight	358.42	358.42	1075.26	1121.31
Crystal system	Triclinic	Monoclinic	Monoclinic	Monoclinic
Space group		P21/n	P21/n	P21/c
a (Å)	8.7711 (6)	9.0828 (3)	9.2118 (2)	17.8201 (5)
b (Å)	10.011 (1)	12.3446 (4)	36.2075 (7)	8.3288 (2)
c (Å)	12.0057 (9)	16.6095 (4)	16.5458 (4)	39.3222 (9)
α (°)	67.978 (8)	90	90	90
β (°)	78.030 (6)	96.320 (2)	97.923 (2)	91.901 (4)
γ (°)	69.224 (8)	90	90	90
V (Å^3)	910.4 (1)	1851.0 (1)	5465.9 (2)	5833.0 (3)
ρcalc (g cm^−3)	1.307	1.286	1.307	1.277
F(000)	378	756	2268	2368
μ (mm^−1)	0.086	0.084	0.085	0.085
T (K)	100 (2)	160 (2)	100 (2)	100 (2)
λ (Å)	0.71073	0.71073	0.71073	0.71073
Reflections collected	16 503	12 420	49 748	39 460
Unique reflections	3998	4066	11 990	12 764
Completeness (%)	99.9	100	99.9	99.9
Redundancy	4.0	3.1	4.1	3.1
Rint	0.035	0.029	0.050	0.075
R1 (F)	0.039	0.052	0.056	0.073
wR2 (F^2)	0.102	0.149	0.121	0.196
Goodness-of-fit	1.042	1.060	1.013	1.024
2θmax	54	54	54	54

2.2. Data collection and structure refinement details

Routine data sets for compounds II, IV and V were collected at 100 K on an Oxford Xcalibur diffractometer with a microfocus X-ray source (Mo Kα), equipped with a Cryojet-HT nitrogen gas-stream cooling device. The variable-temperature data sets for III were collected at 293, 200, 160, 140 and 120 K. In all these cases, data were processed with CrysAlisPro (Oxford Diffraction, 2011). Structure solution and refinements were performed with SHELX2012 (Sheldrick, 2008) using the WinGX suite (Farrugia, 2012).

2.3. High-resolution charge density data collection and structure refinement details of 4-hydroxybenzoic acid:isonicotinamide cocrystal

These data provide the required O—H⋯N synthon data entry into the in-house library which can be used for the subsequent analysis of the polymorphs of orcinol:bipyridine. Data were collected on a single crystal of reasonable size and quality (as was examined under a polarizing microscope) which was affixed to a Hampton Research cryoloop using Paratone-N oil. The crystal was cooled to 100 K with a liquid nitrogen stream using an Oxford cryosystems N₂ open-flow cryostat. High-resolution X-ray data up to (sinθ/λ)_max = 1.08 Å⁻¹ with redundancy (∼ 14) and completeness (∼ 100%) were collected on a Bruker Kappa Apex II CCD diffractometer using Mo Kα radiation at 100 K. Data collection strategies were generated using the COSMO module of the Bruker software suite (Bruker, 2006). The crystal-to-detector distance was fixed at 40 mm and the scan width was 0.5° per frame during the data collection. Cell refinement, data integration and reduction were carried out using the SAINTPLUS program. Numerical absorption correction was done by crystal face indexing. Sorting, scaling and merging of the collected data sets were carried out using the SORTAV program (Blessing, 1997). The crystal structure was solved by direct meth­ods and refined in the spherical-atom approximation using SHELXL2012 (Sheldrick, 2008) from the WinGX suite (Farrugia, 2012). The crystallographic information and multipole refinement details are provided in the supporting information.

2.4. Transferability of multipole parameters using the SBFA

Polymorphs of orcinol (5-methylresorcinol) and 4,4′-bipyridine studied in the present work were divided into chemically reasonable molecular fragments based on their supramolecular environments (supramolecular synthons; Fig. 1). The refined multipole parameters (P_val, P_lm, κ and κ′) present in the in-house library of experimental charge density data sets were used for SBFA transferability to all these target molecules. Scaling and initial refinement of the positional and displacement parameters of all atoms were carried out using the XD2006 package (Volkov et al., 2006). The H atoms were fixed to neutron values and the anisotropic displacement parameters of H atoms were computed using the SHADE2 server (Madsen, 2006; Munshi et al., 2008). Charge neutralization was obtained by fixing the individual atomic monopole to neutral atom values, followed by the refinement of atomic monopoles for all atoms which allowed realistic atomic charge values to be obtained. All other multipole parameters including κ and κ′ were kept fixed during the refinements.

Figure 1 Logical fragments based on supramolecular synthons (color shaded) in forms II through to V. Notice the brown synthon which consists only of a weak C—H⋯N interaction. These fragments may be transferred from structure to structure to generate a `synthetic' charge density map.

2.5. Theoretical evaluation of charge density to authenticate the multipole parameters derived from SBFA

Single-point periodic quantum mechanical calculations at the B3LYP/6-31G(d,p) level were carried out using CRYSTAL09 (Dovesi et al., 2009) with the neutron-normalized geometries obtained from experimental structure refinement. The shrinking factors (IS1, IS2 and IS3) along with the reciprocal lattice vectors were set to 4 (30 k-points in the irreducible Brillouin zone). The bi-electronic Coulomb and exchange series values for the truncation parameter were set as ITOL1 − ITOL4 = 8 and ITOL5 = 17, respectively, for the CRYSTAL09 calculations. The level shifter was set to 0.7 Hartree per cycle. The self-consistent field convergence limit was chosen as ∼ 10⁻⁷ Hartree. The cohesive energy calculation was performed in all cases and the Grimme dispersion corrections along with the basis set superposition error corrections were included in the calculations. For a definition of the cohesive energy and details of its calculation refer to the supporting information. Theoretical structure factors obtained from the CRYSTAL09 single-point calculations for II and III were used in the multipole refinements using the XD software package (Volkov et al., 2006). Molecular geometry and the atomic displacement parameters for all atoms were kept fixed throughout the multipole refinement of the static model. Refinements and analysis of the theoretically obtained charge density data were performed with an unrestricted multipole model to compare the results from the transferred SBFA model. The purpose of the theoretical modeling in the above two cases was to benchmark the quality of SBFA modeled densities.

3. Results and discussion

3.1. Analysis of crystal forms

All five solid forms of orcinol–bipyridine are characterized by O—H⋯N hydrogen bonds between the two components (Fig. 2). These hydrogen bonds form a finite divergent pattern (synthon A) that consists of two orcinol molecules and three bipyridine molecules, seen in form I, or a closed convergent pattern (synthon B) that consists of two orcinol and two bipyridine molecules, seen in the related forms II through to V. The latter pattern was first identified by MacGillivray in his extensive studies of solid-state topochemical reactions of phenol–pyridine cocrystals (Gao et al., 2004; MacGillivray et al., 2008; MacGillivray, 2008). Because synthon B is a zero-dimensional entity, it is possible that it persists in solution. Still, both divergent and convergent possibilities seem to be efficient molecular arrangements that use four O—H⋯N hydrogen bonds each. These assemblies are further supported by weak intermolecular interactions such as C—H⋯N, C—H⋯O, C—H⋯π and π⋯π interactions.

Figure 2 Divergent and convergent arrangement of O—H⋯N hydrogen bonds in (a) form I (synthon A), and (b) forms II–V (synthon B) of orcinol:4,4′-bipyridine cocrystals.

In the triclinic form II (Fig. 3b), the O—H⋯N hydrogen bonds in synthon B are normal (d, θ; 1.74 Å, 177.5°; 1.77 Å, 168.8°) and the arrangement is supported by weak C—H⋯N interactions (2.63 Å, 123.1°) from the orcinol C—H. The structure also contains a `free' bipyridine molecule which is sandwiched between two hydrogen-bonded tetramers (that is, synthon B) and stabilized by π⋯π and C—H⋯N interactions (2.62 Å, 148.5°) from bipyridine C—H.

Figure 3 Orcinol–bipyridine: (a) overlay diagram of forms II and III; (b) arrangement of LSAMs in form II, right, and form III, left; (c) schematic of molecular arrangement along the21-screw axis in form III.

The structure of form II is closely related to that of the new monoclinic form III (P2₁/n), which is also a 2:3 cocrystal. The tetramer synthons B (O—H⋯N, 1.75 Å, 175.2°; 1.76 Å, 175.3°) sandwich the free bipyridine in nearly the same manner. This larger assembly consisting of two tetramers and the sandwiched bipyridine is termed a Long Range Synthon Aufbau Module (LSAM) (Ganguly & Desiraju, 2008, 2010). The LSAM is a late synthon and Fig. 3(a) shows that the LSAMs in forms II and III are exceedingly similar. The advantage in differentiating between small and large synthons lies in the fact that the small synthons do not serve to distinguish well between polymorphs – the larger synthons include degrees of structural detail that permit such an exercise. In other words, the dissimilarity between the forms pertain not to the hydrogen bonding itself but rather to the arrangement of the LSAMs with respect to the crystallographic axes (Fig. 3b). All this clearly indicates that at a molecular recognition level (small supramolecular synthons) both forms are nearly the same, but as the molecular assembly becomes increasingly larger, the forms become different (Fig. 3b). Incidentally, orcinol molecules are nearly parallel to the crystallographic b-axis in form III. Taken with the mutually perpendicular arrangement of orcinol and bipyridine molecules, this leads to a pseudo character for the P2₁/n structure (Fig. 3c) (Sarma & Desiraju, 1986).

We collected single-crystal data of form III at five different temperatures and this showed evidence of a reversible phase transition between 140 and 160 K (Fig. 4). The structural details are given in the supporting information. After cooling through the phase transition, form III provides a new low-temperature crystal structure, form IV, which is modulated along the unique axis so that it is nearly three times the value of that in form III (Fig. 5). The O—H⋯N hydrogen bonds (1.74 Å, 173.9°; 1.74 Å, 176.8°; 1.75 Å, 170.6°; 1.76 Å, 171.9°; 1.77 Å, 177.3°) are again normal and there are also some other weak interactions. Form IV has a better packing than form III as shown from the Kitaigorodskii Packing Indices (KPI) (Table 2).

Table 2
KPI, crystal densities and energies for the compounds in this study

				Normalized†		Per molecule energy‡
	KPI (%)	Calculated crystal density (g cm^−3)	Energy CRYSTAL09 (kJ mol^−1)	CRYSTAL09 (kJ mol^−1)	EML (kJ mol^−1)	CRYSTAL09 (kJ mol^−1)	EML (kJ mol^−1)
Form I§	69.9	1.305	−684.88	−684.88	−	−143.89	−
Form II	70.7	1.308	−567.74	−1135.48	−957.0	−155.10	−153.46
Form III§	69.3	1.286	−634.77	−1269.54	−716.6	−141.54	−130.45
Form IV	70.6	1.307	−1888.43	−1259.58	−697.4	−144.18	−139.54
Form V	68.9	1.282	−925.59	–	–	−144.64	–

†Normalized: energy as a multiple of the (2:3) asymmetric unit.
‡The calculation has been described in the supporting information.
§Data collection at 150 K.

Figure 4 Thermodynamic (DSC) profile of forms II, III and V. Low temperature reversible III → IV phase transition (inset).

Figure 5 Orcinol–bipyridine: structure along the unique axis (shown in red) in forms III (left) and IV (right). Notice the triple modulation in the low temperature form.

It may be noted that the molecular and packing changes in the III → IV transition are subtle. The conformations of the orcinol and bipyridine are largely the same as the corresponding molecular orientations along the unique axis (Fig. 5). The relationship between modulated structures has traditionally been understood in terms of relaxation of symmetry; a translation becomes a pseudo-translation and so on. In the context of the structural landscape, it may be suggested that this relaxed structure represents events that occur later in the reaction coordinate for crystallization. Table 2 shows that the low temperature form IV is more dense and better packed than form III. The relaxation of symmetry allows for a better packing and is in keeping with the idea of a landscape that is a profile of the energy events during crystallization. Fig. 6 shows the positions of the centers and pseudo-centers of inversion in form IV especially with respect to synthon B. In this figure, the symmetry designation of molecules is color coded.

Figure 6 Arrangement of center and pseudo-center related synthons in form IV. Color coding is based on symmetry equivalence: blue: center of inversion; red: pseudo-center of inversion. Molecules of the same color are related by symmetry.

In form V (P2₁/c), the same type of hydrogen bonding (synthon B) is observed that is seen in forms II through to IV. The O—H⋯N hydrogen bonds are normal (1.76 Å, 176.1°; 1.76 Å, 179°; 1.78 Å, 178.5°; 1.78 Å, 175.2°; 1.79 Å, 173.4°; 1.80 Å, 174.8°; 1.80 Å, 173.3°; 1.81 Å, 169.4°). However, form V is different from forms II through to IV in that the `free' bipyridine is missing. We suggest that synthon B can develop into structures II or III by picking up a free bipyridine, or that alternatively it can nucleate and grow as form V so that it is effectively a branch point in the landscape from which the crystallization events can proceed in two entirely different ways, depending on the experimental conditions.

The thermal profile of forms II, III and V in Fig. 4 shows that while form II has a clean single endotherm, the differential scanning calorimetry (DSC) of form III indicates some degree of conversion to form II and possibly the existence of form IV or some other uncharacterized form. Form V is in any case less stable and shows a broad endotherm lower than any of the other forms. Form III is accessible on the landscape and leads to other forms.

3.2. Supramolecular synthon based fragments approach (SBFA) for the compounds in this study and their relative stabilities

The effectiveness of the SBFA method for transferability of multipole charge density parameters is due largely to the ability of the supramolecular synthon to act mechanistically as a modular unit. The electronic features of the synthon may be moved from one structure to another in the charge density analysis; such a procedure provides detail over and above what is obtained at the atomic and covalent bond level in the construction of `synthetic' charge density maps, thereby giving a fine degree of agreement between theory and experiment (Hathwar, Thakur, Dubey et al., 2011; Hathwar, Thakur, Row et al., 2011).

In the context of the crystal landscape, the experimental crystal structures of the compound in question are generally mapped using the computational approach of Crystal Structure Prediction (CSP) (Sarma & Desiraju, 2002; Neumann et al., 2008), in which possible crystal structures are predicted based on the energy–density profile. In spite of recent advances both in the algorithms as well as in increasing computational power, CSP of a multi-component system is still a challenge. Further, CSP protocol only takes into account the thermodynamic factors associated with packing, geometry optimization and clustering. It usually does not consider kinetic factors which are involved during the course of crystallization events. In order to fill this conceptual gap, experimental as well as theoretical charge density methods could be used (Koritsanszky & Coppens, 2001) which provide an energy profile of the immediate molecular vicinity because they address the system in terms of individual interactions. However, these rigorous methods have several hurdles such as the fact that very good crystals are needed, which diffract at high resolution (sinθ/λ ≥ 1.0), that the structures should be free from disorder and modulation, and that limitations like extinction and absorption should not be present. In the present study the multi-component orcinol–bipyridine system is both modulated and disordered and a rigorous charge density study is difficult. The utility of the transferable pseudo-atom databases approach in such situations is documented (Pichon-Pesme et al., 1995; Domagala et al., 2012; Dittrich et al., 2006, 2013; Dominiak et al., 2009; Volkov et al., 2007); we have used the SBFA protocol which we have developed and which is well suited to this situation.

Forms II through to V were accordingly quantitatively rationalized with SBFA. Based on the structural description it is clear that the robustness and modular nature of hydrogen bonds associated with synthon B are the critical factors in applying SBFA to forms II through to V. This is quantified via multipole parameters of the O—H⋯N hydrogen bonds derived from high-resolution X-ray diffraction data. The transferability of the multipole parameters of the O—H⋯N hydrogen bonds in synthon B, and other interactions, in forms II through to V, generate charge density maps and provide the quantitative insights of electronic distribution in the intermolecular region through their topological parameters.

The multi-component systems were divided, as described previously (Hathwar, Thakur, Dubey et al., 2011), into logical fragments based on their synthons, which involve both strong and weak interactions (Fig. 1). Multipole parameters for the strong hydrogen bonds (O—H⋯N) present in all the structures were taken from the experimental data of the 4-hydroxybenzoic acid:isonicotinamide (4HBA:INA) cocrystal (Vishweshwar et al., 2003), while the weaker ones C—H⋯O, C—H⋯N, C—H⋯π were chosen from an in-house library of synthons. The synthesized charge density features from SBFA were visualized through their deformation and Laplacian plots, which were in agreement with multipole refinements done on structure factors obtained from high-level density-functional theory calculations in CRYSTAL09 (Dovesi et al., 2009) (Fig. 7). The topological analysis of the intermolecular region was performed using the Quantum Theory of Atoms in Molecules (QTAIM), resulting in the location of bond-critical points between the strong as well as the weak interactions present in the crystal structures. The comparison was restricted to only forms II and III as our purpose was to verify the validity of the transferred model so that we could gain confidence in proceeding with the two other forms. In forms IV and V, which are more complex, the synthesized features were not compared with their theoretical values and were taken as they are. For form I we felt that the exercise itself was unfeasible because of the non-reproducibility of the form, as well as the slightly poor data quality of the already reported structure.

Figure 7 Comparison of deformation density and Laplacian maps [Δρ(r) and ∇^2ρ(r)] maps, obtained from SBFA (left) and theoretical calculations based on CRYSTAL09 (right), in O2—H2⋯N1 (a, b) and O1—H1⋯N2 (c, d) intermolecular space, respectively. Δρ(r) contours are drawn at ±0.05 e Å^−3. ∇^2ρ(r) (e Å^−5) drawn in logarithmic scale.

In form II, the topological analysis confirmed that O—H⋯N is the strongest interaction in the crystal structure. The remaining interactions present in the structure reflect their strengths in terms of their lower values of ρ and ∇²ρ. Comparison of the topological parameters between the SBFA model and theory deviates in only certain regions particularly for the strong O—H⋯N hydrogen bonds. The observed deviation in the Laplacian can be explained based on our previous work on the carboxylic dimer synthons, where it was attributed to the elongation of the O—H bonds. The comparable values between SBFA and theoretical topological parameters of covalent bonds and other weak intermolecular interactions support the validity of the transferred model (Table 3). The comparison of form III with theory and the topological parameters of forms IV and V have been summarized in the supporting information.

Table 3
Numerical (top) and graphical (bottom) comparison of the topological parameters, SBFA and theory (italics), of form II

Synthon	ρ (e Å^−3)	∇^2ρ (e Å^−5)	Rij (Å)	∊	G (kJ mol^−1 bohr^−3)	V(kJ mol^−1 bohr^−3)	|V|/G
O2—H2⋯N1	0.34	2.5	1.738	0.05	97.24	−127.61	1.31
	0.41	0.8	1.734	0.03	84.77	−147.80	1.74
O1—H1⋯N2	0.31	2.4	1.7663	0.06	85.87	−107.93	1.26
	0.36	1.5	1.7666	0.04	83.58	−125.43	1.50
C9—H9⋯O1	0.05	0.8	2.5076	0.21	16.64	−10.98	0.66
	0.05	0.7	2.4816	0.19	15.02	−10.68	0.71
C20—H20⋯O2	0.03	0.6	2.6806	0.44	11.30	−7.16	0.63
	0.03	0.6	2.6167	0.21	12.12	−7.98	0.66
C11—H11⋯C6	0.04	0.8	2.5472	0.97	16.42	−10.58	0.64
	0.08	0.5	2.5301	0.08	14.02	−13.24	0.94
C4—H4⋯N1	0.04	0.5	2.7078	0.44	9.45	−6.65	0.70
	0.04	0.5	2.6603	0.11	14.71	−9.92	0.67
C8—H8⋯N3	0.03	0.6	2.6795	1.18	12.15	−7.66	0.63
	0.03	0.6	2.633	0.01	11.66	−8.69	0.75

For the calculation of binding energies, it was also found convenient to define a molecular shell based on a coordination envelope around the asymmetric unit. In practice, all molecules that are found 0.2 Å beyond the van der Waals surface of the asymmetric unit (defined in terms of the closest group of bipyridine and orcinol molecules) constitute the shell. The shell consists of O—H⋯N hydrogen bonds, C—H⋯N and C—H⋯O hydrogen bonds and several weak C⋯C interactions. A critical-point search within the shell provides all the required contacts to be considered in the calculation. The Espinosa–Molins–Lecomte method (Espinosa et al., 1998) was used to calculate the interaction energy (E_int) using the Abramov expression (Abramov, 1997) which gives the kinetic and the potential energy density at the bond-critical points. The magnitude of the energy obtained by this approach is an indicator and not an absolute value, and hence a direct comparison with the values obtained from periodic DFT calculation may not be appropriate.

The binding energy, that is the energy of a molecular shell, was used to compute the relative stabilities of the different forms using the EML method (Nelyubina et al., 2010). This was compared with the cohesive energy calculations performed using CRYSTAL09. In single-component crystals with Z′ = 1, the treatment of the cohesive energy is straightforward. When Z′ > 1 the computations are more involved but still manageable. In multi-component systems, however, the complexity of the calculations increases to a level that is unworkably tedious. In our system, the various forms do not even have the same Z′ values and one of them is also a pseudopolymorph. In such a scenario, the SBFA and EML methods provide a simplified method for calculation of energies, and this is a distinct advantage. The CRYSTAL09 and EML methods also have a slightly different physical interpretation which will be more clearly outlined in the next section.

The energies reported in Table 2 are obtained with CRYSTAL09 and EML, where the energy E_coh corresponds to the energy of the defined asymmetric unit. The calculated energies cannot be used directly because the volume of the asymmetric unit is different in the five forms. Still, we attempted the quantification of forms I through to IV as they have the same 2:3 stoichiometric ratio. Even here we need to normalize the values because the number of molecules in the asymmetric unit is different in each of the forms. In this way, we find that form I is the least stable, and that forms II and III are equi­energetic. It was conjectured that the energy values are biased considerably by the complexity of the cocrystal formation and the values of Z′ and hence another calculation based on energy per molecule was performed.

3.3. Structural landscape

The concept of the landscape follows naturally from the phenomena of polymorphism (Bernstein, 2002) and pseudopolymorphism and is conveniently applied to mono-component systems. In two-component systems, like the present case, it seems natural to assume that the earliest stages of recognition (smallest synthons) are heteromolecular in nature, for how else would a two-component system be obtained? The very fact that a two-component crystal AB is even obtained suggests that one or more interactions of the type A⋯B are better than any of the interactions of the type A⋯A or B⋯B (Sarma & Desiraju, 1985). In turn, these stable A⋯B heterosynthons permute themselves in different ways to give various polymorphs, so that one is, in effect, traversing the landscape. It may be supposed that the simple synthon B associates with other such synthons in solution without any symmetry constraints, and as crystallization becomes more enthalpy controlled, these clusters (aggregates, shell) gradually approach the final configurations as seen in forms II and III (more symmetry constraints), and forms IV and V (less symmetry constraints). In effect, the small synthons represent a certain `irreversible' point and all subsequent events follow from it.

Structures II through to V may be understood as representing alternative arrangements of modules, that we have termed LSAMs. At this point, it is worth noting that the LSAM, as we have defined, has some similarity with the `growth unit' as defined by Davey (Davey et al., 2002) with the caveat that Davey`s growth unit may also incorporate solvent. The similarity stems from the fact that all these species are pre-nucleation entities. The modularity of LSAMs permits an analysis of charge density data in terms of contributions from structural fragments that are treated in a similar way to the pseudo-atoms in the classical charge density transferability approaches. The modularity of these structural fragments also helps in their analysis from the viewpoint of the structural landscape. Modularity is the key link that connects all the structures that constitute the landscape.

If there are two steps in the late stages of crystallization, finite strands of alternating bipyridine (three molecules) and orcinol (two molecules), which we have defined as synthon A, crystallize, in the first step, to give form I with O—H⋯N hydrogen bonds in the distance range 1.75–1.81 Å and an angle range 164–179°. This is shown in Fig. 8(a). It is not at all difficult to conceive a process in which successive O—H⋯N hydrogen bonds are made and broken (Fig. 8b) and orcinol molecules rotate nearly 180° so that the structure evolves into that of form II with its closed synthon (Fig. 8c). In this scenario, form I would be a kinetic form. Although not proof, the fact that we were unable to obtain form I again would hint that it is also metastable. To summarize, there are two aggregation possibilities of the LSAMs. In both possibilities the third bipyridine is an active participant either being hydrogen bonded (form I) or facilitating close packing (forms II through to IV). Form V is different and develops independently from synthon B not requiring the free bipyridine. This is shown in Fig. 9.

Figure 8 (a) Finite divergent arrangement (synthon A) of molecules in form I. (b) Possible rearrangement of molecules during the course of crystallization. (c) Finite convergent arrangement (synthon B) of molecules in forms II through to V.

Figure 9 (a) Molecular recognition based on O—H⋯N hydrogen bonds and the formation of synthon B. (b) Various topologies of forms II through to V, anticlockwise, based on synthon B.

During navigation of the nucleation pathway of forms II through to IV, the system exploits the modular nature of synthon B as a means of achieving the structures based on their energies. As we have already discussed, forms II and III are similar at the smaller aggregate, and this suggests that up to a certain point the modular unit follows the same nucleation path, but as the aggregation level becomes larger and larger there are shifts leading to a choice between two different pathways – finally this results in two different crystal structures. The quantitative analysis leading to the estimates of interaction energies using two different approaches (CRYSTAL09 and SBFA/EML) brings out the significance of the regions of the landscape between forms II and III. In practical terms, both forms appear to be practically equivalent in that they lie in nearly the same region of the energy–density plot. On the other hand, form II shows slightly better packing than form III, and after the phase transition, form III converts into form IV which is packed as efficiently as form II (Table 2). This emergence of better packing is the result of the relaxation in the symmetry constraints in form III. In the context of the landscape, such behaviour is interesting. Forms II and IV have nearly the same densities, energies and packing efficiencies but they represent entirely different pathways in the landscape, and their structures are also quite different. The relative stabilities of forms II, III and IV with similar asymmetric units are selected below.

It is unlikely that forms II and IV can interconvert easily, but they have the lowest energies among the forms isolated and studied here. Which is the global minimum? Is there another, yet undiscovered form, which is of even lower energy? If not, is it fair to speak of two independent crystallization pathways, each leading to a stable outcome? In this case, how relevant were early versions of the CSP blind tests that demanded only the top three choices for a molecule or a cocrystal? Information, such as is obtained here, regarding various possibilities of nucleation pathways in the reaction coordinate during the course of crystallization, such as the existence of form III, and which finally leads to form IV, which seems to be just as favourable as form II, conveys that there need not be just one structure at the global minimum. More than ever, there is now a compelling feeling that the concept of `crystal structure' is not unique. The comment needs emphasis: rather than speak of the crystal structure of a molecule, a term that may have only a limited meaning in the landscape context, it may be fairer to speak of a crystal structure of a molecule (in this case a molecular system, because we are dealing with cocrystals). A particular structure is just one of many.

During the solution → crystal pathway, there could be various metastable forms and structural fragments which may not appear in the final crystal structure. These metastable structures are the outcome of crystal synthesis because of the competition between kinetic and thermodynamic factors associated with the transition from an entropy dominated scenario in solution to an enthalpically determined crystal. These (metastable) crystal structures (known as polymorphs or pseudopolymorphs) which encapsulate thermodynamic factors as well as energy–density profiling constitute a large landscape which may be accessed either by the hydrogen-bond hierarchies during the solution to the supersaturated state or via thermal transformations in the final stages of crystallization. In solution, molecules recognize one another based on their complementary hydrogen-bonding functionalities which define the basic kinetic units of the crystal structure, namely supramolecular synthons. Even as the hydrogen-bond hierarchies are established, and based on their respective energies, synthons optimize themselves right from the initial to intermediate to final stages of crystallization until chemically (kinetic) or geometrically (thermodynamic) reasonable structures are obtained for the organic compound in question. This is the final stage of crystallization in which the dichotomies between synthon versus close packing become fully manifest. Alternatively, one might reduce the molecule → crystal progression in the landscape into a discussion of packing (thermodynamic aspects) and synthon theory (kinetic aspects). We would urge an appreciation of both these viewpoints in the current scenario (Kitaigorodskii, 1973; Dunitz & Gavezzotti, 2005; Desiraju, 2007).

4. Conclusions

This work addresses several questions that highlight the difficulties faced in dealing with complex systems in crystal engineering. Our approaches have posed questions that future methodologies should hopefully address. We have shown that the closed zero-dimensional convergent phenol⋯pyridine synthon (synthon B) is robust and constitutes the element of modularity that causes extensive polymorphism in the orcinol−bipyridine system. Within the context of the present example, it is therefore not possible to state that cocrystal formation decreases the likelihood of polymorphism. It is true that the major interaction, namely O—H⋯N, is conserved in all the forms but the polymorphism is caused by a variation in the more minor interactions, in other words in the ways in which synthon B modules are arranged with respect to one another. Larger assemblies of synthon B may be termed as Long Range Synthon Aufbau Modules or LSAM. This work also shows that this collection of polymorphs of orcinol−bipyridine constitutes a landscape which may be studied by an energy profiling and interaction profiling, both of which may be carried out with charge density studies, more particularly with our newly suggested technique of Supramolecular Synthon Based Fragments Approach (SBFA) for transferability of multipole parameters. The synthon is a modular structural unit that lends itself particularly well to the transferability of electron density information in a crystal structure. The polymorphs of orcinol−bipyridine are structurally complex in a manner that renders them problematic for other methods of charge density analysis and our method offers some choice in this regard. The idea of a structural landscape that is defined by polymorphs, solvates and computed structures provides an indication about events in the late stages of crystallization. While computational CSP inputs on the thermodynamics of these events, or vertical profiling of the landscape, charge density methods give information on the interactions themselves and therefore, in principle, can lead to horizontal profiling and a measure of the kinetics that underlie crystallization events because in the end it is the energy and distance dependence of individual interactions that determine actual crystallization pathways which are essentially kinetically governed.

Supporting information

Experimental

(type here to add preparation details)

Refinement

(type here to add refinement details)

Computing details

For all compounds, data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

(II)

Crystal data

1.5(C10H8N2)·1(C7H8O2)	Z = 2
Mr = 358.42	F(000) = 378
Triclinic, P1	Dx = 1.308 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7711 (6) Å	Cell parameters from 7563 reflections
b = 10.0113 (10) Å	θ = 2.4–27.4°
c = 12.0057 (9) Å	µ = 0.09 mm^−1
α = 67.978 (8)°	T = 100 K
β = 78.030 (6)°	Block, colourless
γ = 69.224 (8)°	0.60 × 0.40 × 0.40 mm
V = 910.38 (15) Å^3

Data collection

Xcalibur, Eos, Nova diffractometer	3998 independent reflections
Radiation source: Mova (Mo) X-ray Source	3516 reflections with I > 2σ(I)
mirror	Rint = 0.035
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.1°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −13→12
Tmin = 0.872, Tmax = 1.000	l = −15→15
16515 measured reflections

Refinement

Refinement on F^2	324 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.102	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.2125P] where P = (Fo^2 + 2Fc^2)/3
3998 reflections	(Δ/σ)max < 0.001

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.40093 (12)	0.65915 (11)	0.66072 (9)	0.0226 (3)
N2	−0.38717 (12)	0.72785 (12)	0.98189 (9)	0.0249 (3)
C8	0.34906 (15)	0.73831 (14)	0.73715 (11)	0.0230 (4)
C9	0.19775 (15)	0.75425 (13)	0.80320 (10)	0.0217 (4)
C10	0.09106 (14)	0.68628 (13)	0.79026 (10)	0.0182 (3)
C11	0.14375 (15)	0.60707 (14)	0.70862 (11)	0.0227 (4)
C12	0.29698 (15)	0.59614 (14)	0.64716 (11)	0.0242 (4)
C13	−0.07250 (14)	0.69849 (13)	0.85881 (10)	0.0188 (3)
C14	−0.15520 (15)	0.82019 (14)	0.89995 (11)	0.0228 (4)
C15	−0.30936 (15)	0.82972 (14)	0.96018 (11)	0.0258 (4)
C16	−0.30589 (16)	0.60951 (14)	0.94350 (11)	0.0250 (4)
C17	−0.15130 (15)	0.59012 (14)	0.88303 (11)	0.0231 (4)
N3	−0.39800 (13)	0.98261 (12)	0.64115 (9)	0.0268 (3)
C18	−0.17371 (15)	1.08465 (14)	0.60104 (11)	0.0241 (4)
C19	−0.32696 (16)	1.07400 (15)	0.65361 (12)	0.0275 (4)
C20	−0.31088 (16)	0.89950 (15)	0.57191 (12)	0.0300 (4)
C21	−0.15692 (15)	0.90195 (15)	0.51580 (12)	0.0275 (4)
C22	−0.08276 (14)	0.99691 (12)	0.52930 (10)	0.0182 (3)
O1	0.28063 (10)	0.84314 (9)	0.02579 (7)	0.0229 (3)
O2	0.28284 (10)	0.46048 (9)	0.41895 (7)	0.0223 (3)
C1	−0.05196 (14)	0.75442 (13)	0.24908 (10)	0.0182 (3)
C2	0.03294 (14)	0.82291 (13)	0.14395 (10)	0.0193 (4)
C3	0.20311 (14)	0.77033 (13)	0.13028 (10)	0.0180 (3)
C4	0.29084 (14)	0.64851 (12)	0.22090 (10)	0.0171 (3)
C5	0.20490 (14)	0.57987 (12)	0.32630 (10)	0.0171 (4)
C6	0.03467 (14)	0.63362 (13)	0.34024 (10)	0.0177 (3)
C7	−0.23684 (15)	0.80785 (15)	0.26339 (11)	0.0266 (4)
H8	0.43381	0.79035	0.74494	0.0393
H9	0.16815	0.81882	0.86393	0.0373
H11	0.06358	0.55680	0.69193	0.0349
H12	0.34010	0.53397	0.58402	0.0356
H14	−0.10274	0.90966	0.88311	0.0374
H15	−0.37462	0.92374	0.99310	0.0406
H16	−0.37164	0.52879	0.96307	0.0412
H17	−0.09591	0.49081	0.85537	0.0371
H18	−0.12543	1.16076	0.61731	0.0381
H19	−0.39764	1.14230	0.70949	0.0399
H20	−0.36549	0.82448	0.56042	0.0370
H21	−0.09529	0.82850	0.46234	0.0340
H1	0.40001	0.79089	0.01939	0.0339
H2	0.39697	0.41460	0.38988	0.0336
H2A	−0.03261	0.91735	0.07237	0.0352
H4	0.42331	0.60930	0.21014	0.0364
H6	−0.02856	0.57967	0.42330	0.0348
H7A	−0.28604	0.76173	0.21617	0.0431
H7B	−0.28768	0.77195	0.35540	0.0423
H7C	−0.28960	0.92844	0.22458	0.0424

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0172 (6)	0.0219 (5)	0.0251 (5)	−0.0039 (4)	−0.0005 (4)	−0.0066 (4)
N2	0.0198 (6)	0.0294 (6)	0.0241 (5)	−0.0087 (5)	0.0028 (4)	−0.0088 (5)
C8	0.0183 (7)	0.0248 (7)	0.0277 (6)	−0.0082 (5)	−0.0022 (5)	−0.0089 (5)
C9	0.0196 (7)	0.0240 (6)	0.0248 (6)	−0.0072 (5)	−0.0003 (5)	−0.0119 (5)
C10	0.0165 (6)	0.0172 (6)	0.0196 (6)	−0.0048 (5)	−0.0019 (5)	−0.0048 (5)
C11	0.0202 (7)	0.0244 (6)	0.0274 (6)	−0.0089 (5)	−0.0001 (5)	−0.0118 (5)
C12	0.0229 (7)	0.0247 (6)	0.0255 (6)	−0.0061 (5)	0.0017 (5)	−0.0120 (5)
C13	0.0165 (6)	0.0217 (6)	0.0180 (6)	−0.0058 (5)	−0.0016 (5)	−0.0064 (5)
C14	0.0199 (7)	0.0238 (6)	0.0281 (6)	−0.0095 (5)	0.0008 (5)	−0.0112 (5)
C15	0.0203 (7)	0.0278 (7)	0.0306 (7)	−0.0063 (5)	0.0030 (5)	−0.0146 (6)
C16	0.0222 (7)	0.0267 (7)	0.0273 (6)	−0.0132 (5)	0.0030 (5)	−0.0076 (5)
C17	0.0218 (7)	0.0223 (6)	0.0264 (6)	−0.0077 (5)	0.0004 (5)	−0.0098 (5)
H8	0.0313	0.0492	0.0477	−0.0200	−0.0003	−0.0217
H9	0.0361	0.0427	0.0421	−0.0144	0.0023	−0.0245
H11	0.0316	0.0403	0.0414	−0.0176	0.0022	−0.0194
H12	0.0326	0.0405	0.0379	−0.0107	0.0040	−0.0214
H14	0.0356	0.0355	0.0476	−0.0164	0.0037	−0.0194
H15	0.0359	0.0412	0.0485	−0.0095	0.0068	−0.0266
H16	0.0400	0.0463	0.0467	−0.0261	0.0101	−0.0206
H17	0.0382	0.0347	0.0434	−0.0142	0.0070	−0.0207
N3	0.0191 (6)	0.0308 (6)	0.0330 (6)	−0.0092 (5)	0.0030 (5)	−0.0144 (5)
C18	0.0210 (7)	0.0271 (7)	0.0308 (7)	−0.0111 (5)	0.0034 (5)	−0.0163 (6)
C19	0.0208 (7)	0.0339 (7)	0.0341 (7)	−0.0104 (6)	0.0065 (5)	−0.0207 (6)
C20	0.0226 (8)	0.0333 (7)	0.0442 (8)	−0.0142 (6)	0.0048 (6)	−0.0226 (6)
C21	0.0195 (7)	0.0313 (7)	0.0402 (7)	−0.0103 (6)	0.0065 (6)	−0.0234 (6)
C22	0.0159 (6)	0.0179 (6)	0.0193 (5)	−0.0039 (5)	−0.0021 (5)	−0.0053 (5)
H18	0.0375	0.0371	0.0488	−0.0160	0.0003	−0.0220
H19	0.0340	0.0427	0.0470	−0.0079	0.0051	−0.0272
H20	0.0305	0.0435	0.0470	−0.0187	0.0039	−0.0227
H21	0.0293	0.0364	0.0417	−0.0113	0.0056	−0.0220
O1	0.0184 (5)	0.0249 (5)	0.0206 (4)	−0.0086 (4)	0.0039 (3)	−0.0033 (4)
O2	0.0183 (5)	0.0219 (4)	0.0198 (4)	−0.0026 (3)	0.0008 (3)	−0.0040 (4)
C1	0.0159 (6)	0.0187 (6)	0.0235 (6)	−0.0066 (5)	0.0020 (5)	−0.0114 (5)
C2	0.0179 (7)	0.0181 (6)	0.0203 (6)	−0.0047 (5)	−0.0016 (5)	−0.0055 (5)
C3	0.0202 (7)	0.0179 (6)	0.0186 (5)	−0.0097 (5)	0.0027 (5)	−0.0076 (5)
C4	0.0142 (6)	0.0181 (6)	0.0210 (6)	−0.0058 (5)	0.0013 (5)	−0.0092 (5)
C5	0.0198 (7)	0.0151 (6)	0.0186 (6)	−0.0058 (5)	−0.0010 (5)	−0.0078 (5)
C6	0.0179 (6)	0.0190 (6)	0.0185 (6)	−0.0090 (5)	0.0037 (4)	−0.0084 (5)
C7	0.0164 (7)	0.0305 (7)	0.0278 (6)	−0.0052 (5)	0.0018 (5)	−0.0080 (6)
H1	0.0243	0.0353	0.0349	−0.0068	0.0021	−0.0082
H2	0.0279	0.0335	0.0320	−0.0035	0.0018	−0.0105
H2A	0.0303	0.0321	0.0346	−0.0062	−0.0049	−0.0037
H4	0.0222	0.0403	0.0383	−0.0056	0.0015	−0.0097
H6	0.0320	0.0371	0.0314	−0.0152	0.0049	−0.0069
H7A	0.0354	0.0545	0.0536	−0.0171	−0.0034	−0.0305
H7B	0.0335	0.0558	0.0330	−0.0161	0.0045	−0.0112
H7C	0.0327	0.0307	0.0565	−0.0070	−0.0034	−0.0092

Geometric parameters (Å, °)

O1—C3	1.3709 (14)	C16—H16	1.0800
O2—C5	1.3682 (14)	C17—H17	1.0800
O1—H1	0.9900	C18—C19	1.384 (2)
O2—H2	0.9900	C18—C22	1.3911 (18)
N1—C8	1.3392 (17)	C20—C21	1.383 (2)
N1—C12	1.3425 (18)	C21—C22	1.3968 (19)
N2—C15	1.3396 (18)	C22—C22^i	1.4879 (18)
N2—C16	1.3410 (18)	C18—H18	1.0800
N3—C19	1.3392 (19)	C19—H19	1.0800
N3—C20	1.3309 (18)	C20—H20	1.0800
C8—C9	1.3870 (19)	C21—H21	1.0800
C9—C10	1.3979 (19)	C1—C7	1.511 (2)
C10—C13	1.4872 (18)	C1—C2	1.3932 (17)
C10—C11	1.3922 (18)	C1—C6	1.3922 (17)
C11—C12	1.381 (2)	C2—C3	1.3920 (19)
C13—C14	1.3893 (19)	C3—C4	1.3963 (17)
C13—C17	1.3969 (19)	C4—C5	1.4005 (17)
C14—C15	1.384 (2)	C5—C6	1.3931 (19)
C16—C17	1.383 (2)	C2—H2A	1.0800
C8—H8	1.0800	C4—H4	1.0800
C9—H9	1.0800	C6—H6	1.0800
C11—H11	1.0800	C7—H7A	1.0800
C12—H12	1.0800	C7—H7B	1.0800
C14—H14	1.0800	C7—H7C	1.0800
C15—H15	1.0800
O1···N2^ii	2.7447 (15)	H1···C16^ii	2.7800
O1···C9^iii	3.3926 (15)	H1···H4	2.3200
O2···N1^iv	2.7285 (15)	H2···H20^vi	2.3400
O1···H9^iii	2.4800	H2···H4	2.3400
O1···H2A^v	2.6700	H2···C8^iv	2.7500
O1···H14^i	2.8900	H2···N1^iv	1.7400
O1···H15^i	2.6600	H2···C12^iv	2.6000
O2···H12	2.5500	H2A···H14^iii	2.5100
O2···H7B^vi	2.8300	H2A···C2^v	2.9100
O2···H20^vi	2.6100	H2A···H2A^v	2.0500
O2···H6^vi	2.6500	H2A···H7C	2.5900
N1···C5^iv	3.4319 (17)	H2A···C14^iii	3.0900
N1···C4^iv	3.3495 (17)	H2A···O1^v	2.6700
N1···O2^iv	2.7285 (15)	H4···C12^iv	2.9500
N2···O1^vii	2.7447 (15)	H4···N1^iv	2.6300
N3···C7^viii	3.3891 (19)	H4···H2	2.3400
N1···H4^iv	2.6300	H4···H1	2.3200
N1···H20^ix	2.8800	H6···O2^vi	2.6500
N1···H2^iv	1.7400	H6···H7B	2.4500
N2···H1^vii	1.7600	H6···H11^vi	2.4000
N3···H8^x	2.6200	H6···C6^vi	2.8400
N3···H7C^viii	2.9000	H6···H21	2.5500
C4···N1^iv	3.3495 (17)	H6···H6^vi	1.9500
C5···N1^iv	3.4319 (17)	H7A···C15^iii	2.9200
C6···C11^vi	3.5659 (19)	H7B···O2^vi	2.8300
C7···N3^viii	3.3891 (19)	H7B···H6	2.4500
C9···O1^xi	3.3926 (15)	H7C···N3^viii	2.9000
C11···C6^vi	3.5659 (19)	H7C···H2A	2.5900
C11···C21	3.594 (2)	H8···H20^ix	2.5200
C12···C18^i	3.4648 (18)	H8···C20^ix	2.9400
C14···C19	3.3121 (19)	H8···N3^ix	2.6200
C14···C18	3.5673 (18)	H9···O1^xi	2.4800
C15···C19	3.5734 (19)	H9···H14	2.2200
C18···C12^i	3.4648 (18)	H9···C14	2.7700
C18···C14	3.5673 (18)	H11···C17	2.6900
C19···C15	3.5734 (19)	H11···H6^vi	2.4000
C19···C14	3.3121 (19)	H11···C1^vi	2.9600
C21···C11	3.594 (2)	H11···C6^vi	2.5300
C1···H18^i	2.9500	H11···H17	2.1900
C1···H11^vi	2.9600	H12···O2	2.5500
C1···H21	2.8400	H14···C9	2.7300
C1···H17^vi	2.9400	H14···H9	2.2200
C2···H17^vi	2.9900	H14···C3^i	2.9600
C2···H2A^v	2.9100	H14···C2^i	2.8400
C2···H14^i	2.8400	H14···H2A^xi	2.5100
C3···H17^vi	3.0100	H14···O1^i	2.8900
C3···H14^i	2.9600	H15···H15^xii	2.2000
C4···H19^i	3.0000	H15···O1^i	2.6600
C4···H18^i	3.0300	H16···H16^xiii	2.4300
C4···H17^vi	3.0000	H17···C4^vi	3.0000
C5···H18^i	2.7400	H17···C5^vi	2.9500
C5···H17^vi	2.9500	H17···C11	2.7500
C6···H18^i	2.6900	H17···H11	2.1900
C6···H6^vi	2.8400	H17···C3^vi	3.0100
C6···H11^vi	2.5300	H17···C2^vi	2.9900
C6···H21	2.6700	H17···C6^vi	2.9200
C6···H17^vi	2.9200	H17···C1^vi	2.9400
C7···H19^viii	3.0300	H18···C1^i	2.9500
C7···H21	3.0100	H18···C4^i	3.0300
C8···H2^iv	2.7500	H18···C5^i	2.7400
C8···H20^ix	3.0800	H18···C6^i	2.6900
C9···H14	2.7300	H18···H21^i	1.9900
C11···H17	2.7500	H18···C21^i	2.6600
C12···H2^iv	2.6000	H19···C4^i	3.0000
C12···H4^iv	2.9500	H19···C7^viii	3.0300
C14···H2A^xi	3.0900	H20···N1^x	2.8800
C14···H9	2.7700	H20···C8^x	3.0800
C15···H1^vii	2.6300	H20···H8^x	2.5200
C15···H7A^xi	2.9200	H20···O2^vi	2.6100
C16···H1^vii	2.7800	H20···H2^vi	2.3400
C17···H11	2.6900	H21···C7	3.0100
C18···H21^i	2.6700	H21···C18^i	2.6700
C20···H8^x	2.9400	H21···H18^i	1.9900
C21···H18^i	2.6600	H21···H6	2.5500
H1···C15^ii	2.6300	H21···C1	2.8400
H1···N2^ii	1.7600	H21···C6	2.6700
C3—O1—H1	112.00	N3—C20—C21	124.51 (14)
C5—O2—H2	110.00	C20—C21—C22	120.13 (13)
C8—N1—C12	116.87 (12)	C18—C22—C21	115.59 (12)
C15—N2—C16	116.26 (12)	C21—C22—C22^i	121.95 (11)
C19—N3—C20	115.27 (13)	C18—C22—C22^i	122.46 (12)
N1—C8—C9	123.39 (13)	C22—C18—H18	121.00
C8—C9—C10	119.50 (11)	C19—C18—H18	119.00
C11—C10—C13	120.87 (12)	N3—C19—H19	116.00
C9—C10—C13	122.16 (11)	C18—C19—H19	120.00
C9—C10—C11	116.97 (12)	N3—C20—H20	117.00
C10—C11—C12	119.64 (13)	C21—C20—H20	119.00
N1—C12—C11	123.60 (12)	C20—C21—H21	119.00
C10—C13—C14	121.27 (12)	C22—C21—H21	121.00
C14—C13—C17	116.93 (12)	C2—C1—C7	120.51 (11)
C10—C13—C17	121.79 (12)	C2—C1—C6	119.51 (12)
C13—C14—C15	119.48 (13)	C6—C1—C7	119.96 (11)
N2—C15—C14	124.03 (13)	C1—C2—C3	120.10 (11)
N2—C16—C17	123.78 (13)	O1—C3—C2	117.71 (11)
C13—C17—C16	119.51 (12)	C2—C3—C4	120.74 (11)
C9—C8—H8	121.00	O1—C3—C4	121.55 (12)
N1—C8—H8	116.00	C3—C4—C5	118.94 (12)
C10—C9—H9	123.00	O2—C5—C4	122.10 (11)
C8—C9—H9	118.00	O2—C5—C6	117.68 (10)
C12—C11—H11	120.00	C4—C5—C6	120.21 (11)
C10—C11—H11	120.00	C1—C6—C5	120.49 (11)
C11—C12—H12	120.00	C1—C2—H2A	120.00
N1—C12—H12	116.00	C3—C2—H2A	119.00
C13—C14—H14	121.00	C3—C4—H4	120.00
C15—C14—H14	119.00	C5—C4—H4	121.00
C14—C15—H15	120.00	C1—C6—H6	121.00
N2—C15—H15	116.00	C5—C6—H6	119.00
N2—C16—H16	114.00	C1—C7—H7A	111.00
C17—C16—H16	122.00	C1—C7—H7B	114.00
C13—C17—H17	122.00	C1—C7—H7C	114.00
C16—C17—H17	118.00	H7A—C7—H7B	105.00
C19—C18—C22	119.99 (13)	H7A—C7—H7C	104.00
N3—C19—C18	124.51 (13)	H7B—C7—H7C	109.00
C12—N1—C8—C9	1.55 (19)	C22—C18—C19—N3	0.2 (2)
C8—N1—C12—C11	−1.09 (19)	C19—C18—C22—C21	0.08 (18)
C16—N2—C15—C14	1.21 (19)	C19—C18—C22—C22^i	−179.83 (12)
C15—N2—C16—C17	−0.90 (19)	N3—C20—C21—C22	−0.4 (2)
C20—N3—C19—C18	−0.5 (2)	C20—C21—C22—C18	0.02 (19)
C19—N3—C20—C21	0.6 (2)	C20—C21—C22—C22^i	179.93 (13)
N1—C8—C9—C10	−0.53 (19)	C18—C22—C22^i—C18^i	−180.00 (11)
C8—C9—C10—C13	179.73 (11)	C18—C22—C22^i—C21^i	−0.09 (18)
C8—C9—C10—C11	−0.98 (18)	C21—C22—C22^i—C18^i	0.09 (18)
C13—C10—C11—C12	−179.29 (12)	C21—C22—C22^i—C21^i	180.00 (12)
C9—C10—C13—C14	26.07 (18)	C6—C1—C2—C3	0.22 (19)
C11—C10—C13—C14	−153.19 (12)	C7—C1—C2—C3	−178.32 (12)
C11—C10—C13—C17	25.68 (18)	C2—C1—C6—C5	−0.83 (19)
C9—C10—C13—C17	−155.06 (12)	C7—C1—C6—C5	177.71 (12)
C9—C10—C11—C12	1.41 (18)	C1—C2—C3—O1	−179.11 (11)
C10—C11—C12—N1	−0.4 (2)	C1—C2—C3—C4	0.26 (19)
C17—C13—C14—C15	−0.90 (18)	O1—C3—C4—C5	179.21 (11)
C10—C13—C17—C16	−177.74 (11)	C2—C3—C4—C5	−0.14 (19)
C10—C13—C14—C15	178.02 (11)	C3—C4—C5—O2	−179.74 (11)
C14—C13—C17—C16	1.18 (18)	C3—C4—C5—C6	−0.47 (18)
C13—C14—C15—N2	−0.3 (2)	O2—C5—C6—C1	−179.74 (11)
N2—C16—C17—C13	−0.3 (2)	C4—C5—C6—C1	0.96 (19)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y, z−1; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1; (v) −x, −y+2, −z; (vi) −x, −y+1, −z+1; (vii) x−1, y, z+1; (viii) −x−1, −y+2, −z+1; (ix) x+1, y, z; (x) x−1, y, z; (xi) x, y, z+1; (xii) −x−1, −y+2, −z+2; (xiii) −x−1, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2^ii	0.9900	1.7600	2.7447 (15)	169.00
O2—H2···N1^iv	0.9900	1.7400	2.7285 (15)	177.00
C8—H8···N3^ix	1.0800	2.6200	3.5926 (19)	149.00
C9—H9···O1^xi	1.0800	2.4800	3.3926 (15)	142.00
C12—H12···O2	1.0800	2.5500	3.5238 (16)	150.00

Symmetry codes: (ii) x+1, y, z−1; (iv) −x+1, −y+1, −z+1; (ix) x+1, y, z; (xi) x, y, z+1.

(III_120K)

Crystal data

4.5(C10H8N2)·3(C7H8O2)	F(000) = 2268
Mr = 1075.26	Dx = 1.298 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6738 reflections
a = 9.2233 (3) Å	θ = 2.4–27.5°
b = 36.2938 (12) Å	µ = 0.09 mm^−1
c = 16.5853 (5) Å	T = 120 K
β = 97.827 (3)°	Block, colourless
V = 5500.2 (3) Å^3	0.5 × 0.3 × 0.2 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	12593 independent reflections
Radiation source: Mova (Mo) X-ray Source	8330 reflections with I > 2σ(I)
mirror	Rint = 0.051
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.5°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −45→47
Tmin = 0.998, Tmax = 0.999	l = −21→21
38087 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.067	All H-atom parameters refined
wR(F^2) = 0.164	W = 1/[Σ^2(FO^2) + (0.0474P)^2 + 3.2861P] WHERE P = (FO^2 + 2FC^2)/3
S = 1.03	(Δ/σ)max < 0.001
12593 reflections	Δρmax = 0.25 e Å^−3
970 parameters	Δρmin = −0.28 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.2618 (2)	0.79179 (6)	0.65147 (12)	0.0324 (7)
N2	0.8824 (2)	0.74557 (6)	0.46066 (12)	0.0308 (7)
C1	0.8944 (3)	0.75097 (7)	0.54140 (15)	0.0310 (8)
C2	0.7767 (3)	0.75950 (7)	0.58146 (15)	0.0292 (8)
C3	0.7480 (3)	0.74810 (9)	0.41943 (15)	0.0396 (9)
C4	0.6253 (3)	0.75706 (8)	0.45426 (15)	0.0361 (9)
C5	0.6384 (2)	0.76324 (6)	0.53763 (13)	0.0232 (7)
C6	0.5087 (2)	0.77355 (6)	0.57725 (13)	0.0232 (7)
C7	0.4939 (3)	0.76140 (8)	0.65540 (15)	0.0328 (8)
C8	0.3959 (3)	0.79505 (7)	0.53733 (15)	0.0287 (8)
C9	0.3706 (3)	0.77104 (9)	0.68916 (16)	0.0391 (9)
C10	0.2768 (3)	0.80338 (8)	0.57622 (16)	0.0323 (8)
N3	−0.3059 (2)	0.58399 (6)	1.09124 (12)	0.0303 (7)
N4	0.3135 (2)	0.63038 (6)	0.89798 (12)	0.0306 (7)
C18	0.2026 (3)	0.61013 (8)	0.86000 (15)	0.0314 (8)
C19	0.0798 (3)	0.60072 (7)	0.89410 (14)	0.0279 (8)
C20	0.0670 (2)	0.61216 (7)	0.97302 (13)	0.0248 (7)
C21	0.1811 (3)	0.63344 (7)	1.01320 (15)	0.0296 (8)
C22	0.2997 (3)	0.64165 (8)	0.97374 (16)	0.0332 (8)
C23	−0.0619 (2)	0.60189 (6)	1.01328 (13)	0.0242 (7)
C24	−0.1967 (3)	0.59313 (7)	0.96907 (14)	0.0301 (8)
C25	−0.3143 (3)	0.58463 (7)	1.00978 (14)	0.0302 (8)
C26	−0.0530 (3)	0.60087 (8)	1.09805 (14)	0.0319 (8)
C27	−0.1752 (3)	0.59195 (8)	1.13323 (15)	0.0363 (9)
N5	0.6627 (2)	0.47585 (7)	0.07082 (13)	0.0371 (7)
C28	0.6821 (3)	0.47290 (9)	−0.00673 (16)	0.0396 (9)
C29	0.8104 (3)	0.48145 (8)	−0.03679 (15)	0.0346 (9)
C30	0.9298 (2)	0.49499 (6)	0.01470 (13)	0.0233 (7)
C31	0.9106 (3)	0.49828 (8)	0.09612 (15)	0.0368 (9)
C32	0.7785 (3)	0.48858 (9)	0.12037 (16)	0.0424 (9)
N6	0.7857 (2)	0.31760 (7)	0.38913 (13)	0.0389 (8)
N7	0.1250 (2)	0.35882 (6)	0.54868 (13)	0.0353 (7)
C40	0.2545 (3)	0.35779 (8)	0.59698 (15)	0.0341 (9)
C41	0.3858 (3)	0.35021 (7)	0.56971 (14)	0.0297 (8)
C42	0.3879 (2)	0.34282 (6)	0.48730 (13)	0.0234 (7)
C43	0.2548 (3)	0.34352 (7)	0.43687 (15)	0.0291 (8)
C44	0.1281 (3)	0.35139 (8)	0.46984 (15)	0.0325 (8)
C45	0.5256 (2)	0.33419 (7)	0.45424 (13)	0.0241 (7)
C46	0.6434 (3)	0.31668 (7)	0.50043 (15)	0.0285 (8)
C47	0.7685 (3)	0.30950 (8)	0.46625 (16)	0.0342 (8)
C48	0.6721 (3)	0.33434 (9)	0.34478 (15)	0.0376 (9)
C49	0.5432 (3)	0.34324 (7)	0.37381 (14)	0.0287 (7)
N8	0.1887 (2)	0.57674 (6)	0.58157 (12)	0.0309 (7)
N9	0.8119 (2)	0.54224 (6)	0.38343 (12)	0.0317 (7)
C57	0.6999 (3)	0.54862 (8)	0.50467 (15)	0.0319 (8)
C58	0.5627 (2)	0.55411 (6)	0.46063 (13)	0.0237 (7)
C59	0.5535 (3)	0.55279 (7)	0.37595 (14)	0.0274 (7)
C60	0.6792 (3)	0.54682 (7)	0.34079 (15)	0.0304 (8)
C61	0.4325 (2)	0.56153 (7)	0.50177 (13)	0.0237 (7)
C62	0.3125 (3)	0.58126 (7)	0.46376 (14)	0.0284 (7)
C63	0.1948 (3)	0.58819 (7)	0.50483 (14)	0.0302 (8)
C64	0.4258 (3)	0.54956 (7)	0.58133 (15)	0.0301 (8)
C65	0.3041 (3)	0.55761 (8)	0.61755 (15)	0.0331 (8)
C66	0.8196 (3)	0.54315 (8)	0.46482 (15)	0.0351 (9)
O1	0.02758 (18)	0.40989 (5)	0.32165 (10)	0.0318 (6)
O2	0.05751 (19)	0.54226 (5)	0.30823 (11)	0.0340 (6)
C11	0.4290 (3)	0.46728 (8)	0.20436 (16)	0.0295 (8)
C12	0.1101 (2)	0.50788 (6)	0.29647 (13)	0.0239 (7)
C13	0.0377 (2)	0.47633 (7)	0.31745 (13)	0.0231 (7)
C14	0.0935 (2)	0.44174 (6)	0.30247 (13)	0.0223 (7)
C15	0.2220 (2)	0.43879 (7)	0.26715 (13)	0.0236 (7)
C16	0.2932 (2)	0.47027 (7)	0.24528 (12)	0.0229 (7)
C17	0.2372 (2)	0.50482 (7)	0.26016 (13)	0.0232 (7)
O3	0.56744 (18)	0.62949 (5)	0.82942 (10)	0.0303 (5)
O4	0.61199 (18)	0.76073 (4)	0.87034 (10)	0.0299 (5)
C33	0.9995 (3)	0.69318 (8)	0.76193 (18)	0.0320 (8)
C34	0.7959 (2)	0.72682 (7)	0.81755 (13)	0.0222 (6)
C35	0.8539 (2)	0.69394 (7)	0.79328 (13)	0.0228 (7)
C36	0.7763 (2)	0.66132 (7)	0.79943 (14)	0.0241 (7)
C37	0.6411 (2)	0.66200 (6)	0.82850 (13)	0.0227 (7)
C38	0.5844 (2)	0.69492 (6)	0.85336 (13)	0.0228 (7)
C39	0.6625 (2)	0.72734 (6)	0.84810 (12)	0.0213 (7)
O5	0.51448 (18)	0.70657 (5)	0.22719 (10)	0.0307 (5)
O6	0.46109 (18)	0.57615 (4)	0.17579 (10)	0.0289 (5)
C50	0.0851 (3)	0.64267 (8)	0.29712 (17)	0.0300 (8)
C51	0.4144 (2)	0.60914 (6)	0.20237 (12)	0.0226 (7)
C52	0.2828 (2)	0.60909 (7)	0.23535 (13)	0.0223 (7)
C53	0.2286 (2)	0.64185 (7)	0.26304 (13)	0.0231 (7)
C54	0.3067 (2)	0.67438 (7)	0.25820 (14)	0.0247 (7)
C55	0.4397 (2)	0.67421 (6)	0.22718 (13)	0.0227 (7)
C56	0.4937 (2)	0.64149 (6)	0.19844 (13)	0.0224 (7)
H1	0.998 (3)	0.7487 (8)	0.5716 (17)	0.049 (8)*
H2	0.793 (3)	0.7643 (7)	0.6389 (16)	0.039 (7)*
H3	0.738 (3)	0.7421 (8)	0.3608 (17)	0.050 (8)*
H4	0.532 (3)	0.7576 (8)	0.4220 (16)	0.043 (8)*
H7	0.571 (3)	0.7461 (8)	0.6867 (16)	0.044 (8)*
H8	0.405 (3)	0.8054 (7)	0.4856 (16)	0.037 (7)*
H9	0.356 (3)	0.7618 (8)	0.7446 (16)	0.043 (8)*
H10	0.197 (3)	0.8186 (8)	0.5476 (16)	0.046 (8)*
H18	0.215 (3)	0.6015 (7)	0.8056 (16)	0.039 (7)*
H19	0.002 (3)	0.5851 (8)	0.8631 (16)	0.045 (8)*
H21	0.182 (3)	0.6430 (8)	1.0699 (17)	0.049 (8)*
H22	0.382 (3)	0.6571 (7)	1.0020 (15)	0.035 (7)*
H24	−0.213 (3)	0.5932 (7)	0.9070 (16)	0.043 (8)*
H25	−0.410 (3)	0.5781 (7)	0.9780 (15)	0.038 (7)*
H26	0.039 (3)	0.6074 (7)	1.1328 (15)	0.033 (7)*
H27	−0.171 (3)	0.5912 (8)	1.1931 (18)	0.055 (9)*
H28	0.597 (3)	0.4618 (7)	−0.0443 (15)	0.040 (7)*
H29	0.817 (3)	0.4795 (8)	−0.0942 (16)	0.045 (8)*
H31	0.990 (3)	0.5065 (8)	0.1387 (17)	0.050 (8)*
H32	0.765 (3)	0.4913 (9)	0.1795 (19)	0.063 (9)*
H40	0.254 (2)	0.3632 (7)	0.6588 (15)	0.032 (7)*
H41	0.473 (2)	0.3513 (6)	0.6077 (14)	0.023 (6)*
H43	0.248 (3)	0.3392 (7)	0.3783 (15)	0.035 (7)*
H44	0.032 (3)	0.3524 (7)	0.4329 (15)	0.036 (7)*
H46	0.635 (3)	0.3081 (7)	0.5574 (16)	0.044 (8)*
H47	0.849 (3)	0.2959 (8)	0.4986 (16)	0.045 (8)*
H48	0.685 (3)	0.3398 (8)	0.2859 (17)	0.050 (8)*
H49	0.462 (3)	0.3549 (7)	0.3371 (15)	0.039 (7)*
H57	0.717 (3)	0.5485 (7)	0.5645 (16)	0.041 (8)*
H59	0.462 (3)	0.5558 (7)	0.3405 (15)	0.034 (7)*
H60	0.672 (2)	0.5465 (6)	0.2802 (14)	0.026 (6)*
H62	0.311 (3)	0.5907 (7)	0.4080 (16)	0.039 (7)*
H63	0.109 (3)	0.6034 (8)	0.4796 (16)	0.042 (8)*
H64	0.508 (3)	0.5348 (8)	0.6107 (16)	0.049 (8)*
H65	0.299 (3)	0.5507 (8)	0.6764 (17)	0.048 (8)*
H66	0.920 (3)	0.5411 (7)	0.4949 (15)	0.033 (7)*
H1A	−0.052 (3)	0.4173 (9)	0.357 (2)	0.077 (11)*
H2A	−0.040 (3)	0.5413 (9)	0.3367 (19)	0.071 (10)*
H11A	0.502 (3)	0.4840 (8)	0.2252 (16)	0.040 (8)*
H11B	0.409 (3)	0.4716 (8)	0.1454 (18)	0.054 (9)*
H11C	0.477 (3)	0.4412 (9)	0.2121 (17)	0.055 (9)*
H13	−0.053 (2)	0.4787 (6)	0.3442 (13)	0.020 (6)*
H15	0.262 (2)	0.4141 (7)	0.2586 (14)	0.028 (6)*
H17	0.281 (2)	0.5258 (7)	0.2438 (14)	0.027 (7)*
H3A	0.473 (3)	0.6333 (8)	0.8541 (17)	0.059 (9)*
H4A	0.526 (3)	0.7582 (8)	0.9020 (18)	0.060 (9)*
H33A	1.025 (3)	0.7160 (9)	0.7404 (17)	0.048 (8)*
H33B	1.079 (3)	0.6882 (8)	0.8055 (19)	0.059 (9)*
H33C	1.008 (3)	0.6730 (9)	0.7235 (19)	0.059 (9)*
H34	0.847 (3)	0.7496 (7)	0.8124 (15)	0.034 (7)*
H36	0.815 (3)	0.6374 (7)	0.7820 (14)	0.033 (7)*
H38	0.490 (3)	0.6964 (7)	0.8739 (14)	0.031 (7)*
H5	0.606 (3)	0.7041 (9)	0.1981 (19)	0.065 (10)*
H6	0.550 (3)	0.5788 (9)	0.1432 (18)	0.066 (10)*
H50A	0.052 (3)	0.6167 (8)	0.3082 (16)	0.042 (8)*
H50B	0.090 (3)	0.6578 (8)	0.3488 (18)	0.055 (9)*
H50C	0.005 (3)	0.6530 (8)	0.2598 (17)	0.046 (8)*
H52	0.232 (2)	0.5866 (7)	0.2405 (14)	0.027 (6)*
H54	0.271 (2)	0.6968 (6)	0.2783 (13)	0.020 (6)*
H56	0.588 (2)	0.6419 (7)	0.1746 (14)	0.029 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0266 (11)	0.0398 (13)	0.0320 (11)	0.0043 (10)	0.0085 (9)	−0.0030 (10)
N2	0.0266 (11)	0.0326 (12)	0.0352 (11)	0.0026 (9)	0.0114 (9)	0.0035 (9)
C1	0.0220 (13)	0.0360 (15)	0.0352 (13)	0.0009 (11)	0.0052 (10)	−0.0024 (11)
C2	0.0243 (12)	0.0357 (15)	0.0272 (12)	0.0035 (11)	0.0024 (10)	−0.0029 (11)
C3	0.0367 (15)	0.060 (2)	0.0242 (12)	0.0075 (14)	0.0113 (11)	0.0001 (13)
C4	0.0288 (14)	0.0568 (19)	0.0230 (12)	0.0075 (13)	0.0049 (10)	0.0013 (12)
C5	0.0212 (11)	0.0246 (12)	0.0244 (11)	−0.0017 (10)	0.0050 (9)	0.0014 (9)
C6	0.0214 (11)	0.0242 (12)	0.0240 (11)	−0.0021 (10)	0.0034 (9)	−0.0039 (9)
C7	0.0242 (13)	0.0480 (17)	0.0265 (12)	0.0063 (12)	0.0050 (10)	0.0044 (12)
C8	0.0271 (13)	0.0321 (14)	0.0274 (12)	0.0033 (11)	0.0053 (10)	0.0052 (11)
C9	0.0318 (14)	0.060 (2)	0.0272 (13)	0.0052 (14)	0.0097 (11)	0.0051 (13)
C10	0.0254 (13)	0.0344 (15)	0.0374 (14)	0.0054 (12)	0.0049 (11)	−0.0009 (12)
N3	0.0275 (11)	0.0330 (12)	0.0318 (11)	−0.0002 (9)	0.0090 (9)	−0.0029 (9)
N4	0.0265 (11)	0.0317 (12)	0.0347 (11)	−0.0007 (9)	0.0078 (9)	0.0034 (9)
C18	0.0281 (13)	0.0376 (15)	0.0296 (12)	−0.0019 (12)	0.0079 (10)	0.0003 (11)
C19	0.0213 (12)	0.0355 (15)	0.0268 (12)	−0.0023 (11)	0.0027 (9)	−0.0017 (11)
C20	0.0218 (12)	0.0251 (12)	0.0276 (11)	0.0022 (10)	0.0034 (9)	0.0031 (10)
C21	0.0266 (13)	0.0330 (14)	0.0285 (12)	−0.0034 (11)	0.0016 (10)	−0.0020 (11)
C22	0.0294 (14)	0.0351 (15)	0.0355 (13)	−0.0063 (12)	0.0060 (11)	−0.0004 (12)
C23	0.0237 (12)	0.0226 (12)	0.0266 (11)	0.0012 (10)	0.0041 (9)	0.0002 (10)
C24	0.0250 (12)	0.0398 (15)	0.0254 (12)	−0.0003 (11)	0.0035 (10)	0.0014 (11)
C25	0.0225 (12)	0.0385 (15)	0.0291 (12)	−0.0004 (11)	0.0021 (10)	−0.0037 (11)
C26	0.0280 (13)	0.0405 (16)	0.0264 (12)	−0.0028 (12)	0.0014 (10)	−0.0015 (11)
C27	0.0329 (14)	0.0493 (18)	0.0275 (13)	−0.0048 (13)	0.0067 (11)	−0.0044 (12)
N5	0.0304 (12)	0.0458 (14)	0.0362 (12)	−0.0019 (11)	0.0086 (9)	0.0050 (11)
C28	0.0280 (14)	0.0568 (19)	0.0332 (13)	−0.0104 (14)	0.0015 (11)	0.0013 (13)
C29	0.0304 (14)	0.0498 (18)	0.0235 (12)	−0.0057 (13)	0.0034 (10)	0.0008 (12)
C30	0.0233 (12)	0.0214 (12)	0.0252 (11)	0.0033 (10)	0.0036 (9)	0.0019 (9)
C31	0.0309 (14)	0.0552 (19)	0.0248 (12)	−0.0054 (13)	0.0056 (11)	−0.0057 (12)
C32	0.0344 (15)	0.068 (2)	0.0269 (13)	−0.0022 (14)	0.0113 (11)	−0.0037 (13)
N6	0.0280 (11)	0.0564 (16)	0.0339 (12)	0.0047 (11)	0.0103 (9)	0.0010 (11)
N7	0.0303 (12)	0.0421 (14)	0.0355 (12)	0.0055 (10)	0.0118 (9)	0.0027 (10)
C40	0.0328 (14)	0.0432 (17)	0.0275 (13)	0.0053 (12)	0.0089 (11)	0.0014 (12)
C41	0.0275 (13)	0.0376 (15)	0.0236 (11)	0.0028 (12)	0.0017 (10)	−0.0003 (11)
C42	0.0250 (12)	0.0219 (12)	0.0234 (11)	0.0019 (10)	0.0036 (9)	0.0020 (9)
C43	0.0246 (12)	0.0357 (15)	0.0272 (12)	0.0006 (11)	0.0043 (10)	0.0016 (11)
C44	0.0250 (13)	0.0385 (16)	0.0344 (13)	0.0005 (12)	0.0051 (10)	0.0044 (12)
C45	0.0216 (12)	0.0261 (13)	0.0245 (11)	−0.0012 (10)	0.0031 (9)	−0.0010 (10)
C46	0.0276 (13)	0.0313 (14)	0.0270 (12)	0.0036 (11)	0.0057 (10)	0.0060 (11)
C47	0.0250 (13)	0.0428 (17)	0.0356 (13)	0.0096 (12)	0.0074 (11)	0.0061 (12)
C48	0.0283 (14)	0.0583 (19)	0.0265 (12)	−0.0019 (13)	0.0053 (10)	0.0009 (13)
C49	0.0229 (12)	0.0390 (15)	0.0237 (11)	−0.0012 (11)	0.0013 (9)	0.0024 (11)
N8	0.0235 (10)	0.0365 (13)	0.0342 (11)	0.0020 (10)	0.0091 (9)	0.0048 (10)
N9	0.0290 (11)	0.0324 (12)	0.0349 (11)	0.0036 (10)	0.0089 (9)	−0.0034 (9)
C57	0.0242 (13)	0.0437 (16)	0.0268 (12)	0.0043 (12)	0.0004 (10)	−0.0016 (11)
C58	0.0240 (12)	0.0224 (12)	0.0245 (11)	0.0010 (10)	0.0025 (9)	−0.0014 (9)
C59	0.0235 (12)	0.0312 (14)	0.0263 (11)	0.0006 (11)	−0.0006 (10)	−0.0004 (10)
C60	0.0333 (14)	0.0317 (14)	0.0269 (12)	0.0026 (11)	0.0063 (10)	−0.0021 (11)
C61	0.0196 (11)	0.0264 (13)	0.0247 (11)	−0.0004 (10)	0.0017 (9)	−0.0005 (10)
C62	0.0252 (12)	0.0343 (14)	0.0258 (12)	0.0056 (11)	0.0035 (10)	0.0043 (11)
C63	0.0254 (13)	0.0352 (15)	0.0303 (12)	0.0032 (11)	0.0045 (10)	0.0058 (11)
C64	0.0240 (13)	0.0344 (15)	0.0315 (12)	0.0025 (11)	0.0029 (10)	0.0073 (11)
C65	0.0282 (13)	0.0415 (16)	0.0302 (13)	−0.0003 (12)	0.0065 (10)	0.0067 (12)
C66	0.0226 (13)	0.0491 (18)	0.0330 (13)	0.0058 (12)	0.0021 (10)	−0.0014 (12)
O1	0.0348 (10)	0.0248 (9)	0.0388 (10)	−0.0054 (8)	0.0159 (8)	0.0011 (8)
O2	0.0342 (10)	0.0235 (9)	0.0477 (11)	0.0031 (8)	0.0180 (8)	0.0018 (8)
C11	0.0259 (13)	0.0315 (15)	0.0327 (13)	−0.0010 (12)	0.0096 (11)	−0.0027 (11)
C12	0.0254 (12)	0.0229 (12)	0.0233 (11)	0.0013 (10)	0.0034 (9)	−0.0011 (9)
C13	0.0209 (11)	0.0286 (13)	0.0203 (10)	0.0002 (10)	0.0047 (9)	0.0013 (10)
C14	0.0246 (12)	0.0214 (12)	0.0205 (10)	−0.0044 (10)	0.0013 (9)	0.0007 (9)
C15	0.0265 (12)	0.0217 (12)	0.0225 (11)	0.0011 (10)	0.0032 (9)	−0.0035 (9)
C16	0.0208 (11)	0.0281 (13)	0.0194 (10)	−0.0011 (10)	0.0013 (8)	−0.0025 (9)
C17	0.0236 (12)	0.0229 (12)	0.0231 (11)	−0.0049 (10)	0.0031 (9)	0.0004 (10)
O3	0.0256 (9)	0.0243 (9)	0.0423 (10)	−0.0042 (7)	0.0093 (7)	−0.0034 (8)
O4	0.0309 (9)	0.0225 (9)	0.0388 (10)	0.0012 (8)	0.0143 (8)	−0.0024 (7)
C33	0.0247 (14)	0.0343 (16)	0.0387 (14)	−0.0012 (12)	0.0101 (11)	−0.0009 (13)
C34	0.0214 (11)	0.0238 (12)	0.0209 (10)	−0.0013 (10)	0.0008 (9)	0.0034 (9)
C35	0.0209 (11)	0.0287 (13)	0.0192 (10)	−0.0001 (10)	0.0042 (8)	0.0012 (9)
C36	0.0232 (12)	0.0224 (12)	0.0273 (11)	0.0010 (10)	0.0054 (9)	−0.0045 (10)
C37	0.0230 (12)	0.0223 (12)	0.0217 (10)	−0.0041 (10)	−0.0010 (9)	−0.0001 (9)
C38	0.0202 (12)	0.0264 (13)	0.0225 (11)	0.0014 (10)	0.0051 (9)	−0.0004 (9)
C39	0.0238 (12)	0.0209 (12)	0.0189 (10)	0.0004 (10)	0.0018 (9)	−0.0008 (9)
O5	0.0291 (9)	0.0239 (9)	0.0408 (10)	−0.0064 (8)	0.0111 (8)	−0.0015 (8)
O6	0.0307 (9)	0.0223 (9)	0.0360 (9)	−0.0009 (7)	0.0131 (7)	−0.0041 (7)
C50	0.0251 (13)	0.0291 (14)	0.0382 (14)	−0.0035 (11)	0.0125 (11)	−0.0020 (12)
C51	0.0260 (12)	0.0228 (12)	0.0184 (10)	0.0016 (10)	0.0010 (9)	−0.0015 (9)
C52	0.0237 (12)	0.0210 (12)	0.0223 (11)	−0.0023 (10)	0.0035 (9)	0.0025 (9)
C53	0.0216 (11)	0.0278 (13)	0.0203 (10)	−0.0002 (10)	0.0039 (9)	0.0020 (9)
C54	0.0242 (12)	0.0241 (13)	0.0266 (11)	0.0010 (10)	0.0064 (9)	−0.0011 (10)
C55	0.0225 (11)	0.0222 (12)	0.0232 (11)	−0.0033 (10)	0.0027 (9)	0.0008 (9)
C56	0.0190 (11)	0.0265 (13)	0.0222 (11)	−0.0013 (10)	0.0051 (9)	0.0010 (9)

Geometric parameters (Å, °)

N1—C9	1.339 (4)	C40—C41	1.377 (4)
N1—C10	1.342 (3)	C41—C42	1.396 (3)
O1—C14	1.364 (3)	C42—C45	1.484 (3)
N2—C3	1.335 (3)	C42—C43	1.388 (3)
O2—C12	1.362 (3)	C43—C44	1.386 (4)
N2—C1	1.343 (3)	C45—C49	1.405 (3)
O1—H1A	1.04 (3)	C45—C46	1.395 (3)
O2—H2A	1.07 (3)	C46—C47	1.378 (4)
N3—C25	1.343 (3)	C48—C49	1.380 (4)
N3—C27	1.339 (3)	C40—H40	1.05 (2)
O3—C37	1.363 (3)	C41—H41	0.95 (2)
N4—C22	1.344 (3)	C43—H43	0.98 (2)
O4—C39	1.367 (3)	C44—H44	1.01 (3)
N4—C18	1.345 (3)	C46—H46	1.01 (3)
O3—H3A	1.02 (3)	C47—H47	0.99 (3)
O4—H4A	1.01 (3)	C48—H48	1.02 (3)
O5—C55	1.362 (3)	C49—H49	0.99 (3)
N5—C28	1.327 (3)	C57—C66	1.376 (4)
N5—C32	1.338 (3)	C57—C58	1.387 (3)
O6—C51	1.366 (3)	C58—C59	1.396 (3)
O5—H5	1.03 (3)	C58—C61	1.484 (3)
O6—H6	1.05 (3)	C59—C60	1.384 (4)
N6—C48	1.341 (4)	C61—C64	1.399 (3)
N6—C47	1.343 (3)	C61—C62	1.395 (3)
N7—C40	1.345 (3)	C62—C63	1.381 (4)
N7—C44	1.339 (3)	C64—C65	1.375 (4)
N8—C63	1.347 (3)	C57—H57	0.98 (3)
N8—C65	1.341 (3)	C59—H59	0.97 (3)
N9—C60	1.338 (3)	C60—H60	1.00 (2)
N9—C66	1.343 (3)	C62—H62	0.99 (3)
C1—C2	1.383 (4)	C63—H63	1.01 (3)
C2—C5	1.386 (3)	C64—H64	1.00 (3)
C3—C4	1.378 (4)	C65—H65	1.02 (3)
C4—C5	1.390 (3)	C66—H66	0.99 (3)
C5—C6	1.489 (3)	C11—C16	1.508 (3)
C6—C7	1.393 (3)	C12—C13	1.393 (3)
C6—C8	1.394 (3)	C12—C17	1.393 (3)
C7—C9	1.379 (4)	C13—C14	1.392 (3)
C8—C10	1.381 (4)	C14—C15	1.396 (3)
C1—H1	1.02 (3)	C15—C16	1.390 (3)
C2—H2	0.96 (3)	C16—C17	1.391 (3)
C3—H3	0.99 (3)	C11—H11C	1.05 (3)
C4—H4	0.95 (3)	C11—H11B	0.98 (3)
C7—H7	0.99 (3)	C11—H11A	0.94 (3)
C8—H8	0.95 (3)	C13—H13	1.003 (19)
C9—H9	1.01 (3)	C15—H15	0.99 (2)
C10—H10	0.99 (3)	C17—H17	0.92 (2)
C18—C19	1.376 (4)	C33—C35	1.505 (3)
C19—C20	1.393 (3)	C34—C35	1.390 (3)
C20—C21	1.399 (3)	C34—C39	1.393 (3)
C20—C23	1.488 (3)	C35—C36	1.394 (3)
C21—C22	1.382 (4)	C36—C37	1.397 (3)
C23—C26	1.398 (3)	C37—C38	1.389 (3)
C23—C24	1.392 (3)	C38—C39	1.389 (3)
C24—C25	1.388 (4)	C33—H33C	0.98 (3)
C26—C27	1.377 (4)	C33—H33A	0.94 (3)
C18—H18	0.98 (3)	C33—H33B	0.97 (3)
C19—H19	1.00 (3)	C34—H34	0.96 (3)
C21—H21	1.00 (3)	C36—H36	1.00 (3)
C22—H22	1.01 (3)	C38—H38	0.98 (3)
C24—H24	1.02 (3)	C50—C53	1.509 (3)
C25—H25	0.99 (3)	C51—C56	1.390 (3)
C26—H26	0.99 (3)	C51—C52	1.398 (3)
C27—H27	0.99 (3)	C52—C53	1.392 (3)
C28—C29	1.381 (4)	C53—C54	1.391 (3)
C29—C30	1.388 (3)	C54—C55	1.393 (3)
C30—C30^i	1.490 (3)	C55—C56	1.397 (3)
C30—C31	1.391 (3)	C50—H50A	1.02 (3)
C31—C32	1.380 (4)	C50—H50B	1.01 (3)
C28—H28	1.02 (3)	C50—H50C	0.97 (3)
C29—H29	0.97 (3)	C52—H52	0.95 (2)
C31—H31	0.99 (3)	C54—H54	0.96 (2)
C32—H32	1.01 (3)	C56—H56	1.003 (19)
C9—N1—C10	116.4 (2)	N7—C44—H44	116.9 (15)
C1—N2—C3	116.5 (2)	C47—C46—H46	120.2 (16)
C14—O1—H1A	106.6 (18)	C45—C46—H46	120.2 (16)
C12—O2—H2A	111.7 (18)	C46—C47—H47	118.8 (16)
C25—N3—C27	116.4 (2)	N6—C47—H47	116.7 (16)
C18—N4—C22	116.2 (2)	C49—C48—H48	120.5 (16)
C37—O3—H3A	109.9 (16)	N6—C48—H48	115.4 (16)
C39—O4—H4A	112.3 (17)	C45—C49—H49	120.5 (16)
C28—N5—C32	114.9 (2)	C48—C49—H49	120.0 (15)
C55—O5—H5	111.8 (18)	C58—C57—C66	120.1 (2)
C51—O6—H6	113.0 (18)	C57—C58—C59	116.8 (2)
C47—N6—C48	115.9 (2)	C59—C58—C61	121.8 (2)
C40—N7—C44	116.1 (2)	C57—C58—C61	121.4 (2)
C63—N8—C65	116.6 (2)	C58—C59—C60	119.3 (2)
C60—N9—C66	116.6 (2)	N9—C60—C59	123.7 (2)
N2—C1—C2	123.3 (2)	C62—C61—C64	116.9 (2)
C1—C2—C5	119.8 (2)	C58—C61—C62	121.8 (2)
N2—C3—C4	124.1 (2)	C58—C61—C64	121.3 (2)
C3—C4—C5	119.4 (2)	C61—C62—C63	120.0 (2)
C2—C5—C6	122.0 (2)	N8—C63—C62	123.1 (2)
C2—C5—C4	117.1 (2)	C61—C64—C65	119.3 (2)
C4—C5—C6	120.9 (2)	N8—C65—C64	124.2 (2)
C7—C6—C8	117.3 (2)	N9—C66—C57	123.4 (2)
C5—C6—C8	121.6 (2)	C58—C57—H57	122.8 (16)
C5—C6—C7	121.2 (2)	C66—C57—H57	117.1 (16)
C6—C7—C9	119.2 (2)	C60—C59—H59	118.3 (16)
C6—C8—C10	119.4 (2)	C58—C59—H59	122.4 (16)
N1—C9—C7	124.1 (2)	C59—C60—H60	118.8 (11)
N1—C10—C8	123.7 (2)	N9—C60—H60	117.5 (11)
N2—C1—H1	115.0 (16)	C61—C62—H62	120.8 (16)
C2—C1—H1	121.8 (16)	C63—C62—H62	119.2 (16)
C1—C2—H2	119.4 (17)	N8—C63—H63	115.5 (16)
C5—C2—H2	120.8 (17)	C62—C63—H63	121.4 (16)
C4—C3—H3	119.5 (16)	C65—C64—H64	120.8 (15)
N2—C3—H3	116.4 (16)	C61—C64—H64	119.9 (15)
C5—C4—H4	120.4 (17)	N8—C65—H65	114.7 (16)
C3—C4—H4	120.1 (17)	C64—C65—H65	121.0 (16)
C9—C7—H7	120.1 (16)	N9—C66—H66	114.9 (15)
C6—C7—H7	120.7 (16)	C57—C66—H66	121.6 (15)
C10—C8—H8	120.6 (17)	O2—C12—C17	118.2 (2)
C6—C8—H8	119.9 (17)	C13—C12—C17	120.2 (2)
N1—C9—H9	115.4 (16)	O2—C12—C13	121.66 (18)
C7—C9—H9	120.5 (16)	C12—C13—C14	119.68 (18)
N1—C10—H10	117.2 (16)	O1—C14—C15	117.6 (2)
C8—C10—H10	119.1 (16)	C13—C14—C15	120.0 (2)
N4—C18—C19	124.0 (2)	O1—C14—C13	122.37 (18)
C18—C19—C20	119.5 (2)	C14—C15—C16	120.3 (2)
C19—C20—C21	117.2 (2)	C11—C16—C15	120.6 (2)
C19—C20—C23	121.5 (2)	C15—C16—C17	119.64 (18)
C21—C20—C23	121.3 (2)	C11—C16—C17	119.7 (2)
C20—C21—C22	119.1 (2)	C12—C17—C16	120.2 (2)
N4—C22—C21	124.0 (2)	C16—C11—H11A	112.8 (17)
C20—C23—C26	121.1 (2)	C16—C11—H11B	112.4 (17)
C20—C23—C24	122.1 (2)	H11B—C11—H11C	107 (2)
C24—C23—C26	116.7 (2)	H11A—C11—H11B	107 (2)
C23—C24—C25	119.7 (2)	C16—C11—H11C	112.0 (16)
N3—C25—C24	123.5 (2)	H11A—C11—H11C	106 (2)
C23—C26—C27	119.6 (2)	C14—C13—H13	120.5 (13)
N3—C27—C26	124.2 (2)	C12—C13—H13	119.8 (13)
N4—C18—H18	115.5 (16)	C14—C15—H15	119.0 (12)
C19—C18—H18	120.4 (16)	C16—C15—H15	120.6 (12)
C20—C19—H19	120.3 (16)	C16—C17—H17	120.3 (13)
C18—C19—H19	120.2 (16)	C12—C17—H17	119.4 (13)
C22—C21—H21	117.7 (16)	C35—C34—C39	120.7 (2)
C20—C21—H21	123.2 (16)	C33—C35—C36	120.1 (2)
C21—C22—H22	119.7 (15)	C34—C35—C36	119.10 (18)
N4—C22—H22	116.3 (15)	C33—C35—C34	120.8 (2)
C23—C24—H24	122.0 (16)	C35—C36—C37	120.1 (2)
C25—C24—H24	118.3 (16)	C36—C37—C38	120.5 (2)
N3—C25—H25	117.1 (15)	O3—C37—C38	122.21 (18)
C24—C25—H25	119.5 (15)	O3—C37—C36	117.3 (2)
C23—C26—H26	120.6 (15)	C37—C38—C39	119.39 (18)
C27—C26—H26	119.8 (15)	C34—C39—C38	120.2 (2)
N3—C27—H27	115.2 (16)	O4—C39—C34	117.42 (19)
C26—C27—H27	120.7 (17)	O4—C39—C38	122.38 (17)
N5—C28—C29	124.6 (2)	C35—C33—H33B	111.4 (17)
C28—C29—C30	120.3 (2)	C35—C33—H33A	113.2 (17)
C29—C30—C30^i	122.5 (2)	H33A—C33—H33C	111 (3)
C30^i—C30—C31	121.9 (2)	H33B—C33—H33C	103 (2)
C29—C30—C31	115.6 (2)	C35—C33—H33C	113.1 (17)
C30—C31—C32	119.7 (2)	H33A—C33—H33B	104 (2)
N5—C32—C31	124.9 (2)	C35—C34—H34	120.0 (16)
N5—C28—H28	115.6 (15)	C39—C34—H34	119.3 (16)
C29—C28—H28	119.7 (15)	C35—C36—H36	120.7 (16)
C30—C29—H29	118.8 (17)	C37—C36—H36	119.2 (16)
C28—C29—H29	120.8 (17)	C37—C38—H38	122.6 (15)
C32—C31—H31	117.7 (16)	C39—C38—H38	118.0 (15)
C30—C31—H31	122.6 (16)	O6—C51—C56	122.31 (17)
N5—C32—H32	115.9 (16)	O6—C51—C52	117.00 (19)
C31—C32—H32	119.3 (17)	C52—C51—C56	120.7 (2)
N7—C40—C41	124.0 (2)	C51—C52—C53	119.9 (2)
C40—C41—C42	119.4 (2)	C50—C53—C52	120.9 (2)
C41—C42—C45	122.0 (2)	C52—C53—C54	119.60 (18)
C43—C42—C45	120.8 (2)	C50—C53—C54	119.5 (2)
C41—C42—C43	117.2 (2)	C53—C54—C55	120.4 (2)
C42—C43—C44	119.3 (2)	O5—C55—C54	117.9 (2)
N7—C44—C43	123.9 (2)	O5—C55—C56	121.95 (18)
C46—C45—C49	116.5 (2)	C54—C55—C56	120.2 (2)
C42—C45—C46	122.4 (2)	C51—C56—C55	119.21 (18)
C42—C45—C49	121.1 (2)	C53—C50—H50A	110.5 (16)
C45—C46—C47	119.6 (2)	C53—C50—H50B	112.8 (16)
N6—C47—C46	124.4 (2)	C53—C50—H50C	113.5 (17)
N6—C48—C49	124.1 (2)	H50A—C50—H50B	109 (2)
C45—C49—C48	119.5 (2)	H50A—C50—H50C	105 (2)
N7—C40—H40	117.2 (11)	H50B—C50—H50C	106 (2)
C41—C40—H40	118.8 (11)	C51—C52—H52	120.1 (13)
C42—C41—H41	122.2 (13)	C53—C52—H52	120.0 (13)
C40—C41—H41	118.4 (13)	C53—C54—H54	119.8 (12)
C44—C43—H43	118.8 (16)	C55—C54—H54	119.7 (12)
C42—C43—H43	121.8 (16)	C51—C56—H56	121.4 (15)
C43—C44—H44	119.2 (15)	C55—C56—H56	119.4 (15)
C10—N1—C9—C7	0.2 (4)	C43—C42—C45—C49	30.4 (3)
C9—N1—C10—C8	0.0 (4)	C41—C42—C45—C49	−150.2 (2)
C1—N2—C3—C4	2.4 (4)	C45—C42—C43—C44	179.5 (2)
C3—N2—C1—C2	−1.3 (4)	C41—C42—C43—C44	0.0 (4)
C25—N3—C27—C26	0.7 (4)	C43—C42—C45—C46	−149.3 (2)
C27—N3—C25—C24	−0.3 (4)	C42—C43—C44—N7	0.5 (4)
C18—N4—C22—C21	0.4 (4)	C49—C45—C46—C47	0.5 (4)
C22—N4—C18—C19	−0.1 (4)	C46—C45—C49—C48	0.6 (4)
C28—N5—C32—C31	−0.1 (5)	C42—C45—C46—C47	−179.9 (2)
C32—N5—C28—C29	0.9 (5)	C42—C45—C49—C48	−179.1 (2)
C47—N6—C48—C49	0.0 (4)	C45—C46—C47—N6	−1.4 (4)
C48—N6—C47—C46	1.2 (4)	N6—C48—C49—C45	−0.8 (4)
C44—N7—C40—C41	0.9 (4)	C58—C57—C66—N9	−1.0 (4)
C40—N7—C44—C43	−1.0 (4)	C66—C57—C58—C59	1.6 (4)
C65—N8—C63—C62	−0.4 (4)	C66—C57—C58—C61	−177.6 (2)
C63—N8—C65—C64	0.6 (4)	C57—C58—C61—C62	153.4 (2)
C60—N9—C66—C57	−0.3 (4)	C59—C58—C61—C64	155.4 (2)
C66—N9—C60—C59	0.9 (4)	C57—C58—C61—C64	−25.5 (4)
N2—C1—C2—C5	−0.7 (4)	C59—C58—C61—C62	−25.8 (4)
C1—C2—C5—C6	−178.0 (2)	C57—C58—C59—C60	−1.1 (4)
C1—C2—C5—C4	1.7 (4)	C61—C58—C59—C60	178.1 (2)
N2—C3—C4—C5	−1.4 (5)	C58—C59—C60—N9	−0.2 (4)
C3—C4—C5—C6	179.0 (2)	C62—C61—C64—C65	0.0 (4)
C3—C4—C5—C2	−0.7 (4)	C58—C61—C62—C63	−178.7 (2)
C4—C5—C6—C8	−33.5 (3)	C58—C61—C64—C65	178.9 (2)
C4—C5—C6—C7	145.1 (3)	C64—C61—C62—C63	0.2 (4)
C2—C5—C6—C8	146.2 (2)	C61—C62—C63—N8	0.0 (4)
C2—C5—C6—C7	−35.1 (3)	C61—C64—C65—N8	−0.4 (4)
C8—C6—C7—C9	−0.1 (4)	O2—C12—C13—C14	178.4 (2)
C7—C6—C8—C10	0.3 (4)	C17—C12—C13—C14	0.4 (3)
C5—C6—C8—C10	179.0 (2)	O2—C12—C17—C16	−178.58 (19)
C5—C6—C7—C9	−178.8 (2)	C13—C12—C17—C16	−0.5 (3)
C6—C7—C9—N1	−0.2 (4)	C12—C13—C14—O1	180.00 (19)
C6—C8—C10—N1	−0.3 (4)	C12—C13—C14—C15	0.5 (3)
N4—C18—C19—C20	−0.7 (4)	O1—C14—C15—C16	179.17 (19)
C18—C19—C20—C21	1.0 (4)	C13—C14—C15—C16	−1.3 (3)
C18—C19—C20—C23	−178.5 (2)	C14—C15—C16—C11	−177.8 (2)
C21—C20—C23—C24	156.0 (2)	C14—C15—C16—C17	1.2 (3)
C23—C20—C21—C22	178.8 (2)	C11—C16—C17—C12	178.7 (2)
C19—C20—C23—C24	−24.6 (4)	C15—C16—C17—C12	−0.3 (3)
C19—C20—C21—C22	−0.6 (4)	C39—C34—C35—C33	−178.7 (2)
C19—C20—C23—C26	155.9 (2)	C39—C34—C35—C36	0.4 (3)
C21—C20—C23—C26	−23.5 (4)	C35—C34—C39—O4	−179.66 (19)
C20—C21—C22—N4	−0.1 (4)	C35—C34—C39—C38	−1.1 (3)
C20—C23—C26—C27	178.7 (2)	C33—C35—C36—C37	−180.0 (2)
C24—C23—C26—C27	−0.8 (4)	C34—C35—C36—C37	1.0 (3)
C26—C23—C24—C25	1.2 (4)	C35—C36—C37—O3	176.95 (19)
C20—C23—C24—C25	−178.4 (2)	C35—C36—C37—C38	−1.6 (3)
C23—C24—C25—N3	−0.6 (4)	O3—C37—C38—C39	−177.62 (19)
C23—C26—C27—N3	−0.1 (4)	C36—C37—C38—C39	0.8 (3)
N5—C28—C29—C30	−1.6 (5)	C37—C38—C39—O4	178.98 (19)
C28—C29—C30—C31	1.3 (4)	C37—C38—C39—C34	0.5 (3)
C28—C29—C30—C30^i	−179.4 (2)	O6—C51—C52—C53	−179.55 (19)
C29—C30—C30^i—C29^i	−180.0 (2)	C56—C51—C52—C53	1.4 (3)
C29—C30—C30^i—C31^i	0.7 (4)	O6—C51—C56—C55	−179.65 (19)
C31—C30—C30^i—C31^i	180.0 (2)	C52—C51—C56—C55	−0.6 (3)
C31—C30—C30^i—C29^i	−0.7 (4)	C51—C52—C53—C50	178.6 (2)
C30^i—C30—C31—C32	−179.9 (2)	C51—C52—C53—C54	−0.5 (3)
C29—C30—C31—C32	−0.5 (4)	C50—C53—C54—C55	179.8 (2)
C30—C31—C32—N5	−0.1 (5)	C52—C53—C54—C55	−1.1 (3)
N7—C40—C41—C42	−0.4 (4)	C53—C54—C55—O5	−177.2 (2)
C40—C41—C42—C43	−0.1 (3)	C53—C54—C55—C56	1.9 (3)
C40—C41—C42—C45	−179.5 (2)	O5—C55—C56—C51	178.02 (19)
C41—C42—C45—C46	30.1 (4)	C54—C55—C56—C51	−1.0 (3)

Symmetry codes: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N8^ii	1.04 (3)	1.74 (3)	2.768 (3)	172 (3)
O3—H3A···N4	1.02 (3)	1.73 (3)	2.740 (3)	169 (3)
O4—H4A···N2^iii	1.01 (3)	1.75 (3)	2.765 (3)	178 (2)
O5—H5···N1^iv	1.03 (3)	1.73 (3)	2.750 (3)	170 (3)
O6—H6···N3^v	1.05 (3)	1.69 (3)	2.736 (3)	179 (3)
C2—H2···O5^vi	0.96 (3)	2.57 (3)	3.275 (3)	130 (2)
C28—H28···O6^vii	1.02 (3)	2.57 (3)	3.430 (3)	142 (2)
C47—H47···O4^viii	0.99 (3)	2.50 (3)	3.298 (3)	137 (2)

Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x−1/2, −y+3/2, z+1/2; (iv) x+1/2, −y+3/2, z−1/2; (v) x+1, y, z−1; (vi) x+1/2, −y+3/2, z+1/2; (vii) −x+1, −y+1, −z; (viii) −x+3/2, y−1/2, −z+3/2.

(III_140K)

Crystal data

4.5(C10H8N2)·3(C7H8O2)	F(000) = 2268
Mr = 1075.26	Dx = 1.298 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6337 reflections
a = 9.2233 (3) Å	θ = 2.4–27.5°
b = 36.2938 (12) Å	µ = 0.09 mm^−1
c = 16.5853 (5) Å	T = 140 K
β = 97.827 (3)°	Block, colourless
V = 5500.2 (3) Å^3	0.5 × 0.3 × 0.2 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	12593 independent reflections
Radiation source: Mova (Mo) X-ray Source	8330 reflections with I > 2σ(I)
mirror	Rint = 0.051
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.5°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −45→47
Tmin = 0.998, Tmax = 0.999	l = −21→21
38087 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.067	All H-atom parameters refined
wR(F^2) = 0.164	W = 1/[Σ^2(FO^2) + (0.0475P)^2 + 3.2803P] WHERE P = (FO^2 + 2FC^2)/3
S = 1.03	(Δ/σ)max = 0.001
12593 reflections	Δρmax = 0.25 e Å^−3
970 parameters	Δρmin = −0.28 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.2618 (2)	0.79179 (6)	0.65147 (12)	0.0324 (7)
N2	0.8824 (2)	0.74557 (6)	0.46066 (12)	0.0308 (7)
C1	0.8944 (3)	0.75097 (7)	0.54140 (15)	0.0310 (8)
C2	0.7767 (3)	0.75950 (7)	0.58146 (15)	0.0292 (8)
C3	0.7480 (3)	0.74810 (9)	0.41943 (15)	0.0396 (9)
C4	0.6253 (3)	0.75706 (8)	0.45426 (15)	0.0361 (9)
C5	0.6384 (2)	0.76324 (6)	0.53763 (13)	0.0232 (7)
C6	0.5087 (2)	0.77355 (6)	0.57725 (13)	0.0232 (7)
C7	0.4939 (3)	0.76140 (8)	0.65540 (15)	0.0328 (8)
C8	0.3959 (3)	0.79505 (7)	0.53733 (15)	0.0287 (8)
C9	0.3706 (3)	0.77104 (9)	0.68916 (16)	0.0391 (9)
C10	0.2768 (3)	0.80338 (8)	0.57622 (16)	0.0323 (8)
N3	−0.3059 (2)	0.58399 (6)	1.09124 (12)	0.0303 (7)
N4	0.3135 (2)	0.63038 (6)	0.89798 (12)	0.0306 (7)
C18	0.2026 (3)	0.61013 (8)	0.86000 (15)	0.0314 (8)
C19	0.0798 (3)	0.60072 (7)	0.89410 (14)	0.0279 (8)
C20	0.0670 (2)	0.61216 (7)	0.97302 (13)	0.0248 (7)
C21	0.1811 (3)	0.63344 (7)	1.01320 (15)	0.0296 (8)
C22	0.2997 (3)	0.64165 (8)	0.97374 (16)	0.0332 (8)
C23	−0.0619 (2)	0.60189 (6)	1.01328 (13)	0.0242 (7)
C24	−0.1967 (3)	0.59313 (7)	0.96907 (14)	0.0301 (8)
C25	−0.3143 (3)	0.58463 (7)	1.00978 (14)	0.0302 (8)
C26	−0.0530 (3)	0.60087 (8)	1.09805 (14)	0.0319 (8)
C27	−0.1752 (3)	0.59195 (8)	1.13323 (15)	0.0363 (9)
N5	0.6627 (2)	0.47585 (7)	0.07082 (13)	0.0371 (7)
C28	0.6821 (3)	0.47290 (9)	−0.00673 (16)	0.0396 (9)
C29	0.8104 (3)	0.48145 (8)	−0.03679 (15)	0.0346 (9)
C30	0.9298 (2)	0.49499 (6)	0.01470 (13)	0.0233 (7)
C31	0.9106 (3)	0.49828 (8)	0.09612 (15)	0.0368 (9)
C32	0.7785 (3)	0.48858 (9)	0.12037 (16)	0.0424 (9)
N6	0.7857 (2)	0.31760 (7)	0.38913 (13)	0.0389 (8)
N7	0.1250 (2)	0.35882 (6)	0.54868 (13)	0.0353 (7)
C40	0.2545 (3)	0.35779 (8)	0.59698 (15)	0.0341 (9)
C41	0.3858 (3)	0.35021 (7)	0.56971 (14)	0.0297 (8)
C42	0.3879 (2)	0.34282 (6)	0.48730 (13)	0.0234 (7)
C43	0.2548 (3)	0.34352 (7)	0.43687 (15)	0.0291 (8)
C44	0.1281 (3)	0.35139 (8)	0.46984 (15)	0.0325 (8)
C45	0.5256 (2)	0.33419 (7)	0.45424 (13)	0.0241 (7)
C46	0.6434 (3)	0.31668 (7)	0.50043 (15)	0.0285 (8)
C47	0.7685 (3)	0.30950 (8)	0.46625 (16)	0.0342 (8)
C48	0.6721 (3)	0.33434 (9)	0.34478 (15)	0.0376 (9)
C49	0.5432 (3)	0.34324 (7)	0.37381 (14)	0.0287 (7)
N8	0.1887 (2)	0.57674 (6)	0.58157 (12)	0.0309 (7)
N9	0.8119 (2)	0.54224 (6)	0.38343 (12)	0.0317 (7)
C57	0.6999 (3)	0.54862 (8)	0.50467 (15)	0.0319 (8)
C58	0.5627 (2)	0.55411 (6)	0.46063 (13)	0.0237 (7)
C59	0.5535 (3)	0.55279 (7)	0.37595 (14)	0.0274 (7)
C60	0.6792 (3)	0.54682 (7)	0.34079 (15)	0.0304 (8)
C61	0.4325 (2)	0.56153 (7)	0.50177 (13)	0.0237 (7)
C62	0.3125 (3)	0.58126 (7)	0.46376 (14)	0.0284 (7)
C63	0.1948 (3)	0.58819 (7)	0.50483 (14)	0.0302 (8)
C64	0.4258 (3)	0.54956 (7)	0.58133 (15)	0.0301 (8)
C65	0.3041 (3)	0.55761 (8)	0.61755 (15)	0.0331 (8)
C66	0.8196 (3)	0.54315 (8)	0.46482 (15)	0.0351 (9)
O1	0.02758 (18)	0.40989 (5)	0.32165 (10)	0.0318 (6)
O2	0.05751 (19)	0.54226 (5)	0.30823 (11)	0.0340 (6)
C11	0.4290 (3)	0.46728 (8)	0.20436 (16)	0.0295 (8)
C12	0.1101 (2)	0.50788 (6)	0.29647 (13)	0.0239 (7)
C13	0.0377 (2)	0.47633 (7)	0.31745 (13)	0.0231 (7)
C14	0.0935 (2)	0.44174 (6)	0.30247 (13)	0.0223 (7)
C15	0.2220 (2)	0.43879 (7)	0.26715 (13)	0.0236 (7)
C16	0.2932 (2)	0.47027 (7)	0.24528 (12)	0.0229 (7)
C17	0.2372 (2)	0.50482 (7)	0.26016 (13)	0.0232 (7)
O3	0.56744 (18)	0.62949 (5)	0.82942 (10)	0.0303 (5)
O4	0.61199 (18)	0.76073 (4)	0.87034 (10)	0.0299 (5)
C33	0.9995 (3)	0.69318 (8)	0.76193 (18)	0.0320 (8)
C34	0.7959 (2)	0.72682 (7)	0.81755 (13)	0.0222 (6)
C35	0.8539 (2)	0.69394 (7)	0.79328 (13)	0.0228 (7)
C36	0.7763 (2)	0.66132 (7)	0.79943 (14)	0.0241 (7)
C37	0.6411 (2)	0.66200 (6)	0.82850 (13)	0.0227 (7)
C38	0.5844 (2)	0.69492 (6)	0.85336 (13)	0.0228 (7)
C39	0.6625 (2)	0.72734 (6)	0.84810 (12)	0.0213 (7)
O5	0.51448 (18)	0.70657 (5)	0.22719 (10)	0.0307 (5)
O6	0.46109 (18)	0.57615 (4)	0.17579 (10)	0.0289 (5)
C50	0.0851 (3)	0.64267 (8)	0.29712 (17)	0.0300 (8)
C51	0.4144 (2)	0.60914 (6)	0.20237 (12)	0.0226 (7)
C52	0.2828 (2)	0.60909 (7)	0.23535 (13)	0.0223 (7)
C53	0.2286 (2)	0.64185 (7)	0.26304 (13)	0.0231 (7)
C54	0.3067 (2)	0.67438 (7)	0.25820 (14)	0.0247 (7)
C55	0.4397 (2)	0.67421 (6)	0.22718 (13)	0.0227 (7)
C56	0.4937 (2)	0.64149 (6)	0.19844 (13)	0.0224 (7)
H1	0.998 (3)	0.7487 (8)	0.5716 (17)	0.049 (8)*
H2	0.793 (3)	0.7643 (7)	0.6389 (16)	0.039 (7)*
H3	0.738 (3)	0.7421 (8)	0.3608 (17)	0.050 (8)*
H4	0.532 (3)	0.7576 (8)	0.4220 (16)	0.043 (8)*
H7	0.571 (3)	0.7461 (8)	0.6867 (16)	0.044 (8)*
H8	0.405 (3)	0.8054 (7)	0.4856 (16)	0.037 (7)*
H9	0.356 (3)	0.7618 (8)	0.7446 (16)	0.043 (8)*
H10	0.197 (3)	0.8186 (8)	0.5476 (16)	0.046 (8)*
H18	0.215 (3)	0.6015 (7)	0.8056 (16)	0.039 (7)*
H19	0.002 (3)	0.5851 (8)	0.8631 (16)	0.045 (8)*
H21	0.182 (3)	0.6430 (8)	1.0699 (17)	0.049 (8)*
H22	0.382 (3)	0.6571 (7)	1.0020 (15)	0.035 (7)*
H24	−0.213 (3)	0.5932 (7)	0.9070 (16)	0.043 (8)*
H25	−0.410 (3)	0.5781 (7)	0.9780 (15)	0.038 (7)*
H26	0.039 (3)	0.6074 (7)	1.1328 (15)	0.033 (7)*
H27	−0.171 (3)	0.5912 (8)	1.1931 (18)	0.055 (9)*
H28	0.597 (3)	0.4618 (7)	−0.0443 (15)	0.040 (7)*
H29	0.817 (3)	0.4795 (8)	−0.0942 (16)	0.045 (8)*
H31	0.990 (3)	0.5065 (8)	0.1387 (17)	0.050 (8)*
H32	0.765 (3)	0.4913 (9)	0.1795 (19)	0.063 (9)*
H40	0.254 (2)	0.3632 (7)	0.6588 (15)	0.032 (7)*
H41	0.473 (2)	0.3513 (6)	0.6077 (14)	0.023 (6)*
H43	0.248 (3)	0.3392 (7)	0.3783 (15)	0.035 (7)*
H44	0.032 (3)	0.3524 (7)	0.4329 (15)	0.036 (7)*
H46	0.635 (3)	0.3081 (7)	0.5574 (16)	0.044 (8)*
H47	0.849 (3)	0.2959 (8)	0.4986 (16)	0.045 (8)*
H48	0.685 (3)	0.3398 (8)	0.2859 (17)	0.050 (8)*
H49	0.462 (3)	0.3549 (7)	0.3371 (15)	0.039 (7)*
H57	0.717 (3)	0.5485 (7)	0.5645 (16)	0.041 (8)*
H59	0.462 (3)	0.5558 (7)	0.3405 (15)	0.034 (7)*
H60	0.672 (2)	0.5465 (6)	0.2802 (14)	0.026 (6)*
H62	0.311 (3)	0.5907 (7)	0.4080 (16)	0.039 (7)*
H63	0.109 (3)	0.6034 (8)	0.4796 (16)	0.042 (8)*
H64	0.508 (3)	0.5348 (8)	0.6107 (16)	0.049 (8)*
H65	0.299 (3)	0.5507 (8)	0.6764 (17)	0.048 (8)*
H66	0.920 (3)	0.5411 (7)	0.4949 (15)	0.033 (7)*
H1A	−0.052 (3)	0.4173 (9)	0.357 (2)	0.077 (11)*
H2A	−0.040 (3)	0.5413 (9)	0.3367 (19)	0.071 (10)*
H11A	0.502 (3)	0.4840 (8)	0.2252 (16)	0.040 (8)*
H11B	0.409 (3)	0.4716 (8)	0.1454 (18)	0.054 (9)*
H11C	0.477 (3)	0.4412 (9)	0.2121 (17)	0.055 (9)*
H13	−0.053 (2)	0.4787 (6)	0.3442 (13)	0.020 (6)*
H15	0.262 (2)	0.4141 (7)	0.2586 (14)	0.028 (6)*
H17	0.281 (2)	0.5258 (7)	0.2438 (14)	0.027 (7)*
H3A	0.473 (3)	0.6333 (8)	0.8541 (17)	0.059 (9)*
H4A	0.526 (3)	0.7582 (8)	0.9020 (18)	0.060 (9)*
H33A	1.025 (3)	0.7160 (9)	0.7404 (17)	0.048 (8)*
H33B	1.079 (3)	0.6882 (8)	0.8055 (19)	0.059 (9)*
H33C	1.008 (3)	0.6730 (9)	0.7235 (19)	0.059 (9)*
H34	0.847 (3)	0.7496 (7)	0.8124 (15)	0.034 (7)*
H36	0.815 (3)	0.6374 (7)	0.7820 (14)	0.033 (7)*
H38	0.490 (3)	0.6964 (7)	0.8739 (14)	0.031 (7)*
H5	0.606 (3)	0.7041 (9)	0.1981 (19)	0.065 (10)*
H6	0.550 (3)	0.5788 (9)	0.1432 (18)	0.066 (10)*
H50A	0.052 (3)	0.6167 (8)	0.3082 (16)	0.042 (8)*
H50B	0.090 (3)	0.6578 (8)	0.3488 (18)	0.055 (9)*
H50C	0.005 (3)	0.6530 (8)	0.2598 (17)	0.046 (8)*
H52	0.232 (2)	0.5866 (7)	0.2405 (14)	0.027 (6)*
H54	0.271 (2)	0.6968 (6)	0.2783 (13)	0.020 (6)*
H56	0.588 (2)	0.6419 (7)	0.1746 (14)	0.029 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0266 (11)	0.0398 (13)	0.0320 (11)	0.0043 (10)	0.0085 (9)	−0.0030 (10)
N2	0.0266 (11)	0.0326 (12)	0.0352 (11)	0.0026 (9)	0.0114 (9)	0.0035 (9)
C1	0.0220 (13)	0.0360 (15)	0.0352 (13)	0.0009 (11)	0.0052 (10)	−0.0024 (11)
C2	0.0243 (12)	0.0357 (15)	0.0272 (12)	0.0035 (11)	0.0024 (10)	−0.0029 (11)
C3	0.0367 (15)	0.060 (2)	0.0242 (12)	0.0075 (14)	0.0113 (11)	0.0001 (13)
C4	0.0288 (14)	0.0568 (19)	0.0230 (12)	0.0075 (13)	0.0049 (10)	0.0013 (12)
C5	0.0212 (11)	0.0246 (12)	0.0244 (11)	−0.0017 (10)	0.0050 (9)	0.0014 (9)
C6	0.0214 (11)	0.0242 (12)	0.0240 (11)	−0.0021 (10)	0.0034 (9)	−0.0039 (9)
C7	0.0242 (13)	0.0480 (17)	0.0265 (12)	0.0063 (12)	0.0050 (10)	0.0044 (12)
C8	0.0271 (13)	0.0321 (14)	0.0274 (12)	0.0033 (11)	0.0053 (10)	0.0052 (11)
C9	0.0318 (14)	0.060 (2)	0.0272 (13)	0.0052 (14)	0.0097 (11)	0.0051 (13)
C10	0.0254 (13)	0.0344 (15)	0.0374 (14)	0.0054 (12)	0.0049 (11)	−0.0009 (12)
N3	0.0275 (11)	0.0330 (12)	0.0318 (11)	−0.0002 (9)	0.0090 (9)	−0.0029 (9)
N4	0.0265 (11)	0.0317 (12)	0.0347 (11)	−0.0007 (9)	0.0078 (9)	0.0034 (9)
C18	0.0281 (13)	0.0376 (15)	0.0296 (12)	−0.0019 (12)	0.0079 (10)	0.0003 (11)
C19	0.0213 (12)	0.0355 (15)	0.0268 (12)	−0.0023 (11)	0.0027 (9)	−0.0017 (11)
C20	0.0218 (12)	0.0251 (12)	0.0276 (11)	0.0022 (10)	0.0034 (9)	0.0031 (10)
C21	0.0266 (13)	0.0330 (14)	0.0285 (12)	−0.0034 (11)	0.0016 (10)	−0.0020 (11)
C22	0.0294 (14)	0.0351 (15)	0.0355 (13)	−0.0063 (12)	0.0060 (11)	−0.0004 (12)
C23	0.0237 (12)	0.0226 (12)	0.0266 (11)	0.0012 (10)	0.0041 (9)	0.0002 (10)
C24	0.0250 (12)	0.0398 (15)	0.0254 (12)	−0.0003 (11)	0.0035 (10)	0.0014 (11)
C25	0.0225 (12)	0.0385 (15)	0.0291 (12)	−0.0004 (11)	0.0021 (10)	−0.0037 (11)
C26	0.0280 (13)	0.0405 (16)	0.0264 (12)	−0.0028 (12)	0.0014 (10)	−0.0015 (11)
C27	0.0329 (14)	0.0493 (18)	0.0275 (13)	−0.0048 (13)	0.0067 (11)	−0.0044 (12)
N5	0.0304 (12)	0.0458 (14)	0.0362 (12)	−0.0019 (11)	0.0086 (9)	0.0050 (11)
C28	0.0280 (14)	0.0568 (19)	0.0332 (13)	−0.0104 (14)	0.0015 (11)	0.0013 (13)
C29	0.0304 (14)	0.0498 (18)	0.0235 (12)	−0.0057 (13)	0.0034 (10)	0.0008 (12)
C30	0.0233 (12)	0.0214 (12)	0.0252 (11)	0.0033 (10)	0.0036 (9)	0.0019 (9)
C31	0.0309 (14)	0.0552 (19)	0.0248 (12)	−0.0054 (13)	0.0056 (11)	−0.0057 (12)
C32	0.0344 (15)	0.068 (2)	0.0269 (13)	−0.0022 (14)	0.0113 (11)	−0.0037 (13)
N6	0.0280 (11)	0.0564 (16)	0.0339 (12)	0.0047 (11)	0.0103 (9)	0.0010 (11)
N7	0.0303 (12)	0.0421 (14)	0.0355 (12)	0.0055 (10)	0.0118 (9)	0.0027 (10)
C40	0.0328 (14)	0.0432 (17)	0.0275 (13)	0.0053 (12)	0.0089 (11)	0.0014 (12)
C41	0.0275 (13)	0.0376 (15)	0.0236 (11)	0.0028 (12)	0.0017 (10)	−0.0003 (11)
C42	0.0250 (12)	0.0219 (12)	0.0234 (11)	0.0019 (10)	0.0036 (9)	0.0020 (9)
C43	0.0246 (12)	0.0357 (15)	0.0272 (12)	0.0006 (11)	0.0043 (10)	0.0016 (11)
C44	0.0250 (13)	0.0385 (16)	0.0344 (13)	0.0005 (12)	0.0051 (10)	0.0044 (12)
C45	0.0216 (12)	0.0261 (13)	0.0245 (11)	−0.0012 (10)	0.0031 (9)	−0.0010 (10)
C46	0.0276 (13)	0.0313 (14)	0.0270 (12)	0.0036 (11)	0.0057 (10)	0.0060 (11)
C47	0.0250 (13)	0.0428 (17)	0.0356 (13)	0.0096 (12)	0.0074 (11)	0.0061 (12)
C48	0.0283 (14)	0.0583 (19)	0.0265 (12)	−0.0019 (13)	0.0053 (10)	0.0009 (13)
C49	0.0229 (12)	0.0390 (15)	0.0237 (11)	−0.0012 (11)	0.0013 (9)	0.0024 (11)
N8	0.0235 (10)	0.0365 (13)	0.0342 (11)	0.0020 (10)	0.0091 (9)	0.0048 (10)
N9	0.0290 (11)	0.0324 (12)	0.0349 (11)	0.0036 (10)	0.0089 (9)	−0.0034 (9)
C57	0.0242 (13)	0.0437 (16)	0.0268 (12)	0.0043 (12)	0.0004 (10)	−0.0016 (11)
C58	0.0240 (12)	0.0224 (12)	0.0245 (11)	0.0010 (10)	0.0025 (9)	−0.0014 (9)
C59	0.0235 (12)	0.0312 (14)	0.0263 (11)	0.0006 (11)	−0.0006 (10)	−0.0004 (10)
C60	0.0333 (14)	0.0317 (14)	0.0269 (12)	0.0026 (11)	0.0063 (10)	−0.0021 (11)
C61	0.0196 (11)	0.0264 (13)	0.0247 (11)	−0.0004 (10)	0.0017 (9)	−0.0005 (10)
C62	0.0252 (12)	0.0343 (14)	0.0258 (12)	0.0056 (11)	0.0035 (10)	0.0043 (11)
C63	0.0254 (13)	0.0352 (15)	0.0303 (12)	0.0032 (11)	0.0045 (10)	0.0058 (11)
C64	0.0240 (13)	0.0344 (15)	0.0315 (12)	0.0025 (11)	0.0029 (10)	0.0073 (11)
C65	0.0282 (13)	0.0415 (16)	0.0302 (13)	−0.0003 (12)	0.0065 (10)	0.0067 (12)
C66	0.0226 (13)	0.0491 (18)	0.0330 (13)	0.0058 (12)	0.0021 (10)	−0.0014 (12)
O1	0.0348 (10)	0.0248 (9)	0.0388 (10)	−0.0054 (8)	0.0159 (8)	0.0011 (8)
O2	0.0342 (10)	0.0235 (9)	0.0477 (11)	0.0031 (8)	0.0180 (8)	0.0018 (8)
C11	0.0259 (13)	0.0315 (15)	0.0327 (13)	−0.0010 (12)	0.0096 (11)	−0.0027 (11)
C12	0.0254 (12)	0.0229 (12)	0.0233 (11)	0.0013 (10)	0.0034 (9)	−0.0011 (9)
C13	0.0209 (11)	0.0286 (13)	0.0203 (10)	0.0002 (10)	0.0047 (9)	0.0013 (10)
C14	0.0246 (12)	0.0214 (12)	0.0205 (10)	−0.0044 (10)	0.0013 (9)	0.0007 (9)
C15	0.0265 (12)	0.0217 (12)	0.0225 (11)	0.0011 (10)	0.0032 (9)	−0.0035 (9)
C16	0.0208 (11)	0.0281 (13)	0.0194 (10)	−0.0011 (10)	0.0013 (8)	−0.0025 (9)
C17	0.0236 (12)	0.0229 (12)	0.0231 (11)	−0.0049 (10)	0.0031 (9)	0.0004 (10)
O3	0.0256 (9)	0.0243 (9)	0.0423 (10)	−0.0042 (7)	0.0093 (7)	−0.0034 (8)
O4	0.0309 (9)	0.0225 (9)	0.0388 (10)	0.0012 (8)	0.0143 (8)	−0.0024 (7)
C33	0.0247 (14)	0.0343 (16)	0.0387 (14)	−0.0012 (12)	0.0101 (11)	−0.0009 (13)
C34	0.0214 (11)	0.0238 (12)	0.0209 (10)	−0.0013 (10)	0.0008 (9)	0.0034 (9)
C35	0.0209 (11)	0.0287 (13)	0.0192 (10)	−0.0001 (10)	0.0042 (8)	0.0012 (9)
C36	0.0232 (12)	0.0224 (12)	0.0273 (11)	0.0010 (10)	0.0054 (9)	−0.0045 (10)
C37	0.0230 (12)	0.0223 (12)	0.0217 (10)	−0.0041 (10)	−0.0010 (9)	−0.0001 (9)
C38	0.0202 (12)	0.0264 (13)	0.0225 (11)	0.0014 (10)	0.0051 (9)	−0.0004 (9)
C39	0.0238 (12)	0.0209 (12)	0.0189 (10)	0.0004 (10)	0.0018 (9)	−0.0008 (9)
O5	0.0291 (9)	0.0239 (9)	0.0408 (10)	−0.0064 (8)	0.0111 (8)	−0.0015 (8)
O6	0.0307 (9)	0.0223 (9)	0.0360 (9)	−0.0009 (7)	0.0131 (7)	−0.0041 (7)
C50	0.0251 (13)	0.0291 (14)	0.0382 (14)	−0.0035 (11)	0.0125 (11)	−0.0020 (12)
C51	0.0260 (12)	0.0228 (12)	0.0184 (10)	0.0016 (10)	0.0010 (9)	−0.0015 (9)
C52	0.0237 (12)	0.0210 (12)	0.0223 (11)	−0.0023 (10)	0.0035 (9)	0.0025 (9)
C53	0.0216 (11)	0.0278 (13)	0.0203 (10)	−0.0002 (10)	0.0039 (9)	0.0020 (9)
C54	0.0242 (12)	0.0241 (13)	0.0266 (11)	0.0010 (10)	0.0064 (9)	−0.0011 (10)
C55	0.0225 (11)	0.0222 (12)	0.0232 (11)	−0.0033 (10)	0.0027 (9)	0.0008 (9)
C56	0.0190 (11)	0.0265 (13)	0.0222 (11)	−0.0013 (10)	0.0051 (9)	0.0010 (9)

Geometric parameters (Å, °)

N1—C9	1.339 (4)	C40—C41	1.377 (4)
N1—C10	1.342 (3)	C41—C42	1.396 (3)
O1—C14	1.364 (3)	C42—C45	1.484 (3)
N2—C3	1.335 (3)	C42—C43	1.388 (3)
O2—C12	1.362 (3)	C43—C44	1.386 (4)
N2—C1	1.343 (3)	C45—C49	1.405 (3)
O1—H1A	1.04 (3)	C45—C46	1.395 (3)
O2—H2A	1.07 (3)	C46—C47	1.378 (4)
N3—C25	1.343 (3)	C48—C49	1.380 (4)
N3—C27	1.339 (3)	C40—H40	1.05 (2)
O3—C37	1.363 (3)	C41—H41	0.95 (2)
N4—C22	1.344 (3)	C43—H43	0.98 (2)
O4—C39	1.367 (3)	C44—H44	1.01 (3)
N4—C18	1.345 (3)	C46—H46	1.01 (3)
O3—H3A	1.02 (3)	C47—H47	0.99 (3)
O4—H4A	1.01 (3)	C48—H48	1.02 (3)
O5—C55	1.362 (3)	C49—H49	0.99 (3)
N5—C28	1.327 (3)	C57—C66	1.376 (4)
N5—C32	1.338 (3)	C57—C58	1.387 (3)
O6—C51	1.366 (3)	C58—C59	1.396 (3)
O5—H5	1.03 (3)	C58—C61	1.484 (3)
O6—H6	1.05 (3)	C59—C60	1.384 (4)
N6—C48	1.341 (4)	C61—C64	1.399 (3)
N6—C47	1.343 (3)	C61—C62	1.395 (3)
N7—C40	1.345 (3)	C62—C63	1.381 (4)
N7—C44	1.339 (3)	C64—C65	1.375 (4)
N8—C63	1.347 (3)	C57—H57	0.98 (3)
N8—C65	1.341 (3)	C59—H59	0.97 (3)
N9—C60	1.338 (3)	C60—H60	1.00 (2)
N9—C66	1.343 (3)	C62—H62	0.99 (3)
C1—C2	1.383 (4)	C63—H63	1.01 (3)
C2—C5	1.386 (3)	C64—H64	1.00 (3)
C3—C4	1.378 (4)	C65—H65	1.02 (3)
C4—C5	1.390 (3)	C66—H66	0.99 (3)
C5—C6	1.489 (3)	C11—C16	1.508 (3)
C6—C7	1.393 (3)	C12—C13	1.393 (3)
C6—C8	1.394 (3)	C12—C17	1.393 (3)
C7—C9	1.379 (4)	C13—C14	1.392 (3)
C8—C10	1.381 (4)	C14—C15	1.396 (3)
C1—H1	1.02 (3)	C15—C16	1.390 (3)
C2—H2	0.96 (3)	C16—C17	1.391 (3)
C3—H3	0.99 (3)	C11—H11C	1.05 (3)
C4—H4	0.95 (3)	C11—H11B	0.98 (3)
C7—H7	0.99 (3)	C11—H11A	0.94 (3)
C8—H8	0.95 (3)	C13—H13	1.003 (19)
C9—H9	1.01 (3)	C15—H15	0.99 (2)
C10—H10	0.99 (3)	C17—H17	0.92 (2)
C18—C19	1.376 (4)	C33—C35	1.505 (3)
C19—C20	1.393 (3)	C34—C35	1.390 (3)
C20—C21	1.399 (3)	C34—C39	1.393 (3)
C20—C23	1.488 (3)	C35—C36	1.394 (3)
C21—C22	1.382 (4)	C36—C37	1.397 (3)
C23—C26	1.398 (3)	C37—C38	1.389 (3)
C23—C24	1.392 (3)	C38—C39	1.389 (3)
C24—C25	1.388 (4)	C33—H33C	0.98 (3)
C26—C27	1.377 (4)	C33—H33A	0.94 (3)
C18—H18	0.98 (3)	C33—H33B	0.97 (3)
C19—H19	1.00 (3)	C34—H34	0.96 (3)
C21—H21	1.00 (3)	C36—H36	1.00 (3)
C22—H22	1.01 (3)	C38—H38	0.98 (3)
C24—H24	1.02 (3)	C50—C53	1.509 (3)
C25—H25	0.99 (3)	C51—C56	1.390 (3)
C26—H26	0.99 (3)	C51—C52	1.398 (3)
C27—H27	0.99 (3)	C52—C53	1.392 (3)
C28—C29	1.381 (4)	C53—C54	1.391 (3)
C29—C30	1.388 (3)	C54—C55	1.393 (3)
C30—C30^i	1.490 (3)	C55—C56	1.397 (3)
C30—C31	1.391 (3)	C50—H50A	1.02 (3)
C31—C32	1.380 (4)	C50—H50B	1.01 (3)
C28—H28	1.02 (3)	C50—H50C	0.97 (3)
C29—H29	0.97 (3)	C52—H52	0.95 (2)
C31—H31	0.99 (3)	C54—H54	0.96 (2)
C32—H32	1.01 (3)	C56—H56	1.003 (19)
C9—N1—C10	116.4 (2)	N7—C44—H44	116.9 (15)
C1—N2—C3	116.5 (2)	C47—C46—H46	120.2 (16)
C14—O1—H1A	106.6 (18)	C45—C46—H46	120.2 (16)
C12—O2—H2A	111.7 (18)	C46—C47—H47	118.8 (16)
C25—N3—C27	116.4 (2)	N6—C47—H47	116.7 (16)
C18—N4—C22	116.2 (2)	C49—C48—H48	120.5 (16)
C37—O3—H3A	109.9 (16)	N6—C48—H48	115.4 (16)
C39—O4—H4A	112.3 (17)	C45—C49—H49	120.5 (16)
C28—N5—C32	114.9 (2)	C48—C49—H49	120.0 (15)
C55—O5—H5	111.8 (18)	C58—C57—C66	120.1 (2)
C51—O6—H6	113.0 (18)	C57—C58—C59	116.8 (2)
C47—N6—C48	115.9 (2)	C59—C58—C61	121.8 (2)
C40—N7—C44	116.1 (2)	C57—C58—C61	121.4 (2)
C63—N8—C65	116.6 (2)	C58—C59—C60	119.3 (2)
C60—N9—C66	116.6 (2)	N9—C60—C59	123.7 (2)
N2—C1—C2	123.3 (2)	C62—C61—C64	116.9 (2)
C1—C2—C5	119.8 (2)	C58—C61—C62	121.8 (2)
N2—C3—C4	124.1 (2)	C58—C61—C64	121.3 (2)
C3—C4—C5	119.4 (2)	C61—C62—C63	120.0 (2)
C2—C5—C6	122.0 (2)	N8—C63—C62	123.1 (2)
C2—C5—C4	117.1 (2)	C61—C64—C65	119.3 (2)
C4—C5—C6	120.9 (2)	N8—C65—C64	124.2 (2)
C7—C6—C8	117.3 (2)	N9—C66—C57	123.4 (2)
C5—C6—C8	121.6 (2)	C58—C57—H57	122.8 (16)
C5—C6—C7	121.2 (2)	C66—C57—H57	117.1 (16)
C6—C7—C9	119.2 (2)	C60—C59—H59	118.3 (16)
C6—C8—C10	119.4 (2)	C58—C59—H59	122.4 (16)
N1—C9—C7	124.1 (2)	C59—C60—H60	118.8 (11)
N1—C10—C8	123.7 (2)	N9—C60—H60	117.5 (11)
N2—C1—H1	115.0 (16)	C61—C62—H62	120.8 (16)
C2—C1—H1	121.8 (16)	C63—C62—H62	119.2 (16)
C1—C2—H2	119.4 (17)	N8—C63—H63	115.5 (16)
C5—C2—H2	120.8 (17)	C62—C63—H63	121.4 (16)
C4—C3—H3	119.5 (16)	C65—C64—H64	120.8 (15)
N2—C3—H3	116.4 (16)	C61—C64—H64	119.9 (15)
C5—C4—H4	120.4 (17)	N8—C65—H65	114.7 (16)
C3—C4—H4	120.1 (17)	C64—C65—H65	121.0 (16)
C9—C7—H7	120.1 (16)	N9—C66—H66	114.9 (15)
C6—C7—H7	120.7 (16)	C57—C66—H66	121.6 (15)
C10—C8—H8	120.6 (17)	O2—C12—C17	118.2 (2)
C6—C8—H8	119.9 (17)	C13—C12—C17	120.2 (2)
N1—C9—H9	115.4 (16)	O2—C12—C13	121.66 (18)
C7—C9—H9	120.5 (16)	C12—C13—C14	119.68 (18)
N1—C10—H10	117.2 (16)	O1—C14—C15	117.6 (2)
C8—C10—H10	119.1 (16)	C13—C14—C15	120.0 (2)
N4—C18—C19	124.0 (2)	O1—C14—C13	122.37 (18)
C18—C19—C20	119.5 (2)	C14—C15—C16	120.3 (2)
C19—C20—C21	117.2 (2)	C11—C16—C15	120.6 (2)
C19—C20—C23	121.5 (2)	C15—C16—C17	119.64 (18)
C21—C20—C23	121.3 (2)	C11—C16—C17	119.7 (2)
C20—C21—C22	119.1 (2)	C12—C17—C16	120.2 (2)
N4—C22—C21	124.0 (2)	C16—C11—H11A	112.8 (17)
C20—C23—C26	121.1 (2)	C16—C11—H11B	112.4 (17)
C20—C23—C24	122.1 (2)	H11B—C11—H11C	107 (2)
C24—C23—C26	116.7 (2)	H11A—C11—H11B	107 (2)
C23—C24—C25	119.7 (2)	C16—C11—H11C	112.0 (16)
N3—C25—C24	123.5 (2)	H11A—C11—H11C	106 (2)
C23—C26—C27	119.6 (2)	C14—C13—H13	120.5 (13)
N3—C27—C26	124.2 (2)	C12—C13—H13	119.8 (13)
N4—C18—H18	115.5 (16)	C14—C15—H15	119.0 (12)
C19—C18—H18	120.4 (16)	C16—C15—H15	120.6 (12)
C20—C19—H19	120.3 (16)	C16—C17—H17	120.3 (13)
C18—C19—H19	120.2 (16)	C12—C17—H17	119.4 (13)
C22—C21—H21	117.7 (16)	C35—C34—C39	120.7 (2)
C20—C21—H21	123.2 (16)	C33—C35—C36	120.1 (2)
C21—C22—H22	119.7 (15)	C34—C35—C36	119.10 (18)
N4—C22—H22	116.3 (15)	C33—C35—C34	120.8 (2)
C23—C24—H24	122.0 (16)	C35—C36—C37	120.1 (2)
C25—C24—H24	118.3 (16)	C36—C37—C38	120.5 (2)
N3—C25—H25	117.1 (15)	O3—C37—C38	122.21 (18)
C24—C25—H25	119.5 (15)	O3—C37—C36	117.3 (2)
C23—C26—H26	120.6 (15)	C37—C38—C39	119.39 (18)
C27—C26—H26	119.8 (15)	C34—C39—C38	120.2 (2)
N3—C27—H27	115.2 (16)	O4—C39—C34	117.42 (19)
C26—C27—H27	120.7 (17)	O4—C39—C38	122.38 (17)
N5—C28—C29	124.6 (2)	C35—C33—H33B	111.4 (17)
C28—C29—C30	120.3 (2)	C35—C33—H33A	113.2 (17)
C29—C30—C30^i	122.5 (2)	H33A—C33—H33C	111 (3)
C30^i—C30—C31	121.9 (2)	H33B—C33—H33C	103 (2)
C29—C30—C31	115.6 (2)	C35—C33—H33C	113.1 (17)
C30—C31—C32	119.7 (2)	H33A—C33—H33B	104 (2)
N5—C32—C31	124.9 (2)	C35—C34—H34	120.0 (16)
N5—C28—H28	115.6 (15)	C39—C34—H34	119.3 (16)
C29—C28—H28	119.7 (15)	C35—C36—H36	120.7 (16)
C30—C29—H29	118.8 (17)	C37—C36—H36	119.2 (16)
C28—C29—H29	120.8 (17)	C37—C38—H38	122.6 (15)
C32—C31—H31	117.7 (16)	C39—C38—H38	118.0 (15)
C30—C31—H31	122.6 (16)	O6—C51—C56	122.31 (17)
N5—C32—H32	115.9 (16)	O6—C51—C52	117.00 (19)
C31—C32—H32	119.3 (17)	C52—C51—C56	120.7 (2)
N7—C40—C41	124.0 (2)	C51—C52—C53	119.9 (2)
C40—C41—C42	119.4 (2)	C50—C53—C52	120.9 (2)
C41—C42—C45	122.0 (2)	C52—C53—C54	119.60 (18)
C43—C42—C45	120.8 (2)	C50—C53—C54	119.5 (2)
C41—C42—C43	117.2 (2)	C53—C54—C55	120.4 (2)
C42—C43—C44	119.3 (2)	O5—C55—C54	117.9 (2)
N7—C44—C43	123.9 (2)	O5—C55—C56	121.95 (18)
C46—C45—C49	116.5 (2)	C54—C55—C56	120.2 (2)
C42—C45—C46	122.4 (2)	C51—C56—C55	119.21 (18)
C42—C45—C49	121.1 (2)	C53—C50—H50A	110.5 (16)
C45—C46—C47	119.6 (2)	C53—C50—H50B	112.8 (16)
N6—C47—C46	124.4 (2)	C53—C50—H50C	113.5 (17)
N6—C48—C49	124.1 (2)	H50A—C50—H50B	109 (2)
C45—C49—C48	119.5 (2)	H50A—C50—H50C	105 (2)
N7—C40—H40	117.2 (11)	H50B—C50—H50C	106 (2)
C41—C40—H40	118.8 (11)	C51—C52—H52	120.1 (13)
C42—C41—H41	122.2 (13)	C53—C52—H52	120.0 (13)
C40—C41—H41	118.4 (13)	C53—C54—H54	119.8 (12)
C44—C43—H43	118.8 (16)	C55—C54—H54	119.7 (12)
C42—C43—H43	121.8 (16)	C51—C56—H56	121.4 (15)
C43—C44—H44	119.2 (15)	C55—C56—H56	119.4 (15)
C10—N1—C9—C7	0.2 (4)	C43—C42—C45—C49	30.4 (3)
C9—N1—C10—C8	0.0 (4)	C41—C42—C45—C49	−150.2 (2)
C1—N2—C3—C4	2.4 (4)	C45—C42—C43—C44	179.5 (2)
C3—N2—C1—C2	−1.3 (4)	C41—C42—C43—C44	0.0 (4)
C25—N3—C27—C26	0.7 (4)	C43—C42—C45—C46	−149.3 (2)
C27—N3—C25—C24	−0.3 (4)	C42—C43—C44—N7	0.5 (4)
C18—N4—C22—C21	0.4 (4)	C49—C45—C46—C47	0.5 (4)
C22—N4—C18—C19	−0.1 (4)	C46—C45—C49—C48	0.6 (4)
C28—N5—C32—C31	−0.1 (5)	C42—C45—C46—C47	−179.9 (2)
C32—N5—C28—C29	0.9 (5)	C42—C45—C49—C48	−179.1 (2)
C47—N6—C48—C49	0.0 (4)	C45—C46—C47—N6	−1.4 (4)
C48—N6—C47—C46	1.2 (4)	N6—C48—C49—C45	−0.8 (4)
C44—N7—C40—C41	0.9 (4)	C58—C57—C66—N9	−1.0 (4)
C40—N7—C44—C43	−1.0 (4)	C66—C57—C58—C59	1.6 (4)
C65—N8—C63—C62	−0.4 (4)	C66—C57—C58—C61	−177.6 (2)
C63—N8—C65—C64	0.6 (4)	C57—C58—C61—C62	153.4 (2)
C60—N9—C66—C57	−0.3 (4)	C59—C58—C61—C64	155.4 (2)
C66—N9—C60—C59	0.9 (4)	C57—C58—C61—C64	−25.5 (4)
N2—C1—C2—C5	−0.7 (4)	C59—C58—C61—C62	−25.8 (4)
C1—C2—C5—C6	−178.0 (2)	C57—C58—C59—C60	−1.1 (4)
C1—C2—C5—C4	1.7 (4)	C61—C58—C59—C60	178.1 (2)
N2—C3—C4—C5	−1.4 (5)	C58—C59—C60—N9	−0.2 (4)
C3—C4—C5—C6	179.0 (2)	C62—C61—C64—C65	0.0 (4)
C3—C4—C5—C2	−0.7 (4)	C58—C61—C62—C63	−178.7 (2)
C4—C5—C6—C8	−33.5 (3)	C58—C61—C64—C65	178.9 (2)
C4—C5—C6—C7	145.1 (3)	C64—C61—C62—C63	0.2 (4)
C2—C5—C6—C8	146.2 (2)	C61—C62—C63—N8	0.0 (4)
C2—C5—C6—C7	−35.1 (3)	C61—C64—C65—N8	−0.4 (4)
C8—C6—C7—C9	−0.1 (4)	O2—C12—C13—C14	178.4 (2)
C7—C6—C8—C10	0.3 (4)	C17—C12—C13—C14	0.4 (3)
C5—C6—C8—C10	179.0 (2)	O2—C12—C17—C16	−178.58 (19)
C5—C6—C7—C9	−178.8 (2)	C13—C12—C17—C16	−0.5 (3)
C6—C7—C9—N1	−0.2 (4)	C12—C13—C14—O1	180.00 (19)
C6—C8—C10—N1	−0.3 (4)	C12—C13—C14—C15	0.5 (3)
N4—C18—C19—C20	−0.7 (4)	O1—C14—C15—C16	179.17 (19)
C18—C19—C20—C21	1.0 (4)	C13—C14—C15—C16	−1.3 (3)
C18—C19—C20—C23	−178.5 (2)	C14—C15—C16—C11	−177.8 (2)
C21—C20—C23—C24	156.0 (2)	C14—C15—C16—C17	1.2 (3)
C23—C20—C21—C22	178.8 (2)	C11—C16—C17—C12	178.7 (2)
C19—C20—C23—C24	−24.6 (4)	C15—C16—C17—C12	−0.3 (3)
C19—C20—C21—C22	−0.6 (4)	C39—C34—C35—C33	−178.7 (2)
C19—C20—C23—C26	155.9 (2)	C39—C34—C35—C36	0.4 (3)
C21—C20—C23—C26	−23.5 (4)	C35—C34—C39—O4	−179.66 (19)
C20—C21—C22—N4	−0.1 (4)	C35—C34—C39—C38	−1.1 (3)
C20—C23—C26—C27	178.7 (2)	C33—C35—C36—C37	−180.0 (2)
C24—C23—C26—C27	−0.8 (4)	C34—C35—C36—C37	1.0 (3)
C26—C23—C24—C25	1.2 (4)	C35—C36—C37—O3	176.95 (19)
C20—C23—C24—C25	−178.4 (2)	C35—C36—C37—C38	−1.6 (3)
C23—C24—C25—N3	−0.6 (4)	O3—C37—C38—C39	−177.62 (19)
C23—C26—C27—N3	−0.1 (4)	C36—C37—C38—C39	0.8 (3)
N5—C28—C29—C30	−1.6 (5)	C37—C38—C39—O4	178.98 (19)
C28—C29—C30—C31	1.3 (4)	C37—C38—C39—C34	0.5 (3)
C28—C29—C30—C30^i	−179.4 (2)	O6—C51—C52—C53	−179.55 (19)
C29—C30—C30^i—C29^i	−180.0 (2)	C56—C51—C52—C53	1.4 (3)
C29—C30—C30^i—C31^i	0.7 (4)	O6—C51—C56—C55	−179.65 (19)
C31—C30—C30^i—C31^i	180.0 (2)	C52—C51—C56—C55	−0.6 (3)
C31—C30—C30^i—C29^i	−0.7 (4)	C51—C52—C53—C50	178.6 (2)
C30^i—C30—C31—C32	−179.9 (2)	C51—C52—C53—C54	−0.5 (3)
C29—C30—C31—C32	−0.5 (4)	C50—C53—C54—C55	179.8 (2)
C30—C31—C32—N5	−0.1 (5)	C52—C53—C54—C55	−1.1 (3)
N7—C40—C41—C42	−0.4 (4)	C53—C54—C55—O5	−177.2 (2)
C40—C41—C42—C43	−0.1 (3)	C53—C54—C55—C56	1.9 (3)
C40—C41—C42—C45	−179.5 (2)	O5—C55—C56—C51	178.02 (19)
C41—C42—C45—C46	30.1 (4)	C54—C55—C56—C51	−1.0 (3)

Symmetry codes: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N8^ii	1.04 (3)	1.74 (3)	2.768 (3)	172 (3)
O3—H3A···N4	1.02 (3)	1.73 (3)	2.740 (3)	169 (3)
O4—H4A···N2^iii	1.01 (3)	1.75 (3)	2.765 (3)	178 (2)
O5—H5···N1^iv	1.03 (3)	1.73 (3)	2.750 (3)	170 (3)
O6—H6···N3^v	1.05 (3)	1.69 (3)	2.736 (3)	179 (3)
C2—H2···O5^vi	0.96 (3)	2.57 (3)	3.275 (3)	130 (2)
C28—H28···O6^vii	1.02 (3)	2.57 (3)	3.430 (3)	142 (2)
C47—H47···O4^viii	0.99 (3)	2.50 (3)	3.298 (3)	137 (2)

Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x−1/2, −y+3/2, z+1/2; (iv) x+1/2, −y+3/2, z−1/2; (v) x+1, y, z−1; (vi) x+1/2, −y+3/2, z+1/2; (vii) −x+1, −y+1, −z; (viii) −x+3/2, y−1/2, −z+3/2.

(III_160K)

Crystal data

1.5(C10H8N2)·1(C7H8O2)	F(000) = 756
Mr = 358.42	Dx = 1.286 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3251 reflections
a = 9.0828 (3) Å	θ = 2.4–27.4°
b = 12.3446 (4) Å	µ = 0.08 mm^−1
c = 16.6095 (4) Å	T = 160 K
β = 96.320 (2)°	Block, colourless
V = 1851.00 (10) Å^3	0.5 × 0.4 × 0.36 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	4043 independent reflections
Radiation source: Mova (Mo) X-ray Source	3006 reflections with I > 2σ(I)
mirror	Rint = 0.029
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.0°, θmin = 2.5°
ω scans	h = −11→11
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −15→15
Tmin = 0.762, Tmax = 1.000	l = −21→21
12370 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.052	Secondary atom site location: difference Fourier map
wR(F^2) = 0.149	Hydrogen site location: inferred from neighbouring sites
S = 1.06	H atoms treated by a mixture of independent and constrained refinement
4066 reflections	w = 1/[σ^2(Fo^2) + (0.0684P)^2 + 0.2541P] where P = (Fo^2 + 2Fc^2)/3
324 parameters	(Δ/σ)max < 0.001

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.71125 (18)	0.08114 (13)	0.10674 (9)	0.0399 (6)
N2	1.31872 (18)	0.27921 (14)	−0.08523 (10)	0.0388 (6)
C8	1.3371 (2)	0.24452 (19)	−0.00875 (12)	0.0449 (8)
C9	1.2241 (2)	0.20383 (18)	0.03128 (11)	0.0412 (7)
C10	1.0819 (2)	0.19782 (15)	−0.00788 (10)	0.0301 (6)
C11	1.0615 (2)	0.23741 (18)	−0.08656 (11)	0.0423 (8)
C12	1.1807 (2)	0.27638 (19)	−0.12211 (12)	0.0462 (8)
C13	0.9560 (2)	0.15390 (15)	0.03177 (10)	0.0297 (6)
C14	0.9568 (2)	0.15316 (19)	0.11543 (11)	0.0469 (8)
C15	0.8344 (2)	0.11578 (19)	0.14932 (11)	0.0477 (8)
C16	0.7122 (2)	0.07981 (18)	0.02634 (12)	0.0453 (8)
C17	0.8294 (2)	0.11450 (17)	−0.01273 (11)	0.0399 (7)
N3	0.66703 (19)	0.39633 (15)	0.06610 (10)	0.0496 (7)
C18	0.9222 (2)	0.4458 (2)	0.09287 (12)	0.0529 (9)
C19	0.7908 (3)	0.4061 (2)	0.11530 (13)	0.0581 (9)
C20	0.6761 (2)	0.4276 (2)	−0.00922 (13)	0.0596 (9)
C21	0.8023 (2)	0.4680 (2)	−0.03755 (11)	0.0511 (8)
C22	0.93084 (19)	0.47847 (15)	0.01388 (10)	0.0293 (6)
O1	0.53975 (14)	−0.08776 (10)	−0.18443 (8)	0.0398 (5)
O2	0.54191 (14)	0.30244 (10)	−0.18291 (7)	0.0367 (5)
C1	0.8012 (2)	0.10741 (15)	−0.25035 (10)	0.0292 (6)
C2	0.7349 (2)	0.01028 (15)	−0.23313 (11)	0.0311 (6)
C3	0.6015 (2)	0.01024 (15)	−0.19917 (10)	0.0293 (6)
C4	0.53419 (19)	0.10721 (15)	−0.18196 (10)	0.0278 (6)
C5	0.6021 (2)	0.20429 (15)	−0.19843 (10)	0.0274 (6)
C6	0.7348 (2)	0.20400 (15)	−0.23331 (10)	0.0294 (6)
C7	0.9461 (2)	0.10721 (17)	−0.28667 (12)	0.0446 (8)
H8	1.44873	0.24820	0.02165	0.0610
H9	1.25068	0.17596	0.09300	0.0592
H11	0.95282	0.24073	−0.12062	0.0483
H12	1.16067	0.31049	−0.18240	0.0526
H14	1.05369	0.18000	0.15413	0.0595
H15	0.83681	0.11932	0.21460	0.0650
H16	0.61252	0.04983	−0.00829	0.0525
H17	0.82054	0.10895	−0.07816	0.0488
H18	1.01657	0.44701	0.13882	0.0565
H19	0.79010	0.37814	0.17707	0.0593
H20	0.57439	0.42110	−0.04957	0.0516
H21	0.79865	0.48910	−0.10103	0.0506
H1	0.45130	−0.08208	−0.15457	0.0476
H2	0.46261	0.29791	−0.14647	0.0460
H2A	0.78574	−0.06579	−0.24714	0.0500
H4	0.42875	0.10612	−0.15721	0.0485
H6	0.78379	0.28084	−0.24718	0.0480
H7A	0.97818	0.18482	−0.30867	0.0577
H7B	1.03739	0.09167	−0.24108	0.0576
H7C	0.96023	0.03906	−0.32556	0.0586

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0347 (11)	0.0485 (11)	0.0380 (9)	−0.0074 (9)	0.0102 (8)	0.0036 (8)
N2	0.0319 (10)	0.0441 (11)	0.0428 (10)	−0.0037 (9)	0.0144 (8)	−0.0069 (9)
C8	0.0277 (12)	0.0613 (16)	0.0460 (12)	−0.0041 (11)	0.0056 (10)	−0.0020 (11)
C9	0.0298 (12)	0.0589 (15)	0.0349 (11)	−0.0045 (11)	0.0034 (9)	0.0015 (10)
C10	0.0284 (11)	0.0344 (11)	0.0281 (10)	−0.0015 (10)	0.0061 (8)	−0.0040 (9)
C11	0.0312 (13)	0.0619 (15)	0.0338 (11)	−0.0082 (11)	0.0030 (9)	0.0022 (10)
C12	0.0448 (14)	0.0599 (15)	0.0356 (11)	−0.0081 (13)	0.0126 (10)	0.0025 (11)
C13	0.0258 (11)	0.0352 (11)	0.0286 (10)	0.0005 (10)	0.0057 (8)	0.0001 (9)
C14	0.0325 (13)	0.0784 (17)	0.0296 (11)	−0.0108 (12)	0.0020 (9)	−0.0011 (11)
C15	0.0403 (14)	0.0733 (17)	0.0303 (11)	−0.0095 (13)	0.0078 (10)	0.0024 (11)
C16	0.0376 (13)	0.0610 (16)	0.0375 (11)	−0.0170 (12)	0.0047 (10)	−0.0009 (11)
C17	0.0349 (13)	0.0563 (14)	0.0286 (10)	−0.0111 (11)	0.0045 (9)	−0.0017 (10)
H8	0.0372	0.0828	0.0623	−0.0061	0.0021	−0.0010
H9	0.0492	0.0802	0.0473	−0.0042	0.0008	0.0097
H11	0.0374	0.0637	0.0441	−0.0053	0.0058	0.0041
H12	0.0490	0.0672	0.0432	−0.0091	0.0127	0.0043
H14	0.0488	0.0843	0.0444	−0.0123	0.0004	0.0044
H15	0.0648	0.0946	0.0363	−0.0164	0.0089	0.0076
H16	0.0436	0.0691	0.0455	−0.0126	0.0076	0.0026
H17	0.0464	0.0642	0.0369	−0.0064	0.0095	0.0027
N3	0.0383 (11)	0.0682 (14)	0.0444 (11)	−0.0097 (10)	0.0134 (9)	−0.0005 (10)
C18	0.0330 (13)	0.0917 (19)	0.0335 (11)	−0.0081 (13)	0.0021 (9)	0.0160 (12)
C19	0.0391 (14)	0.095 (2)	0.0414 (13)	−0.0075 (14)	0.0105 (11)	0.0203 (13)
C20	0.0352 (14)	0.106 (2)	0.0379 (12)	−0.0218 (14)	0.0059 (10)	−0.0058 (13)
C21	0.0364 (13)	0.0908 (19)	0.0264 (10)	−0.0163 (13)	0.0044 (9)	0.0008 (11)
C22	0.0278 (11)	0.0331 (11)	0.0275 (10)	0.0008 (9)	0.0054 (8)	−0.0031 (9)
H18	0.0435	0.0834	0.0420	−0.0104	0.0025	−0.0034
H19	0.0529	0.0889	0.0374	−0.0127	0.0111	−0.0012
H20	0.0401	0.0669	0.0471	−0.0066	0.0027	−0.0064
H21	0.0506	0.0625	0.0391	−0.0076	0.0068	0.0002
O1	0.0393 (9)	0.0311 (8)	0.0523 (9)	−0.0069 (7)	0.0195 (7)	−0.0009 (6)
O2	0.0385 (9)	0.0311 (8)	0.0434 (8)	0.0035 (7)	0.0170 (7)	0.0021 (6)
C1	0.0259 (11)	0.0371 (11)	0.0255 (9)	−0.0008 (10)	0.0064 (8)	−0.0003 (9)
C2	0.0323 (12)	0.0304 (11)	0.0317 (10)	0.0021 (10)	0.0087 (9)	−0.0047 (9)
C3	0.0300 (11)	0.0329 (12)	0.0249 (9)	−0.0053 (10)	0.0033 (8)	−0.0018 (9)
C4	0.0252 (11)	0.0356 (11)	0.0234 (9)	−0.0026 (9)	0.0070 (8)	0.0005 (8)
C5	0.0287 (11)	0.0308 (12)	0.0226 (9)	0.0025 (10)	0.0030 (8)	0.0011 (8)
C6	0.0299 (12)	0.0302 (11)	0.0291 (10)	−0.0040 (9)	0.0078 (8)	0.0040 (8)
C7	0.0396 (13)	0.0447 (13)	0.0538 (13)	−0.0028 (11)	0.0249 (11)	−0.0044 (11)
H1	0.0419	0.0497	0.0537	−0.0041	0.0163	0.0023
H2	0.0421	0.0501	0.0475	−0.0021	0.0128	−0.0045
H2A	0.0466	0.0443	0.0614	0.0027	0.0163	−0.0013
H4	0.0391	0.0536	0.0557	−0.0032	0.0176	−0.0016
H6	0.0511	0.0442	0.0507	−0.0085	0.0150	0.0022
H7A	0.0593	0.0525	0.0652	−0.0085	0.0250	0.0049
H7B	0.0434	0.0792	0.0510	−0.0005	0.0082	0.0026
H7C	0.0566	0.0590	0.0641	−0.0073	0.0231	−0.0176

Geometric parameters (Å, °)

O1—C3	1.367 (2)	C16—H16	1.0800
O2—C5	1.365 (2)	C17—H17	1.0800
O1—H1	0.9900	C18—C19	1.379 (3)
O2—H2	0.9900	C18—C22	1.383 (3)
N1—C15	1.327 (2)	C20—C21	1.379 (3)
N1—C16	1.337 (2)	C21—C22	1.375 (3)
N2—C8	1.334 (3)	C22—C22^i	1.484 (2)
N2—C12	1.334 (2)	C18—H18	1.0800
N3—C19	1.321 (3)	C19—H19	1.0800
N3—C20	1.320 (3)	C20—H20	1.0800
C8—C9	1.378 (3)	C21—H21	1.0800
C9—C10	1.383 (3)	C1—C7	1.507 (3)
C10—C13	1.484 (3)	C1—C2	1.386 (3)
C10—C11	1.388 (3)	C1—C6	1.380 (3)
C11—C12	1.376 (3)	C2—C3	1.392 (3)
C13—C14	1.389 (2)	C3—C4	1.388 (3)
C13—C17	1.385 (3)	C4—C5	1.389 (3)
C14—C15	1.380 (3)	C5—C6	1.394 (3)
C16—C17	1.375 (3)	C2—H2A	1.0800
C8—H8	1.0800	C4—H4	1.0800
C9—H9	1.0800	C6—H6	1.0800
C11—H11	1.0800	C7—H7A	1.0800
C12—H12	1.0800	C7—H7B	1.0800
C14—H14	1.0800	C7—H7C	1.0800
C15—H15	1.0800
O1···N1^ii	2.742 (2)	H2···N2^iv	1.7600
O2···C15^iii	3.344 (2)	H2···H20	2.3600
O2···N2^iv	2.747 (2)	H2···H4	2.3900
O2···C20	3.380 (2)	H2A···H14^v	2.4500
O2···C14^iii	3.398 (2)	H2A···C6^vi	2.8600
O1···H9^v	2.5500	H2A···H7C	2.5200
O1···H6^vi	2.6300	H2A···H6^vi	1.9900
O1···H7A^vi	2.8100	H2A···O2^vi	2.6200
O2···H15^iii	2.5700	H4···H2	2.3900
O2···H2A^vii	2.6200	H4···N1^ii	2.8100
O2···H20	2.6400	H4···H1	2.3300
O2···H14^iii	2.7300	H4···N2^iv	2.6900
N1···O1^ii	2.742 (2)	H6···O1^vii	2.6300
N2···O2^viii	2.747 (2)	H6···H7A	2.4400
N2···C4^viii	3.408 (2)	H6···H11	2.5100
N3···C7^ix	3.330 (3)	H6···H14^iii	2.5600
N1···H1^ii	1.7500	H6···C2^vii	2.8500
N1···H4^ii	2.8100	H6···H2A^vii	1.9900
N2···H20^viii	2.9200	H7A···H6	2.4400
N2···H2^viii	1.7600	H7A···O1^vii	2.8100
N2···H4^viii	2.6900	H7C···H2A	2.5200
N3···H7C^ix	2.8500	H7C···H20^vi	2.5300
N3···H8^iv	2.7400	H7C···N3^x	2.8500
C4···N2^iv	3.408 (2)	H8···N3^viii	2.7400
C7···N3^x	3.330 (3)	H9···H14	2.1500
C14···C19	3.467 (3)	H9···O1^v	2.5500
C14···O2^xi	3.398 (2)	H9···C14	2.7500
C15···O2^xi	3.344 (2)	H11···C1	2.9300
C19···C14	3.467 (3)	H11···C6	2.6100
C20···O2	3.380 (2)	H11···C17	2.7100
C1···H18^iii	3.0800	H11···H6	2.5100
C1···H17	2.8500	H11···H17	2.1800
C1···H21^vi	2.9300	H14···C9	2.7100
C1···H11	2.9300	H14···H9	2.1500
C2···H6^vi	2.8500	H14···H2A^v	2.4500
C2···H21^vi	2.7500	H14···C6^xi	2.7500
C2···H17	2.8800	H14···O2^xi	2.7300
C2···H18^iii	2.7900	H14···C5^xi	2.8300
C3···H18^iii	2.7700	H14···H6^xi	2.5600
C3···H17	2.9300	H15···O2^xi	2.5700
C4···H18^iii	3.0400	H16···H16^ii	2.4300
C4···H16	2.9800	H16···C4	2.9800
C4···H19^iii	3.0500	H17···C1	2.8500
C4···H17	2.9600	H17···C2	2.8800
C5···H17	2.9100	H17···C3	2.9300
C5···H14^iii	2.8300	H17···C4	2.9600
C6···H11	2.6100	H17···C5	2.9100
C6···H17	2.8600	H17···C6	2.8600
C6···H2A^vii	2.8600	H17···C11	2.7200
C6···H14^iii	2.7500	H17···H11	2.1800
C8···H2^viii	2.7500	H18···C21^i	2.6900
C9···H14	2.7100	H18···H21^i	2.0200
C11···H17	2.7200	H18···C1^xi	3.0800
C12···H2^viii	2.6500	H18···C2^xi	2.7900
C14···H9	2.7500	H18···C3^xi	2.7700
C15···H1^ii	2.6400	H18···C4^xi	3.0400
C16···H1^ii	2.7300	H19···C4^xi	3.0500
C17···H11	2.7100	H20···O2	2.6400
C18···H21^i	2.6500	H20···N2^iv	2.9200
C21···H18^i	2.6900	H20···H2	2.3600
H1···N1^ii	1.7500	H20···H7C^vii	2.5300
H1···C15^ii	2.6400	H21···C1^vii	2.9300
H1···H4	2.3300	H21···C2^vii	2.7500
H1···C16^ii	2.7300	H21···C18^i	2.6500
H2···C8^iv	2.7500	H21···H18^i	2.0200
H2···C12^iv	2.6500
C3—O1—H1	113.00	N3—C20—C21	124.73 (18)
C5—O2—H2	113.00	C20—C21—C22	120.18 (18)
C15—N1—C16	116.03 (16)	C18—C22—C21	115.41 (17)
C8—N2—C12	116.22 (17)	C21—C22—C22^i	122.06 (16)
C19—N3—C20	114.96 (18)	C18—C22—C22^i	122.53 (16)
N2—C8—C9	123.71 (17)	C22—C18—H18	123.00
C8—C9—C10	119.97 (17)	C19—C18—H18	117.00
C11—C10—C13	121.13 (16)	N3—C19—H19	118.00
C9—C10—C13	122.45 (16)	C18—C19—H19	118.00
C9—C10—C11	116.41 (17)	N3—C20—H20	115.00
C10—C11—C12	119.82 (17)	C21—C20—H20	120.00
N2—C12—C11	123.80 (18)	C20—C21—H21	119.00
C10—C13—C14	121.81 (16)	C22—C21—H21	121.00
C14—C13—C17	116.38 (17)	C2—C1—C7	119.98 (17)
C10—C13—C17	121.78 (15)	C2—C1—C6	119.72 (17)
C13—C14—C15	119.65 (17)	C6—C1—C7	120.29 (17)
N1—C15—C14	124.08 (17)	C1—C2—C3	120.10 (17)
N1—C16—C17	123.94 (18)	O1—C3—C2	117.75 (16)
C13—C17—C16	119.87 (17)	C2—C3—C4	120.40 (17)
C9—C8—H8	120.00	O1—C3—C4	121.85 (16)
N2—C8—H8	116.00	C3—C4—C5	119.23 (16)
C10—C9—H9	122.00	O2—C5—C4	122.20 (16)
C8—C9—H9	118.00	O2—C5—C6	117.60 (16)
C12—C11—H11	119.00	C4—C5—C6	120.19 (17)
C10—C11—H11	122.00	C1—C6—C5	120.34 (17)
C11—C12—H12	118.00	C1—C2—H2A	120.00
N2—C12—H12	118.00	C3—C2—H2A	120.00
C13—C14—H14	120.00	C3—C4—H4	120.00
C15—C14—H14	120.00	C5—C4—H4	121.00
C14—C15—H15	118.00	C1—C6—H6	121.00
N1—C15—H15	118.00	C5—C6—H6	119.00
N1—C16—H16	116.00	C1—C7—H7A	115.00
C17—C16—H16	120.00	C1—C7—H7B	111.00
C13—C17—H17	122.00	C1—C7—H7C	114.00
C16—C17—H17	119.00	H7A—C7—H7B	100.00
C19—C18—C22	120.08 (18)	H7A—C7—H7C	116.00
N3—C19—C18	124.6 (2)	H7B—C7—H7C	99.00
C16—N1—C15—C14	2.6 (3)	C22—C18—C19—N3	−0.2 (4)
C15—N1—C16—C17	−1.9 (3)	C19—C18—C22—C21	0.0 (3)
C12—N2—C8—C9	2.3 (3)	C19—C18—C22—C22^i	−179.8 (2)
C8—N2—C12—C11	−2.0 (3)	N3—C20—C21—C22	−0.2 (4)
C20—N3—C19—C18	0.2 (4)	C20—C21—C22—C18	0.2 (3)
C19—N3—C20—C21	0.0 (3)	C20—C21—C22—C22^i	−180.0 (2)
N2—C8—C9—C10	−0.3 (3)	C18—C22—C22^i—C18^i	−180.0 (2)
C8—C9—C10—C13	179.44 (19)	C18—C22—C22^i—C21^i	−0.2 (3)
C8—C9—C10—C11	−1.9 (3)	C21—C22—C22^i—C18^i	0.2 (3)
C13—C10—C11—C12	−179.18 (19)	C21—C22—C22^i—C21^i	180.0 (2)
C9—C10—C13—C14	24.1 (3)	C6—C1—C2—C3	0.3 (3)
C11—C10—C13—C14	−154.6 (2)	C7—C1—C2—C3	179.64 (16)
C11—C10—C13—C17	23.4 (3)	C2—C1—C6—C5	0.4 (3)
C9—C10—C13—C17	−158.0 (2)	C7—C1—C6—C5	−178.89 (16)
C9—C10—C11—C12	2.1 (3)	C1—C2—C3—O1	179.10 (16)
C10—C11—C12—N2	−0.2 (3)	C1—C2—C3—C4	−0.3 (3)
C17—C13—C14—C15	−0.9 (3)	O1—C3—C4—C5	−179.86 (15)
C10—C13—C17—C16	−176.58 (19)	C2—C3—C4—C5	−0.5 (3)
C10—C13—C14—C15	177.19 (19)	C3—C4—C5—O2	−179.94 (16)
C14—C13—C17—C16	1.5 (3)	C3—C4—C5—C6	1.3 (3)
C13—C14—C15—N1	−1.2 (3)	O2—C5—C6—C1	179.92 (15)
N1—C16—C17—C13	−0.1 (3)	C4—C5—C6—C1	−1.2 (3)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y, −z; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1, y, z; (v) −x+2, −y, −z; (vi) −x+3/2, y−1/2, −z−1/2; (vii) −x+3/2, y+1/2, −z−1/2; (viii) x+1, y, z; (ix) x−1/2, −y+1/2, z+1/2; (x) x+1/2, −y+1/2, z−1/2; (xi) x+1/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^ii	0.9900	1.7500	2.742 (2)	175.00
O2—H2···N2^iv	0.9900	1.7600	2.747 (2)	175.00
C9—H9···O1^v	1.0800	2.5500	3.453 (2)	141.00
C15—H15···O2^xi	1.0800	2.5700	3.344 (2)	128.00

Symmetry codes: (ii) −x+1, −y, −z; (iv) x−1, y, z; (v) −x+2, −y, −z; (xi) x+1/2, −y+1/2, z+1/2.

(III_200K)

Crystal data

1.5(C10H8N2)·1(C7H8O2)	Z = 4
Mr = 358.42	F(000) = 756
Monoclinic, P21/n	Dx = 1.279 Mg m^−3
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.1180 (3) Å	µ = 0.08 mm^−1
b = 12.3427 (4) Å	T = 200 K
c = 16.6400 (4) Å	Block, colourless
β = 96.381 (3)°	0.50 × 0.30 × 0.20 mm
V = 1861.08 (10) Å^3

Data collection

Xcalibur, Eos, Nova diffractometer	4065 independent reflections
Radiation source: Mova (Mo) X-ray Source	2819 reflections with I > 2σ(I)
mirror	Rint = 0.028
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.0°, θmin = 2.5°
ω scans	h = −11→11
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −15→15
Tmin = 0.998, Tmax = 0.999	l = −21→21
12473 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.168	WHERE P = (FO^2 + 2FC^2)/3
S = 1.08	(Δ/σ)max < 0.001
4065 reflections	Δρmax = 0.29 e Å^−3
252 parameters	Δρmin = −0.21 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.45565 (15)	0.70157 (10)	0.17978 (8)	0.0476 (4)
O2	0.46038 (16)	1.09128 (10)	0.18582 (9)	0.0508 (5)
C16	0.19886 (19)	0.89584 (14)	0.24919 (10)	0.0378 (5)
C17	0.26404 (19)	0.79897 (14)	0.23078 (10)	0.0378 (5)
C18	0.39671 (19)	0.79956 (14)	0.19626 (9)	0.0353 (5)
C19	0.46426 (18)	0.89638 (14)	0.18081 (9)	0.0349 (5)
C20	0.39825 (19)	0.99301 (14)	0.19919 (10)	0.0371 (5)
C21	0.26539 (19)	0.99268 (15)	0.23299 (10)	0.0400 (6)
C22	0.0541 (2)	0.89544 (17)	0.28589 (13)	0.0540 (7)
N1	0.78816 (18)	0.58550 (14)	0.39080 (10)	0.0519 (6)
N2	0.18020 (17)	0.77434 (14)	0.58332 (10)	0.0505 (6)
C6	0.7861 (2)	0.58091 (19)	0.47052 (12)	0.0586 (8)
C7	0.6689 (2)	0.61418 (18)	0.50977 (11)	0.0515 (7)
C8	0.54411 (19)	0.65516 (15)	0.46580 (10)	0.0392 (5)
C9	0.5438 (2)	0.6570 (2)	0.38255 (12)	0.0608 (8)
C10	0.6659 (2)	0.6214 (2)	0.34874 (12)	0.0632 (8)
C11	0.41744 (19)	0.69716 (15)	0.50584 (10)	0.0390 (5)
C12	0.4357 (2)	0.7326 (2)	0.58518 (11)	0.0580 (8)
C13	0.3161 (2)	0.7698 (2)	0.62074 (12)	0.0634 (8)
C14	0.1639 (2)	0.7450 (2)	0.50619 (12)	0.0573 (8)
C15	0.2771 (2)	0.70567 (19)	0.46592 (12)	0.0546 (7)
N6	0.6683 (2)	0.40089 (17)	0.06817 (11)	0.0641 (7)
C1	0.9219 (2)	0.4508 (2)	0.09376 (12)	0.0691 (9)
C2	0.7908 (3)	0.4128 (2)	0.11679 (14)	0.0772 (12)
C4	0.6777 (2)	0.4278 (2)	−0.00732 (13)	0.0712 (9)
C5	0.8035 (2)	0.4664 (2)	−0.03679 (12)	0.0624 (8)
C23	0.93106 (18)	0.47943 (15)	0.01427 (10)	0.0386 (6)
H1O	0.535 (3)	0.706 (2)	0.1433 (16)	0.100 (9)*
H2O	0.544 (3)	1.0831 (19)	0.1571 (14)	0.077 (8)*
H17	0.21850	0.73210	0.24170	0.0450*
H19	0.55510	0.89670	0.15780	0.0420*
H21	0.22030	1.05930	0.24500	0.0480*
H22A	0.02260	0.82050	0.29320	0.0810*	0.500
H22B	−0.02110	0.93350	0.24980	0.0810*	0.500
H22C	0.06720	0.93210	0.33850	0.0810*	0.500
H22D	0.02320	0.97020	0.29450	0.0810*	0.500
H22E	0.06690	0.85720	0.33780	0.0810*	0.500
H22F	−0.02140	0.85870	0.24920	0.0810*	0.500
H6	0.87070	0.55300	0.50230	0.0700*
H7	0.67400	0.60890	0.56700	0.0620*
H9	0.45980	0.68270	0.34910	0.0730*
H10	0.66230	0.62250	0.29150	0.0760*
H12	0.53060	0.73120	0.61510	0.0700*
H13	0.33190	0.79370	0.67530	0.0760*
H14	0.06870	0.75150	0.47690	0.0690*
H15	0.25840	0.68450	0.41080	0.0660*
H1	1.00610	0.45720	0.13260	0.0830*
H2	0.78890	0.39390	0.17200	0.0930*
H4	0.59150	0.42020	−0.04460	0.0850*
H5	0.80170	0.48390	−0.09250	0.0750*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0490 (8)	0.0403 (7)	0.0572 (8)	0.0037 (6)	0.0226 (6)	0.0011 (6)
O2	0.0491 (9)	0.0415 (8)	0.0654 (9)	−0.0077 (6)	0.0230 (7)	−0.0009 (6)
C16	0.0343 (9)	0.0477 (11)	0.0326 (8)	−0.0023 (8)	0.0094 (7)	−0.0017 (7)
C17	0.0359 (9)	0.0412 (10)	0.0376 (9)	−0.0039 (8)	0.0105 (7)	0.0039 (7)
C18	0.0362 (9)	0.0394 (10)	0.0310 (8)	0.0023 (8)	0.0068 (7)	0.0017 (7)
C19	0.0317 (9)	0.0437 (10)	0.0304 (8)	−0.0033 (7)	0.0081 (7)	0.0005 (7)
C20	0.0380 (10)	0.0407 (10)	0.0330 (8)	−0.0056 (8)	0.0060 (7)	−0.0005 (7)
C21	0.0386 (10)	0.0425 (10)	0.0404 (9)	0.0011 (8)	0.0108 (7)	−0.0040 (8)
C22	0.0456 (12)	0.0585 (13)	0.0626 (13)	−0.0028 (10)	0.0270 (10)	−0.0031 (10)
N1	0.0442 (10)	0.0633 (11)	0.0505 (9)	0.0094 (8)	0.0150 (8)	−0.0061 (8)
N2	0.0404 (9)	0.0584 (10)	0.0557 (10)	0.0049 (8)	0.0188 (7)	0.0081 (8)
C6	0.0489 (12)	0.0814 (16)	0.0466 (11)	0.0234 (11)	0.0097 (9)	0.0000 (10)
C7	0.0451 (11)	0.0720 (14)	0.0377 (10)	0.0126 (10)	0.0065 (8)	0.0015 (9)
C8	0.0333 (9)	0.0468 (10)	0.0381 (9)	−0.0015 (8)	0.0069 (7)	−0.0005 (8)
C9	0.0400 (11)	0.1028 (19)	0.0400 (10)	0.0142 (12)	0.0061 (8)	0.0013 (11)
C10	0.0496 (12)	0.1012 (19)	0.0404 (10)	0.0120 (12)	0.0123 (9)	−0.0029 (11)
C11	0.0339 (9)	0.0461 (10)	0.0382 (9)	0.0017 (8)	0.0095 (7)	0.0053 (8)
C12	0.0405 (11)	0.0911 (17)	0.0428 (10)	0.0115 (11)	0.0068 (8)	−0.0044 (11)
C13	0.0554 (13)	0.0917 (17)	0.0455 (11)	0.0141 (13)	0.0162 (10)	−0.0027 (11)
C14	0.0356 (11)	0.0795 (16)	0.0575 (12)	0.0063 (10)	0.0089 (9)	0.0023 (11)
C15	0.0393 (11)	0.0790 (15)	0.0457 (10)	0.0080 (10)	0.0052 (8)	−0.0038 (10)
N6	0.0471 (11)	0.0914 (15)	0.0565 (11)	−0.0132 (10)	0.0175 (9)	0.0013 (10)
C1	0.0423 (12)	0.122 (2)	0.0430 (11)	−0.0125 (13)	0.0044 (9)	0.0183 (13)
C2	0.0500 (14)	0.134 (3)	0.0497 (12)	−0.0122 (15)	0.0147 (10)	0.0228 (14)
C4	0.0423 (12)	0.121 (2)	0.0510 (12)	−0.0247 (13)	0.0089 (10)	−0.0088 (13)
C5	0.0444 (12)	0.1058 (19)	0.0373 (10)	−0.0209 (12)	0.0060 (8)	−0.0020 (11)
C23	0.0350 (10)	0.0457 (10)	0.0362 (9)	−0.0001 (8)	0.0083 (7)	−0.0025 (7)

Geometric parameters (Å, °)

O1—C18	1.364 (2)	C6—C7	1.376 (3)
O2—C20	1.367 (2)	C7—C8	1.379 (3)
O1—H1O	1.00 (3)	C8—C11	1.489 (2)
O2—H2O	0.95 (3)	C8—C9	1.385 (3)
N1—C6	1.330 (3)	C9—C10	1.374 (3)
N1—C10	1.325 (3)	C11—C15	1.379 (3)
N2—C13	1.325 (2)	C11—C12	1.383 (3)
N2—C14	1.326 (3)	C12—C13	1.376 (3)
N6—C4	1.311 (3)	C14—C15	1.380 (3)
N6—C2	1.313 (3)	C6—H6	0.9500
C16—C21	1.381 (3)	C7—H7	0.9500
C16—C22	1.515 (3)	C9—H9	0.9500
C16—C17	1.385 (2)	C10—H10	0.9500
C17—C18	1.396 (2)	C12—H12	0.9500
C18—C19	1.382 (2)	C13—H13	0.9500
C19—C20	1.385 (2)	C14—H14	0.9500
C20—C21	1.391 (2)	C15—H15	0.9500
C17—H17	0.9500	C1—C2	1.378 (3)
C19—H19	0.9500	C1—C23	1.381 (3)
C21—H21	0.9500	C4—C5	1.381 (3)
C22—H22D	0.9800	C5—C23	1.372 (3)
C22—H22E	0.9800	C23—C23^i	1.482 (2)
C22—H22B	0.9800	C1—H1	0.9500
C22—H22C	0.9800	C2—H2	0.9500
C22—H22A	0.9800	C4—H4	0.9500
C22—H22F	0.9800	C5—H5	0.9500
O1···C10	3.371 (2)	H1O···H4^iii	2.4600
O1···N2^ii	2.755 (2)	H1O···N2^ii	1.76 (3)
O1···C4^iii	3.389 (3)	H1O···C14^ii	2.75 (3)
O2···N1^iv	2.745 (2)	H1O···C13^ii	2.65 (3)
O1···H21^v	2.7700	H2O···H19	2.3000
O1···H10	2.6800	H2O···N1^iv	1.80 (3)
O1···H4^iii	2.7000	H2O···C6^iv	2.76 (3)
O1···H22D^v	2.8900	H2O···C10^iv	2.70 (3)
O1···H9	2.8200	H4···H1O^iii	2.4600
O2···H15^vi	2.6800	H4···O1^iii	2.7000
O2···H17^vi	2.7500	H5···C16^ii	3.0800
O2···H22A^vi	2.8500	H5···C1^i	2.6500
N1···O2^vii	2.745 (2)	H5···H1^i	2.0700
N2···C19^viii	3.414 (2)	H5···H22C^ii	2.5300
N2···O1^viii	2.755 (2)	H5···C21^ii	2.9000
N6···C22^v	3.333 (3)	H6···C19^ix	3.0600
N1···H2O^vii	1.80 (3)	H7···H12	2.2000
N1···H19^vii	2.9000	H7···C18^ix	3.0100
N2···H19^viii	2.7600	H7···C16^ix	3.0200
N2···H1O^viii	1.76 (3)	H7···C17^ix	2.9800
N6···H22C^v	2.8100	H7···C12	2.7000
N6···H14^v	2.8800	H7···C21^ix	3.0600
N6···H22E^v	2.8400	H7···C19^ix	3.0800
C2···C9^vii	3.499 (3)	H7···C20^ix	3.1000
C4···O1^iii	3.389 (3)	H9···C17	2.8900
C9···C2^iv	3.499 (3)	H9···O1	2.8200
C10···O1	3.371 (2)	H9···C15	2.7100
C19···N2^ii	3.414 (2)	H9···H15	2.2000
C22···N6^vi	3.333 (3)	H9···C18	2.9200
C1···H5^i	2.6500	H10···O1	2.6800
C5···H22C^ii	3.0900	H12···H22F^ix	2.5800
C5···H1^i	2.6600	H12···C16^ix	3.0100
C6···H2O^vii	2.76 (3)	H12···C17^ix	2.7300
C7···H12	2.6900	H12···H7	2.2000
C9···H15	2.7200	H12···C7	2.6900
C10···H22B^v	3.0500	H13···H22F^ix	2.5400
C10···H2O^vii	2.70 (3)	H14···N6^vi	2.8800
C12···H22F^ix	2.9400	H15···C9	2.7200
C12···H7	2.7000	H15···O2^v	2.6800
C13···H22F^ix	2.9300	H15···H9	2.2000
C13···H1O^viii	2.65 (3)	H17···C21^v	2.9900
C14···H1O^viii	2.75 (3)	H17···H22A	2.3400
C15···H9	2.7100	H17···O2^v	2.7500
C16···H5^viii	3.0800	H17···H21^v	2.2100
C16···H12^x	3.0100	H19···H2O	2.3000
C16···H7^x	3.0200	H19···N1^iv	2.9000
C17···H9	2.8900	H19···H1O	2.3700
C17···H21^v	2.9900	H19···N2^ii	2.7600
C17···H7^x	2.9800	H21···O1^vi	2.7700
C17···H12^x	2.7300	H21···H22D	2.3300
C18···H7^x	3.0100	H21···H17^vi	2.2100
C18···H9	2.9200	H21···C17^vi	2.9900
C19···H6^x	3.0600	H22A···O2^v	2.8500
C19···H7^x	3.0800	H22A···H17	2.3400
C20···H1^iv	2.8700	H22B···C10^vi	3.0500
C20···H7^x	3.1000	H22C···H5^viii	2.5300
C21···H17^vi	2.9900	H22C···N6^vi	2.8100
C21···H5^viii	2.9000	H22C···C5^viii	3.0900
C21···H7^x	3.0600	H22D···O1^vi	2.8900
C21···H1^iv	2.9200	H22D···H21	2.3300
H1···H5^i	2.0700	H22E···N6^vi	2.8400
H1···C21^vii	2.9200	H22F···C12^x	2.9400
H1···C20^vii	2.8700	H22F···H13^x	2.5400
H1···C5^i	2.6600	H22F···C13^x	2.9300
H1O···H19	2.3700	H22F···H12^x	2.5800
C18—O1—H1O	113.8 (14)	C6—C7—C8	119.76 (17)
C20—O2—H2O	111.0 (14)	C7—C8—C11	121.71 (15)
C6—N1—C10	115.90 (17)	C9—C8—C11	121.75 (16)
C13—N2—C14	116.22 (17)	C7—C8—C9	116.53 (17)
C2—N6—C4	114.86 (19)	C8—C9—C10	119.51 (18)
C17—C16—C22	120.07 (16)	N1—C10—C9	124.27 (18)
C21—C16—C22	120.20 (16)	C8—C11—C12	121.34 (16)
C17—C16—C21	119.72 (16)	C12—C11—C15	116.27 (17)
C16—C17—C18	119.97 (16)	C8—C11—C15	122.37 (16)
O1—C18—C17	117.20 (15)	C11—C12—C13	119.93 (17)
C17—C18—C19	120.39 (16)	N2—C13—C12	123.82 (19)
O1—C18—C19	122.41 (15)	N2—C14—C15	123.83 (18)
C18—C19—C20	119.34 (15)	C11—C15—C14	119.81 (18)
O2—C20—C19	121.99 (16)	N1—C6—H6	118.00
O2—C20—C21	117.62 (16)	C7—C6—H6	118.00
C19—C20—C21	120.39 (16)	C8—C7—H7	120.00
C16—C21—C20	120.18 (17)	C6—C7—H7	120.00
C18—C17—H17	120.00	C8—C9—H9	120.00
C16—C17—H17	120.00	C10—C9—H9	120.00
C18—C19—H19	120.00	C9—C10—H10	118.00
C20—C19—H19	120.00	N1—C10—H10	118.00
C16—C21—H21	120.00	C11—C12—H12	120.00
C20—C21—H21	120.00	C13—C12—H12	120.00
C16—C22—H22C	109.00	C12—C13—H13	118.00
C16—C22—H22E	109.00	N2—C13—H13	118.00
C16—C22—H22F	110.00	N2—C14—H14	118.00
C16—C22—H22D	109.00	C15—C14—H14	118.00
C16—C22—H22A	109.00	C11—C15—H15	120.00
C16—C22—H22B	109.00	C14—C15—H15	120.00
H22A—C22—H22E	56.00	C2—C1—C23	120.03 (18)
H22A—C22—H22F	56.00	N6—C2—C1	124.9 (2)
H22B—C22—H22C	109.00	N6—C4—C5	124.94 (19)
H22B—C22—H22D	56.00	C4—C5—C23	120.07 (18)
H22B—C22—H22E	141.00	C1—C23—C5	115.22 (16)
H22B—C22—H22F	56.00	C1—C23—C23^i	122.58 (15)
H22C—C22—H22D	56.00	C5—C23—C23^i	122.20 (16)
H22C—C22—H22E	56.00	C2—C1—H1	120.00
H22C—C22—H22F	141.00	C23—C1—H1	120.00
H22D—C22—H22E	109.00	N6—C2—H2	118.00
H22D—C22—H22F	109.00	C1—C2—H2	118.00
H22E—C22—H22F	109.00	N6—C4—H4	118.00
H22A—C22—H22B	109.00	C5—C4—H4	117.00
H22A—C22—H22C	109.00	C4—C5—H5	120.00
H22A—C22—H22D	141.00	C23—C5—H5	120.00
N1—C6—C7	123.97 (18)
C6—N1—C10—C9	2.7 (3)	C7—C8—C11—C15	−158.7 (2)
C10—N1—C6—C7	−2.3 (3)	C11—C8—C9—C10	177.3 (2)
C13—N2—C14—C15	3.6 (3)	C7—C8—C9—C10	−1.6 (3)
C14—N2—C13—C12	−2.9 (3)	C9—C8—C11—C12	−155.8 (2)
C2—N6—C4—C5	−0.2 (4)	C9—C8—C11—C15	22.5 (3)
C4—N6—C2—C1	0.4 (4)	C8—C9—C10—N1	−0.8 (4)
C17—C16—C21—C20	−0.8 (3)	C15—C11—C12—C13	2.4 (3)
C22—C16—C21—C20	−179.92 (16)	C8—C11—C15—C14	179.9 (2)
C22—C16—C17—C18	179.39 (16)	C8—C11—C12—C13	−179.3 (2)
C21—C16—C17—C18	0.2 (2)	C12—C11—C15—C14	−1.8 (3)
C16—C17—C18—O1	179.78 (15)	C11—C12—C13—N2	0.0 (4)
C16—C17—C18—C19	0.5 (2)	N2—C14—C15—C11	−1.3 (4)
C17—C18—C19—C20	−0.6 (2)	C2—C1—C23—C23^i	−179.9 (2)
O1—C18—C19—C20	−179.91 (15)	C23—C1—C2—N6	−0.1 (4)
C18—C19—C20—O2	179.51 (15)	C2—C1—C23—C5	−0.3 (3)
C18—C19—C20—C21	0.1 (2)	N6—C4—C5—C23	−0.2 (4)
C19—C20—C21—C16	0.6 (3)	C4—C5—C23—C1	0.5 (3)
O2—C20—C21—C16	−178.84 (16)	C4—C5—C23—C23^i	−180.0 (2)
N1—C6—C7—C8	0.0 (3)	C1—C23—C23^i—C1^i	−180.0 (2)
C6—C7—C8—C9	1.9 (3)	C1—C23—C23^i—C5^i	−0.5 (3)
C6—C7—C8—C11	−176.97 (19)	C5—C23—C23^i—C1^i	0.5 (3)
C7—C8—C11—C12	23.1 (3)	C5—C23—C23^i—C5^i	180.0 (2)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+1, −y+1, −z; (iv) −x+3/2, y+1/2, −z+1/2; (v) −x+1/2, y−1/2, −z+1/2; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x+3/2, y−1/2, −z+1/2; (viii) x−1/2, −y+3/2, z+1/2; (ix) x+1/2, −y+3/2, z+1/2; (x) x−1/2, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2^ii	1.00 (3)	1.76 (3)	2.755 (2)	175 (2)
O2—H2O···N1^iv	0.95 (3)	1.80 (3)	2.745 (2)	172 (2)

Symmetry codes: (ii) x+1/2, −y+3/2, z−1/2; (iv) −x+3/2, y+1/2, −z+1/2.

(III_296K)

Crystal data

1.5(C10H8N2)·1(C7H8O2)	F(000) = 756
Mr = 358.42	Dx = 1.258 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2861 reflections
a = 9.1938 (4) Å	θ = 2.7–30.2°
b = 12.3828 (6) Å	µ = 0.08 mm^−1
c = 16.7311 (8) Å	T = 296 K
β = 96.358 (4)°	Block, colourless
V = 1893.04 (15) Å^3	0.5 × 0.3 × 0.2 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	4129 independent reflections
Radiation source: Mova (Mo) X-ray Source	2341 reflections with I > 2σ(I)
mirror	Rint = 0.048
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.0°, θmin = 2.7°
ω scans	h = −11→11
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −15→15
Tmin = 0.998, Tmax = 0.999	l = −21→21
13235 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.065	WHERE P = (FO^2 + 2FC^2)/3
wR(F^2) = 0.220	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 0.23 e Å^−3
4129 reflections	Δρmin = −0.18 e Å^−3
253 parameters	Extinction correction: SHELXL, FC^*=KFC[1+0.001XFC^2Λ^3/SIN(2Θ)]^-1/4
0 restraints	Extinction coefficient: 0.016 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.45109 (17)	0.71149 (12)	0.17397 (10)	0.0762 (6)
O2	0.46065 (18)	1.09890 (12)	0.18877 (11)	0.0819 (7)
C16	0.1993 (2)	0.90333 (16)	0.24775 (11)	0.0575 (7)
C17	0.2632 (2)	0.80765 (17)	0.22714 (12)	0.0583 (7)
C18	0.3935 (2)	0.80885 (16)	0.19251 (11)	0.0549 (7)
C19	0.4610 (2)	0.90561 (16)	0.17883 (11)	0.0558 (7)
C20	0.3977 (2)	1.00087 (17)	0.19962 (12)	0.0583 (7)
C21	0.2664 (2)	0.99994 (17)	0.23374 (12)	0.0624 (8)
C22	0.0569 (2)	0.9022 (2)	0.28537 (16)	0.0830 (10)
N1	0.7869 (2)	0.59454 (16)	0.38639 (13)	0.0812 (8)
N2	0.1787 (2)	0.76328 (18)	0.58013 (12)	0.0797 (8)
C6	0.7824 (3)	0.5849 (2)	0.46469 (16)	0.0915 (10)
C7	0.6665 (2)	0.6144 (2)	0.50384 (15)	0.0840 (9)
C8	0.5437 (2)	0.65788 (17)	0.46201 (12)	0.0611 (7)
C9	0.5463 (2)	0.6652 (3)	0.38001 (15)	0.0939 (12)
C10	0.6679 (3)	0.6333 (3)	0.34594 (15)	0.0999 (12)
C11	0.4167 (2)	0.69450 (17)	0.50194 (12)	0.0603 (7)
C12	0.4301 (3)	0.7191 (3)	0.58289 (15)	0.1007 (12)
C13	0.3103 (3)	0.7521 (3)	0.61822 (17)	0.1095 (13)
C14	0.1674 (3)	0.7448 (2)	0.50231 (16)	0.0884 (10)
C15	0.2803 (2)	0.7099 (2)	0.46229 (15)	0.0864 (9)
N6	0.6706 (2)	0.4110 (2)	0.07100 (15)	0.1013 (10)
C1	0.9193 (3)	0.4631 (3)	0.09482 (15)	0.1085 (12)
C2	0.7900 (3)	0.4284 (3)	0.11893 (19)	0.1237 (16)
C4	0.6820 (3)	0.4279 (3)	−0.00456 (17)	0.1050 (13)
C5	0.8065 (2)	0.4625 (3)	−0.03468 (14)	0.0915 (12)
C23	0.9313 (2)	0.48152 (17)	0.01493 (12)	0.0610 (7)
H1O	0.537 (3)	0.720 (2)	0.138 (2)	0.137 (11)*
H2O	0.556 (4)	1.091 (3)	0.160 (2)	0.161 (14)*
H17	0.21860	0.74220	0.23660	0.0700*
H19	0.54850	0.90650	0.15580	0.0670*
H21	0.22380	1.06470	0.24710	0.0750*
H22A	0.02550	0.82900	0.29110	0.1240*	0.500
H22B	−0.01640	0.94110	0.25160	0.1240*	0.500
H22C	0.07130	0.93590	0.33730	0.1240*	0.500
H22D	0.02810	0.97500	0.29560	0.1240*	0.500
H22E	0.07000	0.86290	0.33510	0.1240*	0.500
H22F	−0.01770	0.86810	0.24930	0.1240*	0.500
H6	0.86400	0.55590	0.49510	0.1100*
H7	0.67060	0.60500	0.55920	0.1010*
H9	0.46540	0.69190	0.34780	0.1130*
H10	0.66610	0.63950	0.29040	0.1200*
H12	0.52060	0.71330	0.61350	0.1210*
H13	0.32310	0.76760	0.67290	0.1310*
H14	0.07710	0.75630	0.47270	0.1060*
H15	0.26410	0.69650	0.40730	0.1040*
H1	0.99970	0.47430	0.13280	0.1300*
H2	0.78700	0.41640	0.17360	0.1490*
H4	0.59960	0.41550	−0.04090	0.1260*
H5	0.80570	0.47320	−0.08970	0.1100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0762 (10)	0.0645 (10)	0.0943 (12)	0.0035 (8)	0.0382 (9)	−0.0015 (8)
O2	0.0777 (11)	0.0669 (11)	0.1070 (14)	−0.0113 (8)	0.0369 (10)	−0.0042 (8)
C16	0.0508 (11)	0.0733 (14)	0.0510 (11)	−0.0026 (9)	0.0171 (9)	−0.0029 (9)
C17	0.0555 (11)	0.0649 (13)	0.0570 (11)	−0.0032 (10)	0.0178 (9)	0.0043 (9)
C18	0.0547 (11)	0.0630 (13)	0.0485 (10)	−0.0008 (9)	0.0121 (8)	0.0010 (9)
C19	0.0493 (11)	0.0706 (14)	0.0501 (10)	−0.0005 (9)	0.0174 (8)	0.0009 (9)
C20	0.0563 (11)	0.0638 (13)	0.0563 (11)	−0.0080 (10)	0.0130 (9)	0.0003 (10)
C21	0.0590 (12)	0.0663 (14)	0.0647 (13)	0.0020 (10)	0.0198 (9)	−0.0056 (10)
C22	0.0639 (14)	0.099 (2)	0.0924 (18)	−0.0031 (12)	0.0374 (13)	−0.0024 (13)
N1	0.0678 (12)	0.0969 (15)	0.0822 (14)	0.0136 (10)	0.0230 (11)	−0.0072 (11)
N2	0.0632 (12)	0.0932 (15)	0.0880 (15)	0.0102 (10)	0.0321 (11)	0.0130 (12)
C6	0.0738 (16)	0.127 (2)	0.0757 (16)	0.0328 (15)	0.0176 (13)	0.0059 (15)
C7	0.0660 (14)	0.125 (2)	0.0624 (14)	0.0245 (14)	0.0129 (11)	0.0072 (13)
C8	0.0514 (11)	0.0740 (13)	0.0590 (12)	−0.0050 (10)	0.0117 (9)	−0.0005 (10)
C9	0.0622 (14)	0.156 (3)	0.0652 (15)	0.0205 (15)	0.0143 (11)	0.0068 (15)
C10	0.0763 (16)	0.164 (3)	0.0626 (15)	0.0227 (18)	0.0223 (13)	0.0016 (15)
C11	0.0506 (11)	0.0723 (14)	0.0600 (12)	0.0011 (10)	0.0150 (9)	0.0055 (10)
C12	0.0651 (14)	0.173 (3)	0.0653 (15)	0.0259 (16)	0.0128 (11)	−0.0010 (16)
C13	0.0783 (17)	0.183 (3)	0.0717 (16)	0.0291 (19)	0.0291 (14)	0.0018 (19)
C14	0.0566 (13)	0.122 (2)	0.0885 (18)	0.0120 (13)	0.0171 (12)	0.0078 (16)
C15	0.0571 (14)	0.135 (2)	0.0686 (14)	0.0140 (14)	0.0134 (11)	−0.0024 (14)
N6	0.0699 (14)	0.144 (2)	0.0952 (17)	−0.0139 (12)	0.0321 (13)	0.0069 (14)
C1	0.0631 (14)	0.200 (3)	0.0630 (15)	−0.0214 (18)	0.0102 (12)	0.0178 (18)
C2	0.0732 (18)	0.225 (4)	0.0760 (18)	−0.019 (2)	0.0224 (15)	0.030 (2)
C4	0.0661 (15)	0.170 (3)	0.0812 (18)	−0.0315 (16)	0.0185 (13)	−0.0123 (18)
C5	0.0666 (14)	0.149 (3)	0.0603 (14)	−0.0237 (15)	0.0139 (11)	−0.0054 (15)
C23	0.0532 (11)	0.0752 (14)	0.0567 (12)	−0.0001 (10)	0.0153 (9)	−0.0005 (10)

Geometric parameters (Å, °)

O1—C18	1.366 (2)	C6—C7	1.361 (3)
O2—C20	1.366 (3)	C7—C8	1.371 (3)
O1—H1O	1.05 (3)	C8—C11	1.479 (3)
O2—H2O	1.05 (4)	C8—C9	1.378 (3)
N1—C6	1.321 (3)	C9—C10	1.368 (4)
N1—C10	1.312 (3)	C11—C15	1.366 (3)
N2—C13	1.311 (3)	C11—C12	1.380 (3)
N2—C14	1.315 (3)	C12—C13	1.369 (4)
N6—C4	1.297 (4)	C14—C15	1.366 (3)
N6—C2	1.304 (4)	C6—H6	0.9300
C16—C21	1.378 (3)	C7—H7	0.9300
C16—C22	1.514 (3)	C9—H9	0.9300
C16—C17	1.383 (3)	C10—H10	0.9300
C17—C18	1.387 (3)	C12—H12	0.9300
C18—C19	1.380 (3)	C13—H13	0.9300
C19—C20	1.377 (3)	C14—H14	0.9300
C20—C21	1.391 (3)	C15—H15	0.9300
C17—H17	0.9300	C1—C2	1.366 (4)
C19—H19	0.9300	C1—C23	1.372 (3)
C21—H21	0.9300	C4—C5	1.370 (4)
C22—H22D	0.9600	C5—C23	1.360 (3)
C22—H22E	0.9600	C23—C23^i	1.481 (3)
C22—H22B	0.9600	C1—H1	0.9300
C22—H22C	0.9600	C2—H2	0.9300
C22—H22A	0.9600	C4—H4	0.9300
C22—H22F	0.9600	C5—H5	0.9300
O1···N2^ii	2.769 (2)	H1O···H4^iv	2.5700
O2···N1^iii	2.760 (3)	H1O···H19	2.3300
O1···H9	2.9100	H1O···C14^ii	2.72 (3)
O1···H4^iv	2.7200	H2O···N1^iii	1.71 (4)
O1···H10	2.7600	H2O···C6^iii	2.69 (3)
O1···H21^v	2.8500	H2O···H19	2.2900
O2···H15^vi	2.7500	H2O···C10^iii	2.61 (4)
O2···H17^vi	2.8100	H4···H1O^iv	2.5700
O2···H22A^vi	2.8700	H4···O1^iv	2.7200
N1···O2^vii	2.760 (3)	H5···C1^i	2.6600
N2···O1^viii	2.769 (2)	H5···C21^ii	2.9500
N2···C19^viii	3.441 (3)	H5···H1^i	2.1000
N6···C22^v	3.358 (3)	H7···C18^ix	3.0500
N1···H2O^vii	1.71 (4)	H7···H12	2.1900
N1···H19^vii	2.9100	H7···C17^ix	3.0400
N2···H19^viii	2.7900	H7···C12	2.6900
N2···H1O^viii	1.72 (3)	H9···C15	2.7100
N6···H22E^v	2.9100	H9···C17	2.9600
N6···H22C^v	2.8500	H9···O1	2.9100
C2···C9^vii	3.589 (5)	H9···H15	2.2000
C9···C2^iii	3.589 (5)	H9···C18	2.9800
C19···N2^ii	3.441 (3)	H10···O1	2.7600
C22···N6^vi	3.358 (3)	H12···C16^ix	3.0000
C1···H5^i	2.6600	H12···C7	2.6900
C5···H1^i	2.6700	H12···H7	2.1900
C6···H2O^vii	2.69 (3)	H12···H22F^ix	2.5500
C7···H12	2.6900	H12···C17^ix	2.7800
C9···H15	2.7100	H13···H22F^ix	2.4900
C10···H2O^vii	2.61 (4)	H15···O2^v	2.7500
C12···H7	2.6900	H15···H9	2.2000
C12···H22F^ix	2.9800	H15···C9	2.7100
C13···H1O^viii	2.59 (3)	H17···O2^v	2.8100
C13···H22F^ix	2.9600	H17···C21^v	3.0400
C14···H1O^viii	2.72 (3)	H17···H21^v	2.2700
C15···H9	2.7100	H17···H22A	2.3400
C16···H12^x	3.0000	H19···N2^ii	2.7900
C17···H21^v	3.0400	H19···H1O	2.3300
C17···H12^x	2.7800	H19···H2O	2.2900
C17···H7^x	3.0400	H19···N1^iii	2.9100
C17···H9	2.9600	H21···H17^vi	2.2700
C18···H7^x	3.0500	H21···O1^vi	2.8500
C18···H9	2.9800	H21···C17^vi	3.0400
C20···H1^iii	2.8800	H21···H22D	2.3400
C21···H17^vi	3.0400	H22A···O2^v	2.8700
C21···H5^viii	2.9500	H22A···H17	2.3400
C21···H1^iii	2.9400	H22C···N6^vi	2.8500
H1···C20^vii	2.8800	H22D···H21	2.3400
H1···C5^i	2.6700	H22E···N6^vi	2.9100
H1···H5^i	2.1000	H22F···H13^x	2.4900
H1···C21^vii	2.9400	H22F···C12^x	2.9800
H1O···N2^ii	1.72 (3)	H22F···C13^x	2.9600
H1O···C13^ii	2.59 (3)	H22F···H12^x	2.5500
C18—O1—H1O	112.1 (14)	C6—C7—C8	120.3 (2)
C20—O2—H2O	111 (2)	C7—C8—C11	122.44 (19)
C6—N1—C10	115.4 (2)	C9—C8—C11	122.09 (18)
C13—N2—C14	115.5 (2)	C7—C8—C9	115.47 (19)
C2—N6—C4	114.8 (2)	C8—C9—C10	120.1 (2)
C17—C16—C22	120.43 (18)	N1—C10—C9	124.3 (2)
C21—C16—C22	120.18 (18)	C8—C11—C12	121.44 (19)
C17—C16—C21	119.39 (17)	C12—C11—C15	115.0 (2)
C16—C17—C18	120.35 (19)	C8—C11—C15	123.49 (19)
O1—C18—C17	117.37 (18)	C11—C12—C13	120.1 (2)
C17—C18—C19	120.23 (18)	N2—C13—C12	124.4 (3)
O1—C18—C19	122.40 (17)	N2—C14—C15	124.0 (2)
C18—C19—C20	119.44 (17)	C11—C15—C14	120.9 (2)
O2—C20—C19	122.06 (17)	N1—C6—H6	118.00
O2—C20—C21	117.49 (18)	C7—C6—H6	118.00
C19—C20—C21	120.45 (19)	C8—C7—H7	120.00
C16—C21—C20	120.14 (19)	C6—C7—H7	120.00
C18—C17—H17	120.00	C8—C9—H9	120.00
C16—C17—H17	120.00	C10—C9—H9	120.00
C18—C19—H19	120.00	C9—C10—H10	118.00
C20—C19—H19	120.00	N1—C10—H10	118.00
C16—C21—H21	120.00	C11—C12—H12	120.00
C20—C21—H21	120.00	C13—C12—H12	120.00
C16—C22—H22C	109.00	C12—C13—H13	118.00
C16—C22—H22E	109.00	N2—C13—H13	118.00
C16—C22—H22F	109.00	N2—C14—H14	118.00
C16—C22—H22D	109.00	C15—C14—H14	118.00
C16—C22—H22A	110.00	C11—C15—H15	120.00
C16—C22—H22B	109.00	C14—C15—H15	120.00
H22A—C22—H22E	56.00	C2—C1—C23	120.4 (2)
H22A—C22—H22F	56.00	N6—C2—C1	124.8 (3)
H22B—C22—H22C	109.00	N6—C4—C5	124.8 (3)
H22B—C22—H22D	56.00	C4—C5—C23	120.8 (2)
H22B—C22—H22E	141.00	C1—C23—C5	114.3 (2)
H22B—C22—H22F	56.00	C1—C23—C23^i	122.9 (2)
H22C—C22—H22D	56.00	C5—C23—C23^i	122.75 (19)
H22C—C22—H22E	56.00	C2—C1—H1	120.00
H22C—C22—H22F	141.00	C23—C1—H1	120.00
H22D—C22—H22E	109.00	N6—C2—H2	118.00
H22D—C22—H22F	109.00	C1—C2—H2	118.00
H22E—C22—H22F	110.00	N6—C4—H4	118.00
H22A—C22—H22B	109.00	C5—C4—H4	118.00
H22A—C22—H22C	109.00	C4—C5—H5	120.00
H22A—C22—H22D	141.00	C23—C5—H5	120.00
N1—C6—C7	124.4 (2)
C6—N1—C10—C9	1.6 (5)	C7—C8—C11—C15	−161.4 (2)
C10—N1—C6—C7	−1.6 (4)	C11—C8—C9—C10	178.0 (3)
C13—N2—C14—C15	3.8 (4)	C7—C8—C9—C10	−2.0 (4)
C14—N2—C13—C12	−2.8 (5)	C9—C8—C11—C12	−159.2 (3)
C2—N6—C4—C5	−0.7 (5)	C9—C8—C11—C15	18.6 (4)
C4—N6—C2—C1	0.9 (5)	C8—C9—C10—N1	0.2 (5)
C17—C16—C21—C20	−0.4 (3)	C15—C11—C12—C13	2.4 (4)
C22—C16—C21—C20	179.61 (19)	C8—C11—C15—C14	−179.4 (2)
C22—C16—C17—C18	179.86 (19)	C8—C11—C12—C13	−179.6 (3)
C21—C16—C17—C18	−0.1 (3)	C12—C11—C15—C14	−1.4 (4)
C16—C17—C18—O1	179.69 (17)	C11—C12—C13—N2	−0.4 (6)
C16—C17—C18—C19	0.4 (3)	N2—C14—C15—C11	−1.8 (4)
C17—C18—C19—C20	−0.2 (3)	C2—C1—C23—C23^i	−179.6 (3)
O1—C18—C19—C20	−179.41 (18)	C23—C1—C2—N6	−0.6 (6)
C18—C19—C20—O2	178.88 (18)	C2—C1—C23—C5	0.1 (5)
C18—C19—C20—C21	−0.4 (3)	N6—C4—C5—C23	0.4 (6)
C19—C20—C21—C16	0.7 (3)	C4—C5—C23—C1	0.0 (5)
O2—C20—C21—C16	−178.62 (18)	C4—C5—C23—C23^i	179.7 (3)
N1—C6—C7—C8	−0.3 (4)	C1—C23—C23^i—C1^i	180.0 (3)
C6—C7—C8—C9	2.1 (4)	C1—C23—C23^i—C5^i	−0.3 (4)
C6—C7—C8—C11	−178.0 (2)	C5—C23—C23^i—C1^i	0.3 (4)
C7—C8—C11—C12	20.8 (4)	C5—C23—C23^i—C5^i	180.0 (3)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1, −y+1, −z; (v) −x+1/2, y−1/2, −z+1/2; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x+3/2, y−1/2, −z+1/2; (viii) x−1/2, −y+3/2, z+1/2; (ix) x+1/2, −y+3/2, z+1/2; (x) x−1/2, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2^ii	1.05 (3)	1.72 (3)	2.769 (2)	179 (3)
O2—H2O···N1^iii	1.05 (4)	1.71 (4)	2.760 (3)	173 (3)

Symmetry codes: (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2.

(IV)

Crystal data

4.5(C10H8N2)·3(C7H8O2)	F(000) = 2268
Mr = 1075.26	Dx = 1.307 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10997 reflections
a = 9.2118 (2) Å	θ = 2.4–27.4°
b = 36.2075 (7) Å	µ = 0.09 mm^−1
c = 16.5458 (4) Å	T = 100 K
β = 97.923 (2)°	Block, colourless
V = 5465.9 (2) Å^3	0.5 × 0.3 × 0.2 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	11929 independent reflections
Radiation source: Mova (Mo) X-ray Source	9034 reflections with I > 2σ(I)
mirror	Rint = 0.047
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.0°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −46→46
Tmin = 0.998, Tmax = 0.999	l = −21→21
49594 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.050	Secondary atom site location: difference Fourier map
wR(F^2) = 0.121	Hydrogen site location: inferred from neighbouring sites
S = 1.01	H atoms treated by a mixture of independent and constrained refinement
11990 reflections	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 1.4988P] where P = (Fo^2 + 2Fc^2)/3
970 parameters	(Δ/σ)max = 0.001

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	1.23717 (15)	0.29143 (4)	0.84631 (10)	0.0269 (5)
N2	0.61536 (15)	0.24545 (4)	1.03680 (10)	0.0254 (5)
C1	0.60395 (18)	0.25070 (5)	0.95622 (12)	0.0262 (6)
C2	0.72130 (18)	0.25929 (5)	0.91563 (11)	0.0243 (6)
C3	0.7499 (2)	0.24816 (6)	1.07825 (12)	0.0337 (7)
C4	0.87276 (18)	0.25702 (5)	1.04320 (11)	0.0293 (7)
C5	0.85967 (17)	0.26304 (4)	0.95985 (11)	0.0197 (5)
C6	0.98988 (17)	0.27308 (5)	0.92034 (11)	0.0197 (5)
C7	1.00450 (18)	0.26091 (5)	0.84220 (11)	0.0271 (6)
C8	1.10244 (18)	0.29499 (5)	0.96020 (11)	0.0242 (6)
C9	1.1284 (2)	0.27040 (6)	0.80875 (12)	0.0327 (7)
C10	1.22164 (18)	0.30323 (5)	0.92130 (12)	0.0263 (6)
N3	0.80629 (15)	0.08415 (4)	0.40822 (9)	0.0246 (5)
N4	0.18536 (15)	0.13011 (4)	0.60075 (9)	0.0252 (5)
C18	0.29591 (19)	0.10969 (5)	0.63888 (11)	0.0260 (6)
C19	0.41911 (17)	0.10027 (5)	0.60458 (11)	0.0231 (6)
C20	0.43270 (17)	0.11214 (5)	0.52609 (11)	0.0201 (6)
C21	0.31893 (18)	0.13366 (5)	0.48639 (11)	0.0250 (6)
C22	0.19984 (19)	0.14173 (5)	0.52526 (12)	0.0272 (6)
C23	0.56186 (17)	0.10192 (5)	0.48583 (11)	0.0203 (6)
C24	0.69651 (18)	0.09288 (5)	0.53020 (11)	0.0242 (6)
C25	0.81351 (18)	0.08437 (5)	0.48952 (11)	0.0258 (6)
C26	0.55324 (18)	0.10129 (5)	0.40123 (11)	0.0261 (6)
C27	0.67556 (19)	0.09243 (5)	0.36575 (11)	0.0290 (6)
N5	0.16225 (15)	0.02372 (4)	0.57068 (10)	0.0311 (6)
C28	0.18140 (19)	0.02715 (6)	0.49255 (12)	0.0324 (7)
C29	0.31076 (19)	0.01862 (5)	0.46303 (11)	0.0290 (6)
C30	0.42946 (17)	0.00512 (4)	0.51474 (10)	0.0188 (5)
C31	0.41032 (18)	0.00138 (5)	0.59620 (11)	0.0303 (7)
C32	0.2773 (2)	0.01083 (6)	0.61996 (12)	0.0348 (7)
N6	0.78414 (15)	0.31788 (4)	0.38686 (10)	0.0316 (5)
N7	0.12365 (15)	0.35865 (4)	0.54726 (10)	0.0291 (5)
C40	0.2530 (2)	0.35779 (5)	0.59507 (11)	0.0285 (6)
C41	0.38498 (18)	0.35020 (5)	0.56793 (11)	0.0242 (6)
C42	0.38652 (17)	0.34286 (4)	0.48534 (11)	0.0196 (6)
C43	0.25293 (18)	0.34352 (5)	0.43518 (11)	0.0234 (6)
C44	0.12657 (18)	0.35142 (5)	0.46825 (12)	0.0271 (6)
C45	0.52465 (17)	0.33444 (5)	0.45200 (11)	0.0205 (6)
C46	0.64236 (18)	0.31679 (5)	0.49823 (11)	0.0233 (6)
C47	0.76757 (18)	0.30949 (5)	0.46394 (12)	0.0287 (6)
C48	0.67069 (19)	0.33492 (5)	0.34288 (12)	0.0297 (6)
C49	0.54171 (18)	0.34369 (5)	0.37202 (11)	0.0243 (6)
N8	1.31074 (14)	0.07673 (4)	−0.08233 (9)	0.0247 (5)
N9	0.68766 (15)	0.04247 (4)	0.11643 (9)	0.0258 (5)
C57	0.79925 (18)	0.04874 (5)	−0.00553 (11)	0.0259 (6)
C58	0.93694 (17)	0.05419 (4)	0.03914 (11)	0.0195 (5)
C59	0.94599 (17)	0.05305 (5)	0.12376 (11)	0.0228 (6)
C60	0.82074 (19)	0.04722 (5)	0.15886 (11)	0.0250 (6)
C61	1.06729 (17)	0.06157 (4)	−0.00220 (11)	0.0191 (5)
C62	1.18677 (18)	0.08149 (5)	0.03555 (11)	0.0228 (6)
C63	1.30463 (18)	0.08835 (5)	−0.00575 (11)	0.0246 (6)
C64	1.07385 (17)	0.04927 (5)	−0.08140 (11)	0.0235 (6)
C65	1.19558 (18)	0.05740 (5)	−0.11793 (11)	0.0273 (6)
C66	0.67961 (18)	0.04335 (5)	0.03480 (12)	0.0285 (6)
O1	0.52602 (12)	0.09008 (3)	0.82055 (7)	0.0262 (4)
O2	0.55801 (12)	−0.04257 (3)	0.80841 (8)	0.0285 (4)
C11	0.92827 (18)	0.03260 (5)	0.70416 (11)	0.0248 (6)
C12	0.61001 (17)	−0.00800 (5)	0.79655 (11)	0.0197 (5)
C13	0.53712 (16)	0.02351 (5)	0.81709 (10)	0.0181 (5)
C14	0.59297 (17)	0.05812 (5)	0.80199 (10)	0.0184 (5)
C15	0.72134 (17)	0.06119 (4)	0.76672 (10)	0.0198 (5)
C16	0.79291 (17)	0.02964 (5)	0.74505 (10)	0.0184 (5)
C17	0.73716 (17)	−0.00498 (5)	0.76030 (10)	0.0193 (5)
O3	1.43165 (11)	0.37077 (3)	0.16913 (8)	0.0252 (4)
O4	1.38605 (12)	0.23928 (3)	0.12729 (8)	0.0246 (4)
C33	0.99783 (18)	0.30697 (5)	0.23529 (11)	0.0262 (6)
C34	1.20181 (17)	0.27317 (4)	0.17999 (10)	0.0185 (5)
C35	1.14423 (17)	0.30627 (5)	0.20435 (10)	0.0189 (5)
C36	1.22224 (18)	0.33883 (5)	0.19840 (11)	0.0212 (6)
C37	1.35739 (17)	0.33817 (5)	0.16979 (11)	0.0193 (5)
C38	1.41435 (17)	0.30516 (4)	0.14449 (10)	0.0182 (5)
C39	1.33569 (17)	0.27269 (4)	0.14974 (10)	0.0180 (5)
O5	−0.01628 (12)	0.20676 (3)	0.27021 (8)	0.0245 (4)
O6	0.03955 (12)	0.07623 (3)	0.32396 (7)	0.0239 (4)
C50	0.41503 (18)	0.14274 (5)	0.20178 (11)	0.0250 (6)
C51	0.08603 (17)	0.10925 (4)	0.29683 (10)	0.0186 (5)
C52	0.21742 (17)	0.10937 (4)	0.26402 (10)	0.0183 (5)
C53	0.27144 (17)	0.14211 (5)	0.23578 (10)	0.0181 (5)
C54	0.19231 (17)	0.17463 (5)	0.23984 (11)	0.0200 (5)
C55	0.05944 (17)	0.17436 (5)	0.27076 (11)	0.0190 (5)
C56	0.00592 (16)	0.14167 (5)	0.30020 (10)	0.0182 (5)
H1	0.49426	0.24922	0.92301	0.0386
H2	0.70072	0.26330	0.85019	0.0383
H3	0.75912	0.24153	1.14258	0.0397
H4	0.97837	0.25701	1.08118	0.0394
H7	0.92389	0.24333	0.80722	0.0380
H8	1.09539	0.30597	1.02042	0.0391
H9	1.14086	0.26058	0.74826	0.0378
H10	1.30917	0.31995	0.95281	0.0388
H18	0.28407	0.10000	0.69955	0.0377
H19	0.50080	0.08285	0.63915	0.0375
H21	0.32015	0.14419	0.42522	0.0373
H22	0.11069	0.15848	0.49554	0.0375
H24	0.71228	0.09178	0.59624	0.0374
H25	0.91728	0.07695	0.52482	0.0373
H26	0.45295	0.10747	0.36124	0.0371
H27	0.66729	0.09166	0.29984	0.0370
H28	0.09050	0.03876	0.45200	0.0374
H29	0.31486	0.02230	0.39843	0.0372
H31	0.49682	−0.00826	0.64239	0.0377
H32	0.26408	0.00950	0.68394	0.0378
H40	0.25262	0.36375	0.65917	0.0384
H41	0.48390	0.35015	0.61169	0.0380
H43	0.24672	0.33812	0.37042	0.0380
H44	0.02115	0.35235	0.43015	0.0384
H46	0.63478	0.30776	0.55990	0.0376
H47	0.85766	0.29575	0.50104	0.0373
H48	0.68327	0.34191	0.28058	0.0375
H49	0.45528	0.35728	0.33178	0.0379
H57	0.78044	0.04994	−0.07155	0.0373
H59	1.04941	0.05613	0.16310	0.0369
H60	0.82731	0.04585	0.22465	0.0370
H62	1.18841	0.09179	0.09712	0.0368
H63	1.39620	0.10470	0.02259	0.0369
H64	0.98542	0.03368	−0.11545	0.0373
H65	1.20294	0.04849	−0.17971	0.0373
H66	0.57055	0.04038	0.00142	0.0373
H1O	0.45104	0.08510	0.85682	0.0350
H2O	0.47073	−0.04086	0.83727	0.0353
H11A	1.01154	0.01303	0.72773	0.0442
H11B	0.90792	0.02830	0.63917	0.0437
H11C	0.97827	0.05951	0.71079	0.0439
H13	0.43889	0.02036	0.84564	0.0384
H15	0.76812	0.08794	0.75650	0.0379
H17	0.79283	−0.02952	0.74320	0.0383
H3O	1.52238	0.36762	0.14378	0.0337
H4O	1.46767	0.24216	0.09445	0.0335
H33A	0.96680	0.28052	0.25725	0.0431
H33B	0.90872	0.31270	0.18764	0.0432
H33C	0.99288	0.32820	0.28043	0.0432
H34	1.14408	0.24742	0.18535	0.0369
H36	1.17872	0.36466	0.21773	0.0372
H38	1.51950	0.30460	0.12222	0.0368
H5O	−0.10401	0.20500	0.29869	0.0346
H6O	−0.04615	0.07991	0.35339	0.0342
H50A	0.45030	0.11526	0.18892	0.0432
H50B	0.40629	0.15749	0.14479	0.0433
H50C	0.49940	0.15431	0.24609	0.0431
H52	0.27556	0.08366	0.25889	0.0372
H54	0.23314	0.19982	0.21576	0.0375
H56	−0.09788	0.14235	0.32395	0.0376

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0213 (8)	0.0331 (9)	0.0275 (10)	−0.0018 (7)	0.0076 (8)	0.0027 (8)
N2	0.0230 (8)	0.0267 (9)	0.0288 (10)	−0.0012 (6)	0.0117 (8)	−0.0022 (7)
C1	0.0180 (9)	0.0302 (11)	0.0312 (12)	0.0003 (8)	0.0068 (9)	0.0027 (9)
C2	0.0204 (9)	0.0307 (10)	0.0219 (11)	−0.0007 (8)	0.0030 (9)	0.0039 (9)
C3	0.0307 (11)	0.0522 (14)	0.0201 (11)	−0.0058 (10)	0.0099 (10)	−0.0011 (10)
C4	0.0199 (10)	0.0463 (13)	0.0218 (11)	−0.0057 (9)	0.0038 (9)	−0.0011 (10)
C5	0.0195 (9)	0.0184 (9)	0.0223 (10)	0.0016 (7)	0.0073 (9)	−0.0002 (8)
C6	0.0170 (9)	0.0211 (9)	0.0215 (10)	0.0023 (7)	0.0046 (8)	0.0048 (8)
C7	0.0209 (10)	0.0384 (11)	0.0226 (11)	−0.0048 (8)	0.0049 (9)	−0.0034 (9)
C8	0.0242 (10)	0.0265 (10)	0.0228 (11)	−0.0019 (8)	0.0063 (9)	−0.0027 (9)
C9	0.0265 (10)	0.0490 (13)	0.0244 (12)	−0.0053 (9)	0.0102 (10)	−0.0045 (10)
C10	0.0203 (10)	0.0281 (10)	0.0310 (12)	−0.0039 (8)	0.0058 (9)	−0.0006 (9)
H1	0.0289	0.0499	0.0371	−0.0019	0.0048	0.0004
H2	0.0367	0.0493	0.0295	−0.0014	0.0073	0.0021
H3	0.0388	0.0514	0.0299	−0.0026	0.0084	0.0033
H4	0.0302	0.0522	0.0356	−0.0017	0.0039	0.0008
H7	0.0340	0.0435	0.0371	−0.0073	0.0067	−0.0059
H8	0.0393	0.0479	0.0320	−0.0039	0.0114	−0.0072
H9	0.0379	0.0458	0.0315	−0.0027	0.0110	−0.0061
H10	0.0335	0.0459	0.0376	−0.0080	0.0070	−0.0066
N3	0.0221 (8)	0.0267 (8)	0.0265 (9)	0.0002 (6)	0.0089 (8)	0.0028 (7)
N4	0.0213 (8)	0.0264 (8)	0.0287 (10)	0.0008 (6)	0.0062 (8)	−0.0037 (7)
C18	0.0242 (10)	0.0309 (11)	0.0242 (11)	0.0006 (8)	0.0075 (9)	−0.0006 (9)
C19	0.0185 (9)	0.0273 (10)	0.0235 (11)	0.0013 (7)	0.0031 (9)	0.0004 (8)
C20	0.0183 (9)	0.0192 (9)	0.0234 (11)	−0.0032 (7)	0.0046 (8)	−0.0038 (8)
C21	0.0247 (10)	0.0260 (10)	0.0245 (11)	0.0024 (8)	0.0046 (9)	0.0012 (9)
C22	0.0234 (10)	0.0279 (10)	0.0307 (12)	0.0057 (8)	0.0051 (9)	0.0009 (9)
C23	0.0196 (9)	0.0181 (9)	0.0242 (11)	−0.0014 (7)	0.0064 (9)	−0.0003 (8)
C24	0.0197 (9)	0.0319 (10)	0.0215 (11)	0.0001 (8)	0.0048 (8)	−0.0002 (9)
C25	0.0185 (9)	0.0309 (11)	0.0280 (12)	0.0001 (8)	0.0037 (9)	0.0019 (9)
C26	0.0203 (9)	0.0344 (11)	0.0238 (11)	0.0040 (8)	0.0041 (9)	0.0022 (9)
C27	0.0283 (10)	0.0374 (11)	0.0222 (11)	0.0029 (9)	0.0063 (9)	0.0021 (9)
H18	0.0379	0.0450	0.0322	0.0036	0.0114	0.0062
H19	0.0332	0.0425	0.0374	0.0082	0.0066	0.0064
H21	0.0371	0.0444	0.0318	0.0041	0.0100	0.0064
H22	0.0317	0.0426	0.0388	0.0083	0.0069	0.0056
H24	0.0360	0.0481	0.0289	0.0029	0.0070	0.0014
H25	0.0283	0.0471	0.0361	0.0051	0.0035	0.0023
H26	0.0285	0.0473	0.0352	0.0045	0.0032	0.0018
H27	0.0353	0.0476	0.0289	0.0025	0.0075	0.0001
N5	0.0244 (9)	0.0398 (10)	0.0303 (10)	0.0018 (7)	0.0076 (8)	−0.0025 (8)
C28	0.0222 (10)	0.0471 (13)	0.0274 (12)	0.0098 (9)	0.0022 (9)	0.0003 (10)
C29	0.0258 (10)	0.0411 (12)	0.0207 (11)	0.0047 (9)	0.0054 (9)	0.0005 (9)
C30	0.0188 (9)	0.0162 (9)	0.0222 (10)	−0.0025 (7)	0.0058 (8)	−0.0021 (8)
C31	0.0238 (10)	0.0451 (13)	0.0227 (11)	0.0066 (9)	0.0062 (9)	0.0068 (10)
C32	0.0291 (11)	0.0538 (14)	0.0237 (11)	0.0019 (10)	0.0111 (10)	0.0034 (10)
H28	0.0304	0.0456	0.0362	0.0065	0.0050	0.0045
H29	0.0359	0.0471	0.0302	0.0033	0.0096	0.0030
H31	0.0314	0.0468	0.0350	0.0057	0.0043	0.0047
H32	0.0368	0.0479	0.0304	0.0032	0.0105	0.0022
N6	0.0213 (8)	0.0452 (10)	0.0295 (10)	0.0042 (7)	0.0073 (8)	0.0018 (9)
N7	0.0241 (8)	0.0338 (9)	0.0309 (10)	0.0045 (7)	0.0092 (8)	0.0036 (8)
C40	0.0297 (11)	0.0341 (11)	0.0232 (11)	0.0046 (9)	0.0091 (10)	−0.0003 (9)
C41	0.0211 (9)	0.0284 (10)	0.0232 (11)	0.0034 (8)	0.0036 (9)	0.0010 (9)
C42	0.0198 (9)	0.0164 (9)	0.0239 (11)	0.0012 (7)	0.0079 (9)	0.0023 (8)
C43	0.0204 (9)	0.0271 (10)	0.0232 (11)	−0.0008 (7)	0.0050 (9)	0.0004 (8)
C44	0.0207 (10)	0.0315 (11)	0.0293 (12)	0.0006 (8)	0.0047 (9)	0.0037 (9)
C45	0.0194 (9)	0.0196 (9)	0.0232 (11)	−0.0014 (7)	0.0059 (8)	−0.0013 (8)
C46	0.0228 (9)	0.0257 (10)	0.0223 (10)	0.0031 (8)	0.0068 (9)	0.0049 (8)
C47	0.0213 (10)	0.0357 (11)	0.0299 (12)	0.0071 (8)	0.0065 (9)	0.0056 (10)
C48	0.0244 (10)	0.0431 (12)	0.0230 (11)	−0.0020 (9)	0.0082 (9)	0.0016 (9)
C49	0.0182 (9)	0.0325 (11)	0.0220 (11)	−0.0003 (8)	0.0026 (9)	0.0006 (9)
H40	0.0364	0.0478	0.0325	0.0013	0.0100	−0.0037
H41	0.0294	0.0482	0.0363	0.0015	0.0039	−0.0016
H43	0.0358	0.0477	0.0316	0.0020	0.0082	−0.0024
H44	0.0282	0.0480	0.0390	0.0024	0.0041	−0.0006
H46	0.0371	0.0455	0.0319	0.0033	0.0108	0.0054
H47	0.0312	0.0444	0.0365	0.0070	0.0054	0.0048
H48	0.0369	0.0457	0.0315	0.0036	0.0106	0.0050
H49	0.0318	0.0445	0.0375	0.0072	0.0054	0.0057
N8	0.0190 (8)	0.0285 (8)	0.0277 (9)	−0.0002 (6)	0.0076 (7)	−0.0040 (7)
N9	0.0229 (8)	0.0272 (9)	0.0288 (10)	−0.0031 (6)	0.0085 (8)	0.0020 (8)
C57	0.0210 (9)	0.0354 (11)	0.0211 (11)	−0.0023 (8)	0.0019 (9)	0.0016 (9)
C58	0.0177 (9)	0.0183 (9)	0.0231 (10)	0.0005 (7)	0.0047 (8)	0.0011 (8)
C59	0.0188 (9)	0.0268 (10)	0.0226 (11)	−0.0010 (7)	0.0022 (8)	0.0004 (8)
C60	0.0280 (10)	0.0238 (10)	0.0242 (11)	−0.0009 (8)	0.0072 (9)	0.0034 (8)
C61	0.0163 (9)	0.0195 (9)	0.0218 (10)	0.0020 (7)	0.0037 (8)	0.0008 (8)
C62	0.0211 (9)	0.0258 (10)	0.0219 (11)	−0.0018 (8)	0.0048 (9)	−0.0035 (8)
C63	0.0192 (9)	0.0272 (10)	0.0281 (11)	−0.0031 (7)	0.0062 (9)	−0.0044 (9)
C64	0.0189 (9)	0.0261 (10)	0.0255 (11)	−0.0022 (7)	0.0029 (9)	−0.0056 (9)
C65	0.0240 (10)	0.0341 (11)	0.0248 (11)	0.0007 (8)	0.0073 (9)	−0.0074 (9)
C66	0.0181 (9)	0.0393 (12)	0.0285 (12)	−0.0041 (8)	0.0044 (9)	0.0025 (10)
H57	0.0348	0.0483	0.0293	−0.0027	0.0069	0.0003
H59	0.0272	0.0474	0.0358	−0.0024	0.0032	−0.0006
H60	0.0348	0.0477	0.0294	−0.0013	0.0077	0.0009
H62	0.0364	0.0439	0.0316	−0.0038	0.0095	−0.0063
H63	0.0310	0.0415	0.0386	−0.0086	0.0066	−0.0059
H64	0.0309	0.0433	0.0381	−0.0088	0.0064	−0.0063
H65	0.0367	0.0447	0.0322	−0.0054	0.0109	−0.0068
H66	0.0264	0.0487	0.0366	−0.0026	0.0038	−0.0005
O1	0.0289 (7)	0.0191 (6)	0.0338 (8)	0.0048 (5)	0.0158 (6)	0.0000 (6)
O2	0.0284 (7)	0.0194 (6)	0.0416 (9)	−0.0039 (5)	0.0188 (7)	−0.0027 (6)
C11	0.0221 (9)	0.0252 (10)	0.0289 (11)	0.0005 (8)	0.0096 (9)	0.0030 (9)
C12	0.0183 (9)	0.0200 (9)	0.0212 (10)	−0.0027 (7)	0.0037 (8)	0.0020 (8)
C13	0.0150 (8)	0.0236 (9)	0.0166 (10)	−0.0016 (7)	0.0052 (8)	−0.0010 (8)
C14	0.0196 (9)	0.0196 (9)	0.0163 (10)	0.0040 (7)	0.0035 (8)	0.0001 (8)
C15	0.0212 (9)	0.0195 (9)	0.0194 (10)	−0.0019 (7)	0.0052 (8)	0.0039 (8)
C16	0.0158 (8)	0.0246 (9)	0.0151 (10)	0.0014 (7)	0.0031 (8)	0.0026 (8)
C17	0.0188 (9)	0.0201 (9)	0.0194 (10)	0.0027 (7)	0.0038 (8)	−0.0002 (8)
H1O	0.0334	0.0372	0.0370	0.0002	0.0137	0.0019
H2O	0.0318	0.0372	0.0393	0.0009	0.0137	0.0012
H11A	0.0361	0.0473	0.0503	0.0114	0.0102	0.0130
H11B	0.0394	0.0614	0.0311	−0.0025	0.0070	−0.0030
H11C	0.0431	0.0358	0.0557	−0.0071	0.0167	−0.0046
H13	0.0329	0.0409	0.0445	−0.0002	0.0168	0.0017
H15	0.0373	0.0329	0.0456	−0.0030	0.0131	0.0021
H17	0.0367	0.0341	0.0463	0.0047	0.0140	−0.0004
O3	0.0208 (6)	0.0192 (6)	0.0370 (8)	−0.0044 (5)	0.0094 (6)	−0.0030 (6)
O4	0.0251 (7)	0.0180 (6)	0.0338 (8)	0.0008 (5)	0.0150 (6)	−0.0019 (6)
C33	0.0201 (9)	0.0280 (10)	0.0322 (12)	−0.0013 (8)	0.0102 (9)	−0.0023 (9)
C34	0.0192 (9)	0.0185 (9)	0.0177 (10)	−0.0021 (7)	0.0027 (8)	0.0022 (8)
C35	0.0163 (9)	0.0247 (9)	0.0160 (10)	0.0002 (7)	0.0030 (8)	0.0011 (8)
C36	0.0218 (9)	0.0193 (9)	0.0230 (11)	0.0023 (7)	0.0051 (8)	−0.0036 (8)
C37	0.0183 (9)	0.0201 (9)	0.0190 (10)	−0.0033 (7)	0.0013 (8)	0.0003 (8)
C38	0.0161 (9)	0.0216 (9)	0.0178 (10)	0.0004 (7)	0.0060 (8)	0.0004 (8)
C39	0.0191 (9)	0.0191 (9)	0.0160 (10)	0.0024 (7)	0.0029 (8)	−0.0005 (8)
H3O	0.0303	0.0347	0.0385	0.0001	0.0129	−0.0025
H4O	0.0313	0.0344	0.0371	−0.0008	0.0131	−0.0008
H33A	0.0421	0.0339	0.0562	−0.0004	0.0175	0.0077
H33B	0.0325	0.0601	0.0364	0.0044	0.0023	0.0054
H33C	0.0415	0.0442	0.0462	−0.0030	0.0140	−0.0147
H34	0.0351	0.0317	0.0457	−0.0044	0.0123	−0.0004
H36	0.0365	0.0317	0.0455	0.0031	0.0135	−0.0041
H38	0.0300	0.0384	0.0448	−0.0004	0.0152	−0.0023
O5	0.0216 (6)	0.0197 (6)	0.0346 (8)	0.0047 (5)	0.0122 (6)	0.0017 (6)
O6	0.0242 (6)	0.0194 (6)	0.0307 (8)	0.0002 (5)	0.0130 (6)	0.0036 (6)
C50	0.0236 (10)	0.0238 (10)	0.0297 (11)	0.0014 (8)	0.0117 (9)	0.0003 (9)
C51	0.0198 (9)	0.0195 (9)	0.0165 (10)	−0.0024 (7)	0.0023 (8)	0.0011 (8)
C52	0.0195 (9)	0.0166 (9)	0.0191 (10)	0.0025 (7)	0.0039 (8)	−0.0021 (8)
C53	0.0166 (9)	0.0229 (9)	0.0150 (10)	0.0009 (7)	0.0034 (8)	−0.0005 (8)
C54	0.0203 (9)	0.0199 (9)	0.0206 (10)	−0.0012 (7)	0.0058 (8)	0.0007 (8)
C55	0.0184 (9)	0.0198 (9)	0.0190 (10)	0.0041 (7)	0.0030 (8)	−0.0010 (8)
C56	0.0154 (9)	0.0233 (9)	0.0170 (10)	0.0004 (7)	0.0059 (8)	−0.0006 (8)
H5O	0.0297	0.0368	0.0396	0.0016	0.0125	0.0022
H6O	0.0300	0.0362	0.0388	0.0018	0.0132	0.0005
H50A	0.0418	0.0329	0.0578	0.0032	0.0178	−0.0029
H50B	0.0397	0.0540	0.0375	0.0048	0.0099	0.0137
H50C	0.0331	0.0569	0.0392	−0.0065	0.0040	−0.0091
H52	0.0348	0.0329	0.0460	0.0054	0.0128	0.0010
H54	0.0359	0.0335	0.0451	−0.0011	0.0129	0.0056
H56	0.0295	0.0405	0.0458	0.0019	0.0153	0.0019

Geometric parameters (Å, °)

N1—C9	1.341 (2)	C40—C41	1.381 (3)
N1—C10	1.339 (3)	C41—C42	1.394 (3)
O1—C14	1.366 (2)	C42—C45	1.487 (2)
N2—C3	1.335 (2)	C42—C43	1.386 (2)
O2—C12	1.364 (2)	C43—C44	1.383 (2)
N2—C1	1.337 (3)	C45—C49	1.395 (3)
O1—H1O	0.9900	C45—C46	1.393 (2)
O2—H2O	0.9900	C46—C47	1.379 (2)
N3—C25	1.338 (2)	C48—C49	1.380 (2)
N3—C27	1.342 (2)	C40—H40	1.0800
O3—C37	1.365 (2)	C41—H41	1.0800
N4—C22	1.342 (2)	C43—H43	1.0800
O4—C39	1.3653 (19)	C44—H44	1.0800
N4—C18	1.343 (2)	C46—H46	1.0800
O3—H3O	0.9900	C47—H47	1.0800
O4—H4O	0.9900	C48—H48	1.0800
O5—C55	1.364 (2)	C49—H49	1.0800
N5—C28	1.334 (3)	C57—C66	1.379 (2)
N5—C32	1.330 (2)	C57—C58	1.391 (2)
O6—C51	1.3665 (18)	C58—C59	1.392 (3)
O5—H5O	0.9900	C58—C61	1.486 (2)
O6—H6O	0.9900	C59—C60	1.378 (2)
N6—C48	1.339 (2)	C61—C64	1.393 (3)
N6—C47	1.340 (3)	C61—C62	1.390 (2)
N7—C40	1.337 (2)	C62—C63	1.383 (2)
N7—C44	1.337 (3)	C64—C65	1.377 (2)
N8—C63	1.344 (2)	C57—H57	1.0800
N8—C65	1.338 (2)	C59—H59	1.0800
N9—C60	1.337 (2)	C60—H60	1.0800
N9—C66	1.343 (2)	C62—H62	1.0800
C1—C2	1.384 (2)	C63—H63	1.0800
C2—C5	1.386 (2)	C64—H64	1.0800
C3—C4	1.379 (3)	C65—H65	1.0800
C4—C5	1.385 (3)	C66—H66	1.0800
C5—C6	1.488 (2)	C11—C16	1.502 (2)
C6—C7	1.390 (3)	C12—C13	1.390 (2)
C6—C8	1.397 (2)	C12—C17	1.392 (2)
C7—C9	1.379 (3)	C13—C14	1.390 (2)
C8—C10	1.380 (2)	C14—C15	1.393 (2)
C1—H1	1.0800	C15—C16	1.390 (2)
C2—H2	1.0800	C16—C17	1.391 (3)
C3—H3	1.0800	C11—H11C	1.0800
C4—H4	1.0800	C11—H11B	1.0800
C7—H7	1.0800	C11—H11A	1.0800
C8—H8	1.0800	C13—H13	1.0800
C9—H9	1.0800	C15—H15	1.0800
C10—H10	1.0800	C17—H17	1.0800
C18—C19	1.380 (2)	C33—C35	1.507 (2)
C19—C20	1.390 (3)	C34—C35	1.393 (2)
C20—C21	1.395 (2)	C34—C39	1.394 (2)
C20—C23	1.488 (2)	C35—C36	1.391 (2)
C21—C22	1.377 (2)	C36—C37	1.392 (2)
C23—C26	1.391 (3)	C37—C38	1.393 (2)
C23—C24	1.391 (2)	C38—C39	1.390 (2)
C24—C25	1.382 (2)	C33—H33C	1.0800
C26—C27	1.378 (2)	C33—H33A	1.0800
C18—H18	1.0800	C33—H33B	1.0800
C19—H19	1.0800	C34—H34	1.0800
C21—H21	1.0800	C36—H36	1.0800
C22—H22	1.0800	C38—H38	1.0800
C24—H24	1.0800	C50—C53	1.507 (2)
C25—H25	1.0800	C51—C56	1.392 (2)
C26—H26	1.0800	C51—C52	1.393 (2)
C27—H27	1.0800	C52—C53	1.391 (2)
C28—C29	1.384 (3)	C53—C54	1.391 (2)
C29—C30	1.382 (2)	C54—C55	1.390 (2)
C30—C30^i	1.496 (2)	C55—C56	1.396 (2)
C30—C31	1.390 (2)	C50—H50A	1.0800
C31—C32	1.381 (3)	C50—H50B	1.0800
C28—H28	1.0800	C50—H50C	1.0800
C29—H29	1.0800	C52—H52	1.0800
C31—H31	1.0800	C54—H54	1.0800
C32—H32	1.0800	C56—H56	1.0800
O6···C28	3.412 (2)	H4···C8	2.8000
O6···N3^ii	2.7329 (18)	H4···C35^xi	2.9700
O1···H36^iii	2.8700	H4···H34^xi	2.1700
O1···H18	2.8100	H4O···H38	2.3400
O3···H49^iv	2.7100	H5O···H56	2.3100
O4···H54^iv	2.6000	H6O···C27^ii	2.6400
O4···H9^v	2.8700	H6O···H28	2.4300
O5···H33A^ii	2.6800	H6O···H56	2.3500
O5···H34^ii	2.6300	H6O···C25^ii	2.7500
O6···H17^i	2.6400	H6O···N3^ii	1.7400
O6···H28	2.5100	H7···C39^iii	2.6800
N1···O5^vi	2.7452 (19)	H7···C34^iii	2.7900
N2···O4^vii	2.7614 (19)	H7···H2	2.3800
N3···O6^iv	2.7329 (18)	H7···C2	2.8200
N3···C56^iv	3.438 (2)	H8···H4	2.3700
N4···O3^viii	2.7335 (18)	H8···C34^xi	2.9400
N5···C11^ii	3.307 (2)	H8···C4	2.7800
N6···C33	3.418 (2)	H8···C35^xi	3.0100
N7···C50^iii	3.404 (2)	H9···H3^v	2.1900
N8···O1^ix	2.7617 (18)	H9···O4^iii	2.8700
N8···C13^ix	3.433 (2)	H11A···H17	2.5800
N9···C13^i	3.440 (2)	H11A···H32^iv	2.5300
N9···O2^i	2.7283 (18)	H11B···C28^i	2.9900
N1···H5O^vi	1.7600	H11B···C29^i	2.9800
N1···H56^vi	2.8900	H11B···N5^iv	2.7400
N2···H38^vii	2.7800	H11B···H25	2.6000
N2···H4O^vii	1.7700	H11C···O3^iii	2.6400
N2···H47^iii	2.8000	H11C···H15	2.4000
N3···H56^iv	2.7400	H13···H2O	2.2400
N3···H6O^iv	1.7400	H13···H1O	2.3500
N4···H3O^viii	1.7500	H15···O3^iii	2.6800
N4···H38^viii	2.8600	H15···H36^iii	1.9700
N5···H11B^ii	2.7400	H15···H11C	2.4000
N6···H33C	2.8100	H15···C36^iii	2.8300
N6···H44^iv	2.5300	H17···H29^i	2.4300
N7···H63^viii	2.4700	H17···H11A	2.5800
N7···H50B^iii	2.8000	H18···O1	2.8100
N8···H1O^ix	1.7700	H19···C15	2.8300
N8···H66^iv	2.9100	H19···H24	2.1900
N8···H13^ix	2.7100	H19···C14	2.8500
N9···H13^i	2.6700	H19···C24	2.7400
N9···H2O^i	1.7400	H21···C52	2.9800
C2···C55^x	3.571 (3)	H21···C51	3.0800
C2···O5^x	3.262 (2)	H21···C26	2.7200
C4···C34^xi	3.572 (2)	H21···H26	2.1800
C7···C39^iii	3.560 (2)	H24···C19	2.7400
C11···N5^iv	3.307 (2)	H24···O3^iii	2.5900
C12···C31	3.579 (3)	H24···C36^iii	3.0200
C18···C32	3.595 (3)	H24···H19	2.1900
C19···C32	3.514 (3)	H24···C15	3.0200
C19···C31	3.584 (3)	H24···C37^iii	3.0400
C24···C37^iii	3.580 (3)	H25···H11B	2.6000
C24···O3^iii	3.215 (2)	H25···H28^iv	2.5400
C26···C52	3.588 (2)	H26···C52	2.5200
C27···C31^i	3.563 (3)	H26···H21	2.1800
C28···O6	3.412 (2)	H26···C50	2.9100
C31···C12	3.579 (3)	H26···C21	2.7200
C31···C19	3.584 (3)	H26···H52	2.3500
C31···C27^i	3.563 (3)	H26···C53	2.7800
C32···C19	3.514 (3)	H28···O6	2.5100
C32···C18	3.595 (3)	H28···H6O	2.4300
C33···N6	3.418 (2)	H28···H25^ii	2.5400
C37···C49^iv	3.543 (3)	H29···C31^i	2.6600
C39···C7^v	3.560 (2)	H29···C17^i	2.6800
C41···C58^iii	3.536 (2)	H29···H31^i	2.0100
C44···O1^xii	3.270 (2)	H29···H17^i	2.4300
C45···C62^iii	3.583 (3)	H29···C16^i	3.0800
C47···O4^iii	3.287 (2)	H31···C12	2.6200
C49···C37^ii	3.543 (3)	H31···H29^i	2.0100
C52···C26	3.588 (2)	H31···C29^i	2.6800
C56···N3^ii	3.438 (2)	H31···C17	2.7400
C57···C14^xiii	3.493 (2)	H31···C13	3.0900
C59···O6^iv	3.411 (2)	H32···H11A^ii	2.5300
C60···O6^iv	3.333 (2)	H33A···O5^iv	2.6800
C1···H47^iii	3.0000	H33A···H34	2.4600
C1···H4O^vii	2.7700	H33C···N6	2.8100
C2···H7	2.8200	H33C···H36	2.5000
C3···H4O^vii	2.6600	H34···C54^iv	2.8000
C4···H8	2.7800	H34···H33A	2.4600
C7···H2	2.8200	H34···H54^iv	1.9500
C8···H4	2.8000	H34···O5^iv	2.6300
C9···H5O^vi	2.6500	H36···H33C	2.5000
C9···H50C^x	3.0900	H38···H3O	2.3100
C10···H5O^vi	2.7700	H38···H4O	2.3400
C12···H31	2.6200	H40···C56^x	3.0700
C13···H31	3.0900	H41···H46	2.3100
C14···H19	2.8500	H41···C46	2.8100
C15···H19	2.8300	H41···C54^x	2.8000
C15···H36^iii	2.8200	H41···C55^x	2.7700
C15···H24	3.0200	H43···C35^ii	3.0100
C16···H29^i	3.0800	H43···H49	2.2200
C17···H31	2.7400	H43···C36^ii	2.8200
C17···H29^i	2.6800	H43···C49	2.7200
C18···H3O^viii	2.6600	H44···N6^ii	2.5300
C18···H33B^iii	3.0700	H44···H63^viii	2.5600
C19···H36^iii	3.1000	H44···C47^ii	2.9200
C19···H24	2.7400	H44···O1^xii	2.7700
C21···H26	2.7200	H46···C54^x	3.0200
C22···H3O^viii	2.7400	H46···H41	2.3100
C24···H19	2.7400	H46···C41	2.7900
C25···H6O^iv	2.7500	H47···N2^v	2.8000
C26···H21	2.7200	H47···C1^v	3.0000
C27···H56^iv	2.9200	H47···O4^iii	2.4300
C27···H6O^iv	2.6400	H47···H4O^iii	2.2100
C28···H11B^i	2.9900	H47···H1^v	2.5200
C29···H11B^i	2.9800	H49···H43	2.2200
C29···H31^i	2.6800	H49···C43	2.7400
C31···H29^i	2.6600	H49···O3^ii	2.7100
C34···H7^v	2.7900	H49···C36^ii	2.9400
C34···H54^iv	2.7300	H49···C37^ii	2.7900
C35···H43^iv	3.0100	H50A···H52	2.4000
C36···H43^iv	2.8200	H50A···O2^i	2.6300
C36···H49^iv	2.9400	H52···H26	2.3500
C37···H49^iv	2.7900	H52···C17^i	2.8700
C39···H7^v	2.6800	H52···H17^i	2.0600
C39···H54^iv	3.0500	H52···H50A	2.4000
C41···H46	2.7900	H52···O2^i	2.5000
C43···H49	2.7400	H54···O4^ii	2.6000
C44···H63^viii	2.8900	H54···C39^ii	3.0500
C46···H41	2.8100	H54···H34^ii	1.9500
C47···H44^iv	2.9200	H54···C34^ii	2.7300
C49···H43	2.7200	H56···H5O	2.3100
C50···H26	2.9100	H56···H6O	2.3500
C51···H21	3.0800	H56···N3^ii	2.7400
C52···H17^i	2.8900	H56···C27^ii	2.9200
C52···H26	2.5200	H57···C13^xiii	2.8600
C52···H21	2.9800	H57···C14^xiii	2.5400
C53···H26	2.7800	H57···C15^xiii	2.6900
C54···H34^ii	2.8000	H57···C64	2.7300
C57···H64	2.7200	H57···H64	2.1900
C59···H62	2.7200	H59···O6^iv	2.7700
C60···H2O^i	2.7000	H59···C51^iv	2.9200
C62···H59	2.7600	H59···C52^iv	2.8600
C63···H1O^ix	2.8000	H59···C62	2.7600
C63···H66^iv	2.9900	H59···H62	2.2100
C64···H57	2.7300	H60···O6^iv	2.6200
C65···H13^ix	2.7500	H60···H6O^iv	2.5900
C65···H1O^ix	2.6400	H62···C52^iv	2.8100
C66···H2O^i	2.6900	H62···C53^iv	2.9500
H1···H47^iii	2.5200	H62···C59	2.7200
H1O···H13	2.3500	H62···H59	2.2100
H2···C54^x	2.8900	H64···C11^xiii	2.9600
H2···O5^x	2.4900	H64···C15^xiii	3.0700
H2···C7	2.8200	H64···C16^xiii	2.7100
H2···H7	2.3800	H64···C57	2.7200
H2···C55^x	2.8400	H64···H57	2.1900
H2O···H13	2.2400	H65···C11^xiii	3.0100
H3···H9^iii	2.1900	H65···H11A^xiii	2.5200
H3O···H38	2.3100	H65···H11C^xiii	2.5900
H4···C34^xi	2.5100	H65···H13^ix	2.3800
H4···H8	2.3700	H66···C13^xiii	3.0800
C9—N1—C10	116.25 (15)	N7—C44—H44	115.00
C1—N2—C3	116.23 (15)	C47—C46—H46	120.00
C14—O1—H1O	111.00	C45—C46—H46	121.00
C12—O2—H2O	110.00	C46—C47—H47	118.00
C25—N3—C27	116.23 (15)	N6—C47—H47	118.00
C18—N4—C22	116.33 (15)	C49—C48—H48	119.00
C37—O3—H3O	111.00	N6—C48—H48	117.00
C39—O4—H4O	112.00	C45—C49—H49	122.00
C28—N5—C32	115.22 (15)	C48—C49—H49	119.00
C55—O5—H5O	113.00	C58—C57—C66	119.61 (17)
C51—O6—H6O	111.00	C57—C58—C59	117.01 (15)
C47—N6—C48	116.04 (15)	C59—C58—C61	121.89 (15)
C40—N7—C44	115.95 (15)	C57—C58—C61	121.09 (16)
C63—N8—C65	116.44 (14)	C58—C59—C60	119.42 (15)
C60—N9—C66	116.40 (15)	N9—C60—C59	123.98 (17)
N2—C1—C2	123.82 (16)	C62—C61—C64	117.01 (15)
C1—C2—C5	119.25 (17)	C58—C61—C62	121.77 (16)
N2—C3—C4	123.98 (18)	C58—C61—C64	121.21 (15)
C3—C4—C5	119.45 (16)	C61—C62—C63	119.88 (17)
C2—C5—C6	122.03 (16)	N8—C63—C62	123.20 (16)
C2—C5—C4	117.24 (15)	C61—C64—C65	119.21 (16)
C4—C5—C6	120.74 (15)	N8—C65—C64	124.25 (17)
C7—C6—C8	117.29 (15)	N9—C66—C57	123.59 (16)
C5—C6—C8	121.48 (16)	C58—C57—H57	123.00
C5—C6—C7	121.23 (15)	C66—C57—H57	118.00
C6—C7—C9	119.08 (16)	C60—C59—H59	119.00
C6—C8—C10	119.29 (17)	C58—C59—H59	122.00
N1—C9—C7	124.22 (18)	C59—C60—H60	120.00
N1—C10—C8	123.85 (16)	N9—C60—H60	116.00
N2—C1—H1	116.00	C61—C62—H62	121.00
C2—C1—H1	120.00	C63—C62—H62	120.00
C1—C2—H2	118.00	N8—C63—H63	117.00
C5—C2—H2	122.00	C62—C63—H63	120.00
C4—C3—H3	120.00	C65—C64—H64	119.00
N2—C3—H3	115.00	C61—C64—H64	122.00
C5—C4—H4	122.00	N8—C65—H65	115.00
C3—C4—H4	119.00	C64—C65—H65	121.00
C9—C7—H7	118.00	N9—C66—H66	115.00
C6—C7—H7	122.00	C57—C66—H66	121.00
C10—C8—H8	120.00	O2—C12—C17	117.85 (15)
C6—C8—H8	121.00	C13—C12—C17	120.30 (16)
N1—C9—H9	117.00	O2—C12—C13	121.81 (14)
C7—C9—H9	119.00	C12—C13—C14	119.53 (15)
N1—C10—H10	117.00	O1—C14—C15	117.52 (15)
C8—C10—H10	119.00	C13—C14—C15	120.24 (15)
N4—C18—C19	123.79 (17)	O1—C14—C13	122.24 (14)
C18—C19—C20	119.54 (16)	C14—C15—C16	120.16 (15)
C19—C20—C21	117.00 (15)	C11—C16—C15	120.67 (15)
C19—C20—C23	121.46 (15)	C15—C16—C17	119.58 (15)
C21—C20—C23	121.54 (16)	C11—C16—C17	119.75 (15)
C20—C21—C22	119.57 (17)	C12—C17—C16	120.18 (16)
N4—C22—C21	123.77 (17)	C16—C11—H11A	113.00
C20—C23—C26	121.08 (15)	C16—C11—H11B	113.00
C20—C23—C24	122.16 (16)	H11B—C11—H11C	104.00
C24—C23—C26	116.77 (15)	H11A—C11—H11B	106.00
C23—C24—C25	119.62 (16)	C16—C11—H11C	113.00
N3—C25—C24	123.86 (16)	H11A—C11—H11C	107.00
C23—C26—C27	119.72 (16)	C14—C13—H13	122.00
N3—C27—C26	123.80 (17)	C12—C13—H13	119.00
N4—C18—H18	117.00	C14—C15—H15	121.00
C19—C18—H18	120.00	C16—C15—H15	119.00
C20—C19—H19	122.00	C16—C17—H17	119.00
C18—C19—H19	119.00	C12—C17—H17	120.00
C22—C21—H21	118.00	C35—C34—C39	120.40 (14)
C20—C21—H21	122.00	C33—C35—C36	120.32 (16)
C21—C22—H22	121.00	C34—C35—C36	119.19 (15)
N4—C22—H22	116.00	C33—C35—C34	120.47 (15)
C23—C24—H24	122.00	C35—C36—C37	120.30 (16)
C25—C24—H24	119.00	C36—C37—C38	120.58 (16)
N3—C25—H25	117.00	O3—C37—C38	121.99 (14)
C24—C25—H25	119.00	O3—C37—C36	117.43 (15)
C23—C26—H26	122.00	C37—C38—C39	119.07 (15)
C27—C26—H26	118.00	C34—C39—C38	120.44 (14)
N3—C27—H27	117.00	O4—C39—C34	117.35 (13)
C26—C27—H27	119.00	O4—C39—C38	122.19 (14)
N5—C28—C29	123.82 (17)	C35—C33—H33B	112.00
C28—C29—C30	120.46 (17)	C35—C33—H33A	113.00
C29—C30—C30^i	122.32 (15)	H33A—C33—H33C	111.00
C30^i—C30—C31	121.60 (14)	H33B—C33—H33C	106.00
C29—C30—C31	116.08 (15)	C35—C33—H33C	112.00
C30—C31—C32	119.23 (16)	H33A—C33—H33B	102.00
N5—C32—C31	125.18 (18)	C35—C34—H34	120.00
N5—C28—H28	116.00	C39—C34—H34	119.00
C29—C28—H28	120.00	C35—C36—H36	120.00
C30—C29—H29	121.00	C37—C36—H36	120.00
C28—C29—H29	118.00	C37—C38—H38	121.00
C32—C31—H31	118.00	C39—C38—H38	120.00
C30—C31—H31	122.00	O6—C51—C56	122.20 (14)
N5—C32—H32	115.00	O6—C51—C52	117.33 (13)
C31—C32—H32	119.00	C52—C51—C56	120.46 (14)
N7—C40—C41	124.43 (17)	C51—C52—C53	120.25 (14)
C40—C41—C42	119.03 (16)	C50—C53—C52	120.74 (15)
C41—C42—C45	121.85 (15)	C52—C53—C54	119.40 (15)
C43—C42—C45	121.06 (16)	C50—C53—C54	119.85 (15)
C41—C42—C43	117.09 (15)	C53—C54—C55	120.37 (16)
C42—C43—C44	119.53 (17)	O5—C55—C54	117.83 (15)
N7—C44—C43	123.98 (16)	O5—C55—C56	121.79 (14)
C46—C45—C49	116.75 (15)	C54—C55—C56	120.38 (16)
C42—C45—C46	122.12 (16)	C51—C56—C55	119.12 (14)
C42—C45—C49	121.13 (15)	C53—C50—H50A	111.00
C45—C46—C47	119.59 (17)	C53—C50—H50B	112.00
N6—C47—C46	124.02 (16)	C53—C50—H50C	110.00
N6—C48—C49	124.16 (18)	H50A—C50—H50B	106.00
C45—C49—C48	119.44 (16)	H50A—C50—H50C	107.00
N7—C40—H40	117.00	H50B—C50—H50C	111.00
C41—C40—H40	119.00	C51—C52—H52	120.00
C42—C41—H41	122.00	C53—C52—H52	120.00
C40—C41—H41	119.00	C53—C54—H54	119.00
C44—C43—H43	120.00	C55—C54—H54	121.00
C42—C43—H43	121.00	C51—C56—H56	122.00
C43—C44—H44	121.00	C55—C56—H56	119.00
C10—N1—C9—C7	0.6 (3)	C43—C42—C45—C49	30.5 (2)
C9—N1—C10—C8	−0.1 (3)	C41—C42—C45—C49	−149.91 (17)
C3—N2—C1—C2	−1.4 (3)	C43—C42—C45—C46	−148.98 (18)
C1—N2—C3—C4	2.1 (3)	C41—C42—C43—C44	0.3 (2)
C27—N3—C25—C24	−0.7 (3)	C45—C42—C43—C44	179.94 (15)
C25—N3—C27—C26	0.8 (3)	C42—C43—C44—N7	0.0 (3)
C22—N4—C18—C19	−0.5 (3)	C42—C45—C46—C47	179.63 (16)
C18—N4—C22—C21	0.4 (3)	C49—C45—C46—C47	0.2 (3)
C28—N5—C32—C31	0.4 (3)	C46—C45—C49—C48	0.5 (3)
C32—N5—C28—C29	−0.8 (3)	C42—C45—C49—C48	−179.02 (16)
C47—N6—C48—C49	−0.5 (3)	C45—C46—C47—N6	−1.0 (3)
C48—N6—C47—C46	1.2 (3)	N6—C48—C49—C45	−0.3 (3)
C40—N7—C44—C43	−0.2 (3)	C66—C57—C58—C59	1.4 (2)
C44—N7—C40—C41	0.2 (3)	C66—C57—C58—C61	−177.54 (15)
C63—N8—C65—C64	0.5 (3)	C58—C57—C66—N9	−1.0 (3)
C65—N8—C63—C62	−0.6 (3)	C57—C58—C59—C60	−0.9 (2)
C66—N9—C60—C59	0.5 (3)	C61—C58—C59—C60	178.01 (15)
C60—N9—C66—C57	0.1 (3)	C57—C58—C61—C62	152.85 (17)
N2—C1—C2—C5	−0.4 (3)	C57—C58—C61—C64	−26.1 (2)
C1—C2—C5—C6	−178.57 (16)	C59—C58—C61—C62	−26.0 (2)
C1—C2—C5—C4	1.5 (2)	C59—C58—C61—C64	155.10 (16)
N2—C3—C4—C5	−1.1 (3)	C58—C59—C60—N9	0.0 (3)
C3—C4—C5—C2	−0.8 (3)	C58—C61—C62—C63	−178.73 (15)
C3—C4—C5—C6	179.27 (17)	C64—C61—C62—C63	0.2 (2)
C4—C5—C6—C7	145.41 (17)	C58—C61—C64—C65	178.67 (15)
C2—C5—C6—C8	145.62 (18)	C62—C61—C64—C65	−0.3 (2)
C2—C5—C6—C7	−34.6 (2)	C61—C62—C63—N8	0.2 (3)
C4—C5—C6—C8	−34.4 (2)	C61—C64—C65—N8	−0.1 (3)
C8—C6—C7—C9	1.0 (3)	O2—C12—C13—C14	−178.50 (15)
C5—C6—C7—C9	−178.86 (17)	C17—C12—C13—C14	−0.7 (3)
C5—C6—C8—C10	179.35 (16)	O2—C12—C17—C16	178.48 (15)
C7—C6—C8—C10	−0.5 (3)	C13—C12—C17—C16	0.6 (3)
C6—C7—C9—N1	−1.1 (3)	C12—C13—C14—O1	179.77 (15)
C6—C8—C10—N1	0.0 (3)	C12—C13—C14—C15	−0.2 (2)
N4—C18—C19—C20	−0.1 (3)	O1—C14—C15—C16	−178.78 (14)
C18—C19—C20—C23	−178.52 (17)	C13—C14—C15—C16	1.2 (2)
C18—C19—C20—C21	0.7 (3)	C14—C15—C16—C11	177.72 (15)
C23—C20—C21—C22	178.48 (17)	C14—C15—C16—C17	−1.3 (2)
C19—C20—C23—C26	155.66 (18)	C11—C16—C17—C12	−178.61 (16)
C21—C20—C23—C26	−23.5 (3)	C15—C16—C17—C12	0.4 (2)
C19—C20—C21—C22	−0.7 (3)	C39—C34—C35—C33	178.61 (15)
C21—C20—C23—C24	155.96 (18)	C39—C34—C35—C36	−0.2 (2)
C19—C20—C23—C24	−24.9 (3)	C35—C34—C39—O4	179.73 (15)
C20—C21—C22—N4	0.2 (3)	C35—C34—C39—C38	0.8 (2)
C26—C23—C24—C25	0.9 (3)	C33—C35—C36—C37	−179.97 (16)
C24—C23—C26—C27	−0.8 (3)	C34—C35—C36—C37	−1.1 (3)
C20—C23—C26—C27	178.70 (17)	C35—C36—C37—O3	−176.91 (16)
C20—C23—C24—C25	−178.63 (17)	C35—C36—C37—C38	1.9 (3)
C23—C24—C25—N3	−0.1 (3)	O3—C37—C38—C39	177.47 (15)
C23—C26—C27—N3	−0.1 (3)	C36—C37—C38—C39	−1.3 (3)
N5—C28—C29—C30	1.1 (3)	C37—C38—C39—O4	−178.91 (15)
C28—C29—C30—C30^i	178.86 (16)	C37—C38—C39—C34	−0.1 (3)
C28—C29—C30—C31	−0.9 (3)	O6—C51—C52—C53	−179.58 (14)
C31—C30—C30^i—C29^i	−0.3 (2)	C56—C51—C52—C53	1.3 (2)
C29—C30—C30^i—C29^i	180.00 (16)	O6—C51—C56—C55	−179.48 (15)
C29—C30—C30^i—C31^i	0.3 (2)	C52—C51—C56—C55	−0.4 (2)
C30^i—C30—C31—C32	−179.24 (16)	C51—C52—C53—C50	178.71 (15)
C31—C30—C30^i—C31^i	−180.00 (16)	C51—C52—C53—C54	−0.7 (2)
C29—C30—C31—C32	0.5 (2)	C50—C53—C54—C55	179.73 (16)
C30—C31—C32—N5	−0.3 (3)	C52—C53—C54—C55	−0.9 (3)
N7—C40—C41—C42	0.1 (3)	C53—C54—C55—O5	−177.38 (16)
C40—C41—C42—C43	−0.3 (2)	C53—C54—C55—C56	1.8 (3)
C40—C41—C42—C45	−179.93 (17)	O5—C55—C56—C51	178.02 (15)
C41—C42—C45—C46	30.6 (2)	C54—C55—C56—C51	−1.1 (3)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) x−1/2, −y+1/2, z+1/2; (iv) x+1, y, z; (v) x+1/2, −y+1/2, z−1/2; (vi) x+3/2, −y+1/2, z+1/2; (vii) x−1, y, z+1; (viii) x−3/2, −y+1/2, z+1/2; (ix) x+1, y, z−1; (x) x+1/2, −y+1/2, z+1/2; (xi) x, y, z+1; (xii) x−1/2, −y+1/2, z−1/2; (xiii) x, y, z−1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6O···N3^ii	0.9900	1.7400	2.7329 (18)	177.00
C2—H2···O5^x	1.0800	2.4900	3.262 (2)	127.00
C24—H24···O3^iii	1.0800	2.5900	3.215 (2)	116.00
C28—H28···O6	1.0800	2.5100	3.412 (2)	141.00
C44—H44···N6^ii	1.0800	2.5300	3.474 (2)	145.00
C47—H47···O4^iii	1.0800	2.4300	3.287 (2)	135.00
C52—H52···O2^i	1.0800	2.5000	3.4999 (19)	152.00
C54—H54···O4^ii	1.0800	2.6000	3.612 (2)	156.00

Symmetry codes: (ii) x−1, y, z; (x) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z+1/2; (i) −x+1, −y, −z+1.

(V)

Crystal data

4(C10H8N2)·4(C7H8O2)	F(000) = 2368
Mr = 1121.31	Dx = 1.277 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4047 reflections
a = 17.8201 (5) Å	θ = 2.3–29.6°
b = 8.3288 (2) Å	µ = 0.09 mm^−1
c = 39.3222 (9) Å	T = 100 K
β = 91.901 (2)°	Block, colourless
V = 5833.0 (3) Å^3	0.61 × 0.15 × 0.15 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	12681 independent reflections
Radiation source: Mova (Mo) X-ray Source	7472 reflections with I > 2σ(I)
mirror	Rint = 0.075
Detector resolution: 16.0839 pixels mm^-1	θmax = 27.1°, θmin = 2.4°
ω scans	h = −22→22
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→10
Tmin = 0.374, Tmax = 1.000	l = −49→50
39290 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.073	All H-atom parameters refined
wR(F^2) = 0.152	w = 1/[σ^2(Fo^2) + (0.0321P)^2 + 2.7881P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
12809 reflections	Δρmax = 0.37 e Å^−3
1013 parameters	Δρmin = −0.34 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.02208 (12)	0.2466 (3)	0.22883 (6)	0.0287 (8)
N2	0.38758 (11)	0.1758 (3)	0.16174 (6)	0.0288 (8)
C28	0.07146 (16)	0.1368 (3)	0.24029 (7)	0.0319 (10)
C29	0.14370 (15)	0.1228 (3)	0.22898 (7)	0.0267 (9)
C30	0.16858 (14)	0.2269 (3)	0.20399 (6)	0.0205 (8)
C31	0.11848 (14)	0.3445 (3)	0.19275 (6)	0.0235 (9)
C32	0.04683 (14)	0.3493 (3)	0.20549 (7)	0.0269 (9)
C33	0.24454 (14)	0.2107 (3)	0.18969 (6)	0.0194 (8)
C34	0.30184 (14)	0.1250 (3)	0.20659 (7)	0.0268 (9)
C35	0.37103 (14)	0.1124 (3)	0.19189 (7)	0.0310 (10)
C36	0.33219 (14)	0.2559 (3)	0.14547 (7)	0.0285 (9)
C37	0.26111 (14)	0.2768 (3)	0.15823 (7)	0.0264 (9)
N3	0.10850 (12)	0.2943 (3)	0.33339 (6)	0.0317 (8)
N4	0.47078 (13)	0.3747 (3)	0.26297 (6)	0.0386 (9)
C18	0.12138 (14)	0.3985 (3)	0.30838 (7)	0.0308 (10)
C19	0.19067 (15)	0.4193 (3)	0.29421 (7)	0.0285 (10)
C20	0.25188 (14)	0.3286 (3)	0.30572 (7)	0.0236 (9)
C21	0.23886 (15)	0.2204 (4)	0.33160 (8)	0.0399 (11)
C22	0.16769 (16)	0.2069 (4)	0.34443 (8)	0.0442 (11)
C23	0.32737 (14)	0.3472 (3)	0.29101 (7)	0.0246 (9)
C24	0.33873 (16)	0.4291 (4)	0.26130 (8)	0.0436 (11)
C25	0.40991 (18)	0.4408 (4)	0.24837 (9)	0.0482 (12)
C26	0.45968 (17)	0.2986 (5)	0.29162 (9)	0.0631 (14)
C27	0.39068 (17)	0.2828 (4)	0.30639 (8)	0.0556 (13)
N5	0.29603 (12)	0.6213 (3)	0.03604 (6)	0.0321 (8)
N6	0.62959 (12)	0.8610 (3)	−0.04542 (6)	0.0284 (8)
C59	0.29929 (15)	0.6306 (3)	0.00190 (8)	0.0339 (10)
C60	0.36236 (15)	0.6768 (3)	−0.01507 (7)	0.0292 (9)
C61	0.42775 (14)	0.7144 (3)	0.00347 (6)	0.0218 (9)
C62	0.42483 (15)	0.7047 (3)	0.03874 (7)	0.0306 (10)
C63	0.35903 (16)	0.6596 (4)	0.05374 (7)	0.0360 (11)
C64	0.49749 (14)	0.7641 (3)	−0.01360 (6)	0.0205 (8)
C65	0.49514 (14)	0.8343 (3)	−0.04585 (7)	0.0265 (9)
C66	0.56144 (15)	0.8803 (3)	−0.06042 (7)	0.0292 (9)
C67	0.63129 (14)	0.7924 (3)	−0.01451 (7)	0.0293 (9)
C68	0.56822 (14)	0.7420 (3)	0.00204 (7)	0.0270 (9)
N7	0.11800 (12)	0.1056 (3)	0.45567 (6)	0.0294 (8)
N8	−0.19737 (13)	0.4442 (3)	0.53624 (6)	0.0341 (9)
C1	−0.19085 (18)	0.4472 (4)	0.50260 (8)	0.0479 (12)
C2	−0.12965 (18)	0.3887 (4)	0.48595 (8)	0.0470 (11)
C3	−0.07009 (15)	0.3221 (3)	0.50387 (7)	0.0257 (9)
C4	−0.07659 (17)	0.3177 (5)	0.53883 (8)	0.0618 (13)
C5	−0.14011 (17)	0.3778 (5)	0.55365 (8)	0.0608 (13)
C6	−0.00437 (14)	0.2517 (3)	0.48704 (7)	0.0239 (8)
C7	−0.00158 (16)	0.2344 (4)	0.45226 (7)	0.0517 (13)
C8	0.05938 (16)	0.1625 (4)	0.43799 (7)	0.0473 (13)
C9	0.05742 (19)	0.1966 (4)	0.50538 (7)	0.0542 (13)
C10	0.11567 (18)	0.1241 (4)	0.48916 (8)	0.0559 (13)
O1	0.24498 (10)	0.0206 (2)	0.07759 (5)	0.0323 (7)
O2	0.16477 (9)	0.5727 (2)	0.06969 (4)	0.0286 (6)
C52	0.00690 (15)	0.1766 (4)	0.12539 (7)	0.0373 (11)
C53	0.07697 (14)	0.2204 (3)	0.10704 (6)	0.0263 (9)
C54	0.12920 (15)	0.1020 (3)	0.09971 (7)	0.0268 (9)
C55	0.19445 (14)	0.1407 (3)	0.08313 (6)	0.0246 (9)
C56	0.20719 (14)	0.2979 (3)	0.07257 (6)	0.0224 (8)
C57	0.15506 (14)	0.4167 (3)	0.07975 (6)	0.0230 (9)
C58	0.09050 (14)	0.3793 (3)	0.09736 (7)	0.0255 (9)
O3	0.52856 (9)	0.1242 (2)	0.13783 (5)	0.0337 (7)
O4	0.61829 (10)	0.3810 (3)	0.24125 (5)	0.0455 (8)
C38	0.57007 (13)	0.2551 (3)	0.18980 (7)	0.0266 (9)
C39	0.58501 (14)	0.1856 (3)	0.15851 (6)	0.0232 (9)
C40	0.65811 (14)	0.1772 (3)	0.14747 (6)	0.0252 (9)
C41	0.71688 (14)	0.2426 (3)	0.16704 (7)	0.0253 (9)
C42	0.70248 (14)	0.3116 (3)	0.19837 (7)	0.0288 (9)
C43	0.62926 (14)	0.3163 (3)	0.20973 (7)	0.0290 (10)
C44	0.79550 (15)	0.2422 (3)	0.15338 (7)	0.0365 (10)
O5	−0.12707 (9)	0.2439 (2)	0.24705 (4)	0.0279 (6)
O6	−0.02968 (9)	0.2475 (2)	0.36290 (4)	0.0319 (7)
C45	−0.07556 (13)	0.2474 (3)	0.30457 (7)	0.0227 (8)
C46	−0.08828 (14)	0.2429 (3)	0.33934 (7)	0.0238 (9)
C47	−0.16097 (14)	0.2310 (3)	0.35108 (6)	0.0254 (9)
C48	−0.22183 (14)	0.2279 (3)	0.32799 (7)	0.0253 (9)
C49	−0.20979 (14)	0.2312 (3)	0.29312 (7)	0.0263 (9)
C50	−0.13674 (14)	0.2406 (3)	0.28168 (6)	0.0220 (8)
C51	−0.30076 (15)	0.2230 (3)	0.34093 (8)	0.0391 (11)
O7	0.23681 (10)	−0.0375 (2)	0.42344 (5)	0.0325 (7)
O8	0.33017 (9)	0.5032 (2)	0.43093 (5)	0.0286 (7)
C11	0.28125 (14)	0.2349 (3)	0.42780 (6)	0.0232 (8)
C12	0.29112 (15)	0.0755 (3)	0.41805 (7)	0.0256 (9)
C13	0.35656 (15)	0.0276 (3)	0.40263 (7)	0.0264 (9)
C14	0.41226 (14)	0.1392 (3)	0.39611 (6)	0.0251 (9)
C15	0.40231 (14)	0.2999 (3)	0.40514 (6)	0.0240 (9)
C16	0.33720 (14)	0.3458 (3)	0.42137 (6)	0.0227 (9)
C17	0.48367 (15)	0.0865 (3)	0.37940 (7)	0.0332 (10)
H28	0.05272	0.05363	0.25940	0.0421
H29	0.18046	0.02938	0.23903	0.0416
H31	0.13108	0.43084	0.17314	0.0410
H32	0.00602	0.43806	0.19690	0.0415
H34	0.29586	0.07107	0.23141	0.0417
H35	0.41579	0.04676	0.20499	0.0422
H36	0.34534	0.30571	0.12093	0.0413
H37	0.21831	0.34363	0.14407	0.0408
H18	0.07289	0.46939	0.30052	0.0428
H19	0.19710	0.50522	0.27384	0.0423
H21	0.28456	0.14725	0.34178	0.0430
H22	0.15692	0.12174	0.36450	0.0433
H24	0.29278	0.48580	0.24714	0.0422
H25	0.41867	0.50052	0.22437	0.0428
H26	0.51049	0.24904	0.30328	0.0440
H27	0.38860	0.21678	0.33007	0.0433
H59	0.24713	0.60032	−0.01150	0.0406
H60	0.36179	0.68057	−0.04261	0.0415
H61	0.47433	0.73261	0.05434	0.0429
H63	0.35515	0.65232	0.08113	0.0416
H65	0.44123	0.85729	−0.05844	0.0428
H66	0.55819	0.93352	−0.08555	0.0448
H67	0.68626	0.77368	−0.00259	0.0462
H68	0.57669	0.68818	0.02695	0.0441
H1	−0.23983	0.49554	0.48914	0.0495
H2	−0.12845	0.39889	0.45851	0.0472
H4	−0.03230	0.26415	0.55458	0.0486
H5	−0.14409	0.37273	0.58105	0.0507
H7	−0.05016	0.25805	0.43574	0.0458
H8	0.06114	0.14488	0.41073	0.0444
H9	0.06264	0.21135	0.53272	0.0473
H10	0.16785	0.09307	0.50245	0.0460
H1O	0.29195	0.06070	0.06772	0.0377
H2O	0.21233	0.58979	0.05779	0.0373
H52A	−0.02461	0.08439	0.11207	0.0471
H52B	−0.03302	0.27289	0.12750	0.0470
H52C	0.02024	0.13269	0.15063	0.0471
H54	0.11925	−0.02074	0.10746	0.0408
H56	0.25856	0.33182	0.06049	0.0406
H58	0.05065	0.47326	0.10284	0.0406
H3O	0.47806	0.14789	0.14645	0.0392
H4O	0.56403	0.38212	0.24613	0.0410
H38	0.51360	0.26289	0.19903	0.0431
H40	0.66668	0.12227	0.12294	0.0448
H42	0.74628	0.36162	0.21492	0.0467
H44A	0.80838	0.12450	0.14383	0.0534
H44B	0.79979	0.32880	0.13320	0.0534
H44C	0.83655	0.27161	0.17312	0.0541
H5O	−0.07274	0.24276	0.24231	0.0392
H6O	0.01797	0.26638	0.35118	0.0404
H45	−0.01895	0.25843	0.29564	0.0429
H47	−0.16938	0.22182	0.37816	0.0457
H49	−0.25719	0.23779	0.27521	0.0448
H51A	−0.31292	0.32243	0.35736	0.0532
H51B	−0.31108	0.11478	0.35503	0.0531
H51C	−0.34141	0.22690	0.32005	0.0529
H7O	0.19270	0.01336	0.43379	0.0413
H8O	0.28288	0.52093	0.44301	0.0423
H11	0.22944	0.27271	0.43903	0.0448
H13	0.36245	−0.09791	0.39606	0.0441
H15	0.44419	0.38987	0.39981	0.0451
H17A	0.47291	0.02473	0.35568	0.0502
H17B	0.51908	0.18820	0.37455	0.0510
H17C	0.51534	0.00901	0.39646	0.0511

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0303 (13)	0.0308 (14)	0.0256 (14)	−0.0010 (11)	0.0081 (11)	−0.0029 (12)
N2	0.0188 (12)	0.0379 (14)	0.0296 (14)	0.0003 (11)	−0.0014 (11)	−0.0009 (12)
C28	0.0376 (18)	0.0304 (17)	0.0284 (17)	−0.0007 (14)	0.0123 (14)	0.0017 (14)
C29	0.0303 (16)	0.0247 (16)	0.0253 (16)	0.0021 (13)	0.0051 (13)	0.0039 (13)
C30	0.0233 (14)	0.0199 (14)	0.0183 (14)	−0.0036 (12)	0.0000 (12)	−0.0053 (12)
C31	0.0273 (15)	0.0260 (15)	0.0176 (15)	0.0008 (12)	0.0048 (12)	0.0042 (13)
C32	0.0254 (16)	0.0336 (17)	0.0218 (16)	0.0044 (13)	0.0037 (13)	0.0004 (14)
C33	0.0218 (14)	0.0189 (14)	0.0174 (14)	−0.0021 (11)	−0.0015 (11)	−0.0038 (12)
C34	0.0258 (15)	0.0303 (16)	0.0243 (16)	−0.0017 (13)	−0.0010 (13)	0.0074 (14)
C35	0.0233 (16)	0.0334 (17)	0.0358 (18)	0.0008 (13)	−0.0061 (14)	0.0056 (15)
C36	0.0216 (15)	0.0439 (18)	0.0202 (15)	−0.0012 (14)	0.0039 (12)	0.0016 (15)
C37	0.0224 (15)	0.0363 (17)	0.0203 (15)	0.0049 (13)	−0.0017 (12)	0.0043 (14)
H28	0.0414	0.0478	0.0374	−0.0010	0.0074	0.0086
H29	0.0387	0.0461	0.0402	0.0058	0.0027	0.0063
H31	0.0401	0.0455	0.0378	−0.0006	0.0065	0.0082
H32	0.0360	0.0460	0.0427	0.0051	0.0031	0.0060
H34	0.0417	0.0534	0.0304	0.0021	0.0046	0.0063
H35	0.0364	0.0539	0.0363	0.0070	0.0002	0.0053
H36	0.0396	0.0526	0.0318	0.0008	0.0056	0.0069
H37	0.0352	0.0499	0.0373	0.0047	0.0002	0.0059
N3	0.0228 (13)	0.0404 (15)	0.0318 (14)	−0.0003 (11)	−0.0016 (11)	0.0028 (13)
N4	0.0285 (14)	0.0575 (18)	0.0302 (15)	−0.0034 (13)	0.0051 (12)	−0.0152 (14)
C18	0.0226 (16)	0.0301 (17)	0.0393 (19)	−0.0003 (13)	−0.0067 (14)	0.0013 (15)
C19	0.0262 (16)	0.0307 (17)	0.0283 (17)	−0.0011 (13)	−0.0043 (13)	0.0031 (14)
C20	0.0224 (15)	0.0241 (15)	0.0240 (16)	0.0001 (12)	−0.0018 (12)	−0.0064 (13)
C21	0.0276 (17)	0.051 (2)	0.041 (2)	0.0067 (15)	−0.0010 (15)	0.0186 (17)
C22	0.0296 (18)	0.059 (2)	0.044 (2)	0.0044 (16)	0.0016 (16)	0.0226 (18)
C23	0.0266 (16)	0.0273 (16)	0.0199 (16)	−0.0014 (13)	−0.0009 (13)	−0.0087 (13)
C24	0.0357 (19)	0.049 (2)	0.047 (2)	0.0114 (16)	0.0132 (16)	0.0108 (18)
C25	0.046 (2)	0.049 (2)	0.051 (2)	0.0048 (17)	0.0226 (18)	0.0084 (18)
C26	0.0295 (19)	0.122 (3)	0.038 (2)	0.021 (2)	0.0053 (17)	0.019 (2)
C27	0.0292 (18)	0.101 (3)	0.037 (2)	0.0150 (19)	0.0054 (16)	0.028 (2)
H18	0.0355	0.0505	0.0424	0.0060	0.0026	0.0044
H19	0.0410	0.0488	0.0374	0.0004	0.0048	0.0073
H21	0.0371	0.0521	0.0398	0.0068	0.0013	0.0044
H22	0.0430	0.0510	0.0362	0.0015	0.0061	0.0075
H24	0.0347	0.0532	0.0386	0.0037	−0.0008	0.0044
H25	0.0398	0.0550	0.0337	−0.0007	0.0038	0.0062
H26	0.0345	0.0589	0.0384	0.0053	−0.0011	0.0033
H27	0.0420	0.0556	0.0325	0.0021	0.0032	0.0059
N5	0.0272 (13)	0.0387 (15)	0.0307 (15)	−0.0045 (11)	0.0067 (11)	0.0079 (13)
N6	0.0242 (13)	0.0366 (14)	0.0248 (14)	0.0018 (11)	0.0059 (11)	0.0049 (12)
C59	0.0275 (16)	0.0392 (18)	0.0348 (19)	−0.0098 (14)	−0.0011 (14)	0.0078 (16)
C60	0.0295 (16)	0.0368 (17)	0.0213 (15)	−0.0072 (13)	0.0001 (13)	0.0031 (14)
C61	0.0249 (15)	0.0215 (15)	0.0191 (15)	0.0009 (12)	0.0014 (12)	0.0014 (12)
C62	0.0273 (16)	0.0455 (19)	0.0187 (15)	−0.0048 (14)	−0.0016 (13)	0.0005 (14)
C63	0.0332 (18)	0.052 (2)	0.0229 (17)	−0.0062 (15)	0.0048 (14)	0.0043 (15)
C64	0.0252 (14)	0.0185 (14)	0.0179 (14)	0.0002 (12)	0.0022 (12)	−0.0026 (12)
C65	0.0236 (15)	0.0313 (16)	0.0245 (16)	−0.0014 (12)	0.0008 (13)	0.0018 (14)
C66	0.0278 (16)	0.0360 (17)	0.0238 (16)	0.0036 (13)	−0.0003 (13)	0.0074 (14)
C67	0.0233 (15)	0.0399 (18)	0.0247 (16)	0.0007 (13)	0.0000 (13)	0.0022 (15)
C68	0.0276 (15)	0.0332 (16)	0.0201 (15)	0.0008 (13)	−0.0004 (12)	0.0032 (14)
H59	0.0322	0.0523	0.0371	−0.0059	−0.0016	0.0006
H60	0.0397	0.0548	0.0303	−0.0041	0.0028	0.0026
H61	0.0328	0.0578	0.0379	−0.0067	−0.0022	0.0001
H63	0.0393	0.0554	0.0302	−0.0045	0.0030	0.0011
H65	0.0313	0.0558	0.0412	−0.0012	−0.0009	0.0068
H66	0.0395	0.0585	0.0364	−0.0034	0.0028	0.0109
H67	0.0307	0.0650	0.0429	−0.0019	−0.0010	0.0074
H68	0.0384	0.0590	0.0349	−0.0021	0.0012	0.0091
N7	0.0277 (13)	0.0354 (14)	0.0253 (14)	−0.0030 (11)	0.0035 (11)	−0.0039 (12)
N8	0.0309 (14)	0.0380 (15)	0.0340 (16)	0.0001 (12)	0.0086 (12)	−0.0054 (13)
C1	0.056 (2)	0.054 (2)	0.034 (2)	0.0321 (18)	0.0082 (17)	0.0060 (17)
C2	0.064 (2)	0.052 (2)	0.0256 (18)	0.0327 (18)	0.0101 (16)	0.0069 (17)
C3	0.0260 (15)	0.0280 (16)	0.0233 (16)	−0.0048 (13)	0.0033 (13)	−0.0046 (14)
C4	0.0275 (18)	0.132 (3)	0.0256 (19)	0.017 (2)	−0.0029 (15)	−0.008 (2)
C5	0.0304 (19)	0.125 (3)	0.0269 (19)	0.012 (2)	0.0008 (16)	−0.014 (2)
C6	0.0233 (14)	0.0267 (15)	0.0220 (15)	−0.0055 (13)	0.0047 (12)	−0.0027 (14)
C7	0.0248 (17)	0.106 (3)	0.0241 (17)	0.0104 (18)	−0.0022 (14)	−0.007 (2)
C8	0.0239 (17)	0.099 (3)	0.0192 (16)	0.0024 (18)	0.0020 (14)	−0.0091 (18)
C9	0.068 (2)	0.077 (3)	0.0176 (17)	0.042 (2)	0.0018 (17)	−0.0017 (18)
C10	0.060 (2)	0.085 (3)	0.0225 (18)	0.045 (2)	−0.0036 (17)	−0.0025 (19)
H1	0.0421	0.0679	0.0388	0.0124	0.0033	0.0028
H2	0.0472	0.0646	0.0302	0.0075	0.0063	0.0012
H4	0.0454	0.0647	0.0358	0.0128	0.0022	0.0017
H5	0.0521	0.0702	0.0303	0.0117	0.0080	0.0004
H7	0.0390	0.0627	0.0355	0.0066	0.0002	−0.0001
H8	0.0456	0.0596	0.0284	0.0053	0.0042	−0.0031
H9	0.0496	0.0638	0.0286	0.0087	0.0036	−0.0041
H10	0.0407	0.0617	0.0354	0.0092	−0.0007	−0.0029
O1	0.0305 (11)	0.0340 (11)	0.0329 (12)	0.0020 (9)	0.0098 (9)	0.0037 (10)
O2	0.0260 (10)	0.0310 (11)	0.0295 (12)	−0.0032 (9)	0.0100 (9)	0.0053 (9)
C52	0.0322 (17)	0.051 (2)	0.0292 (18)	−0.0090 (15)	0.0104 (14)	−0.0016 (16)
C53	0.0220 (15)	0.0392 (18)	0.0180 (15)	−0.0088 (13)	0.0035 (12)	−0.0015 (14)
C54	0.0306 (16)	0.0282 (16)	0.0217 (16)	−0.0069 (13)	0.0022 (13)	0.0028 (13)
C55	0.0241 (15)	0.0341 (17)	0.0156 (15)	−0.0021 (13)	−0.0005 (12)	0.0007 (13)
C56	0.0185 (14)	0.0335 (16)	0.0155 (14)	−0.0035 (12)	0.0036 (11)	0.0015 (13)
C57	0.0218 (15)	0.0314 (16)	0.0157 (14)	−0.0040 (13)	−0.0004 (12)	−0.0004 (13)
C58	0.0221 (15)	0.0317 (16)	0.0230 (16)	0.0009 (13)	0.0037 (12)	−0.0009 (14)
H1O	0.0343	0.0421	0.0370	−0.0010	0.0061	0.0025
H2O	0.0322	0.0415	0.0387	−0.0019	0.0069	0.0019
H52A	0.0456	0.0520	0.0438	−0.0138	0.0042	−0.0095
H52B	0.0412	0.0442	0.0562	0.0063	0.0105	0.0048
H52C	0.0433	0.0644	0.0334	−0.0019	−0.0001	0.0110
H54	0.0430	0.0367	0.0429	−0.0021	0.0062	0.0052
H56	0.0337	0.0455	0.0430	−0.0024	0.0094	0.0036
H58	0.0366	0.0403	0.0451	0.0037	0.0076	0.0005
O3	0.0229 (10)	0.0537 (13)	0.0241 (11)	0.0042 (9)	−0.0031 (9)	−0.0141 (10)
O4	0.0254 (11)	0.0838 (16)	0.0273 (12)	−0.0104 (11)	0.0030 (9)	−0.0242 (12)
C38	0.0150 (14)	0.0413 (17)	0.0237 (15)	0.0005 (13)	0.0049 (12)	−0.0050 (14)
C39	0.0226 (15)	0.0300 (16)	0.0167 (15)	0.0035 (12)	−0.0047 (12)	−0.0007 (13)
C40	0.0266 (15)	0.0342 (16)	0.0148 (14)	0.0078 (13)	0.0030 (12)	0.0015 (13)
C41	0.0206 (14)	0.0322 (16)	0.0231 (15)	0.0049 (13)	0.0031 (12)	0.0115 (14)
C42	0.0229 (15)	0.0420 (18)	0.0212 (16)	−0.0042 (13)	−0.0030 (13)	0.0014 (14)
C43	0.0241 (16)	0.0445 (18)	0.0185 (16)	−0.0002 (13)	0.0006 (13)	−0.0057 (14)
C44	0.0259 (16)	0.052 (2)	0.0317 (17)	0.0033 (15)	0.0048 (13)	0.0117 (16)
H3O	0.0320	0.0513	0.0345	0.0018	0.0040	−0.0026
H4O	0.0313	0.0556	0.0361	−0.0006	0.0026	−0.0035
H38	0.0314	0.0595	0.0387	0.0000	0.0056	−0.0041
H40	0.0403	0.0624	0.0319	0.0020	0.0044	−0.0058
H42	0.0347	0.0666	0.0384	−0.0035	−0.0025	−0.0058
H44A	0.0459	0.0584	0.0563	0.0040	0.0097	−0.0066
H44B	0.0442	0.0705	0.0457	0.0040	0.0064	0.0166
H44C	0.0376	0.0858	0.0386	−0.0020	−0.0038	−0.0048
O5	0.0237 (10)	0.0421 (11)	0.0180 (10)	−0.0030 (9)	0.0028 (8)	−0.0022 (10)
O6	0.0277 (11)	0.0477 (13)	0.0200 (10)	−0.0067 (9)	−0.0014 (9)	0.0016 (10)
C45	0.0172 (13)	0.0274 (15)	0.0236 (15)	−0.0012 (12)	0.0037 (12)	0.0000 (13)
C46	0.0245 (15)	0.0257 (15)	0.0211 (15)	−0.0012 (12)	−0.0022 (12)	0.0002 (13)
C47	0.0280 (15)	0.0288 (16)	0.0197 (15)	−0.0027 (13)	0.0062 (12)	−0.0001 (13)
C48	0.0234 (15)	0.0265 (16)	0.0263 (16)	0.0000 (12)	0.0059 (12)	−0.0012 (14)
C49	0.0178 (14)	0.0311 (16)	0.0298 (16)	−0.0011 (12)	−0.0017 (12)	0.0001 (14)
C50	0.0245 (15)	0.0234 (15)	0.0181 (14)	0.0007 (12)	0.0031 (12)	−0.0037 (13)
C51	0.0240 (16)	0.050 (2)	0.044 (2)	0.0020 (15)	0.0120 (14)	0.0060 (17)
H5O	0.0316	0.0512	0.0350	−0.0010	0.0045	0.0009
H6O	0.0348	0.0530	0.0337	−0.0005	0.0060	0.0003
H45	0.0327	0.0586	0.0377	−0.0016	0.0068	0.0005
H47	0.0430	0.0640	0.0303	0.0005	0.0066	0.0023
H49	0.0350	0.0627	0.0366	−0.0009	−0.0004	0.0036
H51A	0.0476	0.0604	0.0522	0.0000	0.0123	−0.0110
H51B	0.0479	0.0574	0.0547	0.0005	0.0119	0.0158
H51C	0.0398	0.0805	0.0381	−0.0003	−0.0008	0.0045
O7	0.0338 (11)	0.0304 (11)	0.0338 (12)	−0.0041 (9)	0.0086 (9)	−0.0075 (10)
O8	0.0313 (11)	0.0261 (11)	0.0289 (12)	−0.0003 (9)	0.0081 (9)	−0.0047 (9)
C11	0.0237 (14)	0.0301 (16)	0.0158 (14)	0.0025 (13)	0.0007 (11)	−0.0020 (13)
C12	0.0293 (16)	0.0283 (17)	0.0192 (15)	−0.0029 (13)	0.0002 (13)	−0.0011 (13)
C13	0.0356 (17)	0.0233 (15)	0.0203 (16)	0.0004 (13)	0.0013 (13)	−0.0045 (13)
C14	0.0274 (16)	0.0330 (17)	0.0149 (15)	0.0051 (13)	0.0013 (12)	−0.0002 (13)
C15	0.0235 (15)	0.0289 (16)	0.0195 (15)	−0.0028 (12)	0.0005 (12)	0.0003 (13)
C16	0.0287 (16)	0.0258 (15)	0.0135 (14)	−0.0001 (13)	−0.0004 (12)	−0.0005 (13)
C17	0.0337 (17)	0.0404 (18)	0.0260 (17)	0.0043 (14)	0.0065 (14)	−0.0061 (15)
H7O	0.0387	0.0485	0.0370	0.0041	0.0074	−0.0036
H8O	0.0390	0.0499	0.0383	0.0025	0.0066	−0.0054
H11	0.0389	0.0526	0.0434	0.0047	0.0097	−0.0053
H13	0.0460	0.0442	0.0424	0.0033	0.0063	−0.0057
H15	0.0405	0.0500	0.0450	−0.0040	0.0062	−0.0036
H17A	0.0462	0.0689	0.0353	0.0021	0.0000	−0.0152
H17B	0.0459	0.0517	0.0559	−0.0046	0.0104	−0.0030
H17C	0.0483	0.0667	0.0382	0.0143	0.0014	0.0076

Geometric parameters (Å, °)

O1—C55	1.368 (3)	C60—H60	1.0800
O2—C57	1.371 (3)	C62—H61	1.0800
O1—H1O	0.9900	C63—H63	1.0800
O2—H2O	0.9900	C65—H65	1.0800
N1—C28	1.337 (4)	C66—H66	1.0800
N1—C32	1.340 (4)	C67—H67	1.0800
N2—C36	1.337 (3)	C68—H68	1.0800
N2—C35	1.340 (4)	C1—C2	1.379 (5)
O3—C39	1.371 (3)	C2—C3	1.372 (4)
O4—C43	1.372 (3)	C3—C4	1.384 (4)
O3—H3O	0.9900	C3—C6	1.485 (4)
O4—H4O	0.9900	C4—C5	1.384 (5)
N3—C22	1.342 (4)	C6—C7	1.378 (4)
N3—C18	1.337 (4)	C6—C9	1.375 (4)
N4—C26	1.313 (4)	C7—C8	1.376 (4)
N4—C25	1.330 (4)	C9—C10	1.376 (5)
O5—C50	1.379 (3)	C1—H1	1.0800
O6—C46	1.373 (3)	C2—H2	1.0800
O5—H5O	0.9900	C4—H4	1.0800
O6—H6O	0.9900	C5—H5	1.0800
N5—C63	1.340 (4)	C7—H7	1.0800
N5—C59	1.348 (4)	C8—H8	1.0800
N6—C67	1.343 (4)	C9—H9	1.0800
N6—C66	1.342 (3)	C10—H10	1.0800
O7—C12	1.372 (3)	C52—C53	1.508 (4)
O8—C16	1.371 (3)	C53—C54	1.393 (4)
O7—H7O	0.9900	C53—C58	1.400 (4)
O8—H8O	0.9900	C54—C55	1.390 (4)
N7—C8	1.323 (4)	C55—C56	1.394 (4)
N7—C10	1.328 (4)	C56—C57	1.393 (4)
N8—C1	1.332 (4)	C57—C58	1.398 (4)
N8—C5	1.330 (4)	C52—H52C	1.0800
C28—C29	1.381 (4)	C52—H52A	1.0800
C29—C30	1.394 (4)	C52—H52B	1.0800
C30—C33	1.489 (4)	C54—H54	1.0800
C30—C31	1.388 (4)	C56—H56	1.0800
C31—C32	1.388 (4)	C58—H58	1.0800
C33—C37	1.395 (4)	C38—C39	1.393 (4)
C33—C34	1.396 (4)	C38—C43	1.390 (4)
C34—C35	1.383 (4)	C39—C40	1.388 (4)
C36—C37	1.389 (4)	C40—C41	1.390 (4)
C28—H28	1.0800	C41—C44	1.517 (4)
C29—H29	1.0800	C41—C42	1.391 (4)
C31—H31	1.0800	C42—C43	1.394 (4)
C32—H32	1.0800	C38—H38	1.0800
C34—H34	1.0800	C40—H40	1.0800
C35—H35	1.0800	C42—H42	1.0800
C36—H36	1.0800	C44—H44C	1.0800
C37—H37	1.0800	C44—H44A	1.0800
C18—C19	1.382 (4)	C44—H44B	1.0800
C19—C20	1.390 (4)	C45—C50	1.392 (3)
C20—C21	1.385 (4)	C45—C46	1.394 (4)
C20—C23	1.490 (4)	C46—C47	1.393 (4)
C21—C22	1.385 (4)	C47—C48	1.391 (4)
C23—C27	1.372 (4)	C48—C51	1.512 (4)
C23—C24	1.374 (4)	C48—C49	1.395 (4)
C24—C25	1.386 (4)	C49—C50	1.394 (4)
C26—C27	1.383 (4)	C45—H45	1.0800
C18—H18	1.0800	C47—H47	1.0800
C19—H19	1.0800	C49—H49	1.0800
C21—H21	1.0800	C51—H51B	1.0800
C22—H22	1.0800	C51—H51C	1.0800
C24—H24	1.0800	C51—H51A	1.0800
C25—H25	1.0800	C11—C16	1.389 (4)
C26—H26	1.0800	C11—C12	1.395 (4)
C27—H27	1.0800	C12—C13	1.391 (4)
C59—C60	1.381 (4)	C13—C14	1.390 (4)
C60—C61	1.390 (4)	C14—C15	1.398 (4)
C61—C64	1.491 (3)	C14—C17	1.516 (4)
C61—C62	1.392 (4)	C15—C16	1.396 (3)
C62—C63	1.382 (4)	C11—H11	1.0800
C64—C65	1.396 (4)	C13—H13	1.0800
C64—C68	1.396 (4)	C15—H15	1.0800
C65—C66	1.384 (4)	C17—H17A	1.0800
C67—C68	1.383 (4)	C17—H17B	1.0800
C59—H59	1.0800	C17—H17C	1.0800
O1···N6^i	2.785 (3)	C63···H2O	2.6900
O1···C1^ii	3.324 (4)	C65···H60	2.7100
O1···C2^ii	3.366 (4)	C66···H1O^i	2.6800
O2···C7^iii	3.294 (3)	C67···H1^viii	2.9000
O2···N5	2.755 (3)	C67···H1O^i	2.8200
O2···C47^iii	3.386 (3)	C67···H56^i	2.9000
O3···C66^i	3.393 (3)	C68···H61	2.6900
O3···N2	2.745 (3)	H1···O1^iii	2.6300
O4···C35^iv	3.260 (3)	H1···C67^xii	2.9000
O4···C34^iv	3.189 (3)	H1···H67^xii	2.3600
O4···N4	2.791 (3)	H1···N6^xii	2.9100
O5···C29^iii	3.310 (3)	H1···H1O^iii	2.4500
O5···N1	2.776 (3)	H1O···N6^i	1.8000
O6···C8	3.381 (3)	H1O···H56	2.3500
O6···N3	2.784 (3)	H1O···H1^ii	2.4500
O7···N7	2.773 (3)	H1O···C66^i	2.6800
O7···C59^v	3.336 (4)	H1O···C67^i	2.8200
O8···C40^iv	3.419 (3)	H2···O1^iii	2.6800
O1···H1^ii	2.6300	H2···C54^iii	2.8500
O1···H2^ii	2.6800	H2···H7	2.0500
O2···H7^iii	2.5600	H2···C55^iii	2.8300
O2···H47^iii	2.4000	H2···C7	2.6600
O3···H66^i	2.5800	H2O···N5	1.7600
O4···H35^iv	2.6100	H2O···H56	2.3000
O4···H34^iv	2.4300	H2O···C63	2.6900
O5···H29^iii	2.6300	H2O···C59	2.7500
O5···H28^iii	2.9100	H3O···H38	2.3500
O6···H8	2.5900	H3O···C35	2.6700
O6···H54^iii	2.7800	H3O···C36	2.7500
O6···H7	2.9000	H3O···N2	1.7500
O6···H58^ii	2.6800	H3O···H66^i	2.5500
O7···H59^v	2.6100	H4···C9	2.6100
O7···H60^v	2.8200	H4···H9	1.9700
O7···H44B^vi	2.5600	H4···C53^v	2.7900
O8···H40^iv	2.3400	H4···C58^v	2.9700
N1···O5	2.776 (3)	H4···C52^v	2.8900
N2···O3	2.745 (3)	H4···H52A^v	2.5900
N3···O6	2.784 (3)	H4O···H38	2.2600
N4···O4	2.791 (3)	H4O···H35^iv	2.3800
N5···O2	2.755 (3)	H4O···N4	1.8100
N6···O1^i	2.785 (3)	H4O···C26	2.7100
N6···C56^i	3.400 (3)	H4O···C25	2.7900
N7···O7	2.773 (3)	H5···H52A^v	2.4400
N7···C11	3.322 (3)	H5O···C32	2.7600
N8···C11^vii	3.394 (3)	H5O···H45	2.2800
N8···O8^vii	2.768 (3)	H5O···N1	1.7900
N1···H28^iii	2.9300	H5O···C28	2.7200
N1···H5O	1.7900	H6O···H45	2.2600
N1···H45	2.7500	H6O···N3	1.7900
N2···H38	2.7400	H6O···C22	2.7400
N2···H3O	1.7500	H6O···C18	2.7600
N3···H6O	1.7900	H7···O6	2.9000
N3···H45	2.6900	H7···C2	2.7000
N4···H38	2.8100	H7···O2^ii	2.5600
N4···H35^iv	2.7500	H7···H2	2.0500
N4···H4O	1.8100	H7O···C10	2.7700
N5···H56	2.6900	H7O···C8	2.6900
N5···H2O	1.7600	H7O···N7	1.7800
N6···H1^viii	2.9100	H7O···H11	2.2600
N6···H56^i	2.6400	H7O···H59^v	2.5200
N6···H1O^i	1.8000	H8···O6	2.5900
N7···H7O	1.7800	H8···H22	2.5400
N7···H11	2.5300	H8···H58^ii	2.5000
N8···H8O^vii	1.7800	H8O···H11	2.2800
N8···H11^vii	2.6200	H9···C53^v	2.9800
C1···C59^ii	3.271 (4)	H9···C57^v	2.6600
C1···O1^iii	3.324 (4)	H9···C56^v	2.9700
C2···C55^iii	3.593 (4)	H9···C4	2.6500
C2···O1^iii	3.366 (4)	H9···C58^v	2.6800
C7···O2^ii	3.294 (3)	H9···H4	1.9700
C8···O6	3.381 (3)	H10···C57^v	3.0600
C9···C57^v	3.483 (4)	H10···C56^v	2.9600
C11···N7	3.322 (3)	H10···C59^v	2.9900
C12···C60^v	3.567 (4)	H10···H59^v	2.2200
C13···C40^vi	3.526 (4)	H11···H8O	2.2800
C18···C28	3.543 (4)	H11···H7O	2.2600
C18···C44^iv	3.536 (4)	H11···N7	2.5300
C19···C44^iv	3.392 (4)	H13···C39^vi	2.9800
C19···C41^iv	3.481 (4)	H13···H60^v	2.5100
C19···O5^iii	3.332 (3)	H13···C40^vi	2.5600
C24···C34	3.374 (4)	H13···H40^vi	2.5000
C24···C43^iv	3.461 (4)	H15···O3^iv	2.5100
C25···C38^iv	3.582 (4)	H15···H17B	2.3800
C25···C35	3.577 (4)	H17A···C38^vi	2.9600
C28···C18	3.543 (4)	H17A···H27	2.3900
C29···O5^ii	3.310 (3)	H17A···C39^vi	3.0500
C29···C45^ii	3.590 (4)	H17B···H15	2.3800
C29···C50^ii	3.213 (4)	H18···H45	2.4000
C29···C49^ii	3.584 (4)	H19···C50^iii	3.1000
C31···C52	3.546 (4)	H19···C24	2.6600
C31···C50^iii	3.461 (4)	H19···O5^iii	2.4700
C31···C45^iii	3.444 (4)	H19···H24	2.0400
C31···C53	3.579 (3)	H21···C14	3.0700
C31···C46^iii	3.584 (4)	H21···H27	2.0100
C32···C52	3.514 (4)	H21···C13	2.8600
C32···C45^iii	3.380 (4)	H21···C27	2.6400
C34···C24	3.374 (4)	H21···C12	3.0600
C34···O4^vi	3.189 (3)	H22···H8	2.5400
C35···O4^vi	3.260 (3)	H22···H44B^vi	2.5600
C35···C25	3.577 (4)	H24···H19	2.0400
C36···C56	3.589 (4)	H24···H49^iii	2.3500
C36···C55	3.543 (4)	H24···C19	2.7000
C37···C56	3.476 (4)	H24···C49^iii	2.9500
C37···C55	3.344 (4)	H27···H17A	2.3900
C37···C54	3.547 (4)	H27···H21	2.0100
C38···C25^vi	3.582 (4)	H27···C21	2.6700
C40···C13^iv	3.526 (4)	H27···C15	3.0300
C41···C19^vi	3.481 (4)	H27···C14	2.7000
C43···C24^vi	3.461 (4)	H27···C17	2.7600
C44···C19^vi	3.392 (4)	H28···H45	2.5900
C44···C18^vi	3.536 (4)	H28···C32^ii	2.8500
C45···C29^iii	3.590 (4)	H28···H32^ii	2.2600
C45···C32^ii	3.380 (4)	H28···N1^ii	2.9300
C45···C31^ii	3.444 (4)	H28···O5^ii	2.9100
C46···C31^ii	3.584 (4)	H29···H34	2.1200
C47···O2^ii	3.386 (3)	H29···C34	2.6700
C49···C29^iii	3.584 (4)	H29···C50^ii	2.6500
C50···C29^iii	3.213 (4)	H29···C49^ii	2.8400
C50···C31^ii	3.461 (4)	H29···O5^ii	2.6300
C52···C32	3.514 (4)	H31···C58	3.0700
C52···C31	3.546 (4)	H31···C46^iii	2.7500
C53···C31	3.579 (3)	H31···C37	2.7300
C54···C37	3.547 (4)	H31···C48^iii	2.9600
C55···C37	3.344 (4)	H31···C45^iii	2.9600
C55···C2^ii	3.593 (4)	H31···C47^iii	2.7300
C55···C36	3.543 (4)	H31···H37	2.0900
C56···C37	3.476 (4)	H32···C45^iii	2.8600
C56···C36	3.589 (4)	H32···H28^iii	2.2600
C56···N6^i	3.400 (3)	H34···C29	2.7400
C57···C9^ix	3.483 (4)	H34···H29	2.1200
C59···O7^ix	3.336 (4)	H34···O4^vi	2.4300
C59···C1^iii	3.271 (4)	H35···N4^vi	2.7500
C60···C12^ix	3.567 (4)	H35···O4^vi	2.6100
C62···C66^x	3.567 (4)	H35···H4O^vi	2.3800
C65···O8^xi	3.336 (3)	H35···H38	2.5200
C66···O3^i	3.393 (3)	H35···C26^vi	3.0300
C66···C62^x	3.567 (4)	H36···C56	3.0600
C68···C16^iv	3.510 (4)	H37···C58	2.8900
C1···H59^ii	3.0800	H37···C57	2.8000
C1···H8O^vii	2.7500	H37···C54	3.0700
C2···H7	2.7000	H37···H31	2.0900
C4···H9	2.6500	H37···C55	2.9500
C5···H8O^vii	2.6900	H37···C53	3.0500
C5···H52A^v	3.0500	H37···C56	2.8400
C7···H2	2.6600	H37···C31	2.6600
C8···H7O	2.6900	H38···H3O	2.3500
C8···H58^ii	2.9500	H38···N2	2.7400
C9···H4	2.6100	H38···H35	2.5200
C10···H59^v	3.0000	H38···H4O	2.2600
C10···H7O	2.7700	H38···N4	2.8100
C12···H21	3.0600	H38···C35	2.8400
C12···H60^v	2.9000	H40···H13^iv	2.5000
C13···H21	2.8600	H42···H44C	2.4600
C13···H60^v	2.7600	H44A···C19^vi	2.9800
C14···H21	3.0700	H44A···C18^vi	2.9100
C14···H27	2.7000	H44B···O7^iv	2.5600
C15···H27	3.0300	H44C···H42	2.4600
C16···H40^iv	2.8900	H45···C18	2.7900
C17···H27	2.7600	H45···H6O	2.2600
C18···H6O	2.7600	H45···H18	2.4000
C18···H45	2.7900	H45···N3	2.6900
C18···H44A^iv	2.9100	H45···N1	2.7500
C19···H24	2.7000	H45···H5O	2.2800
C19···H44A^iv	2.9800	H45···C28	2.9300
C21···H27	2.6700	H45···H28	2.5900
C22···H6O	2.7400	H47···H54^iii	2.3800
C24···H19	2.6600	H47···O2^ii	2.4000
C25···H4O	2.7900	H47···C57^ii	3.0400
C26···H4O	2.7100	H49···H51C	2.3500
C26···H35^iv	3.0300	H51B···C37^ii	3.0000
C27···H21	2.6400	H51B···C36^ii	3.0100
C28···H45	2.9300	H51C···H49	2.3500
C28···H5O	2.7200	H52A···H4^ix	2.5900
C29···H34	2.7400	H52A···H5^ix	2.4400
C31···H37	2.6600	H52A···C5^ix	3.0500
C31···H52C	2.9500	H52B···H58	2.4600
C32···H52C	2.8400	H52C···C32	2.8400
C32···H5O	2.7600	H52C···C31	2.9500
C32···H28^iii	2.8500	H54···H47^ii	2.3800
C34···H29	2.6700	H54···C46^ii	2.9400
C35···H3O	2.6700	H54···C47^ii	2.7200
C35···H38	2.8400	H54···O6^ii	2.7800
C36···H3O	2.7500	H56···H2O	2.3000
C36···H51B^iii	3.0100	H56···N6^i	2.6400
C37···H51B^iii	3.0000	H56···H1O	2.3500
C37···H31	2.7300	H56···N5	2.6900
C38···H17A^iv	2.9600	H56···C67^i	2.9000
C39···H13^iv	2.9800	H58···O6^iii	2.6800
C39···H17A^iv	3.0500	H58···C8^iii	2.9500
C40···H13^iv	2.5600	H58···H8^iii	2.5000
C45···H31^ii	2.9600	H58···H52B	2.4600
C45···H32^ii	2.8600	H59···H7O^ix	2.5200
C46···H31^ii	2.7500	H59···H10^ix	2.2200
C46···H54^iii	2.9400	H59···C10^ix	3.0000
C47···H31^ii	2.7300	H59···C1^iii	3.0800
C47···H54^iii	2.7200	H59···O7^ix	2.6100
C48···H31^ii	2.9600	H60···C65	2.7100
C49···H29^iii	2.8400	H60···H65	2.1500
C50···H29^iii	2.6500	H60···O7^ix	2.8200
C52···H4^ix	2.8900	H60···O8^xi	2.8800
C53···H37	3.0500	H60···H13^ix	2.5100
C53···H9^ix	2.9800	H60···C12^ix	2.9000
C53···H4^ix	2.7900	H60···C13^ix	2.7600
C54···H2^ii	2.8500	H61···C68	2.6900
C54···H37	3.0700	H61···H68	2.1800
C55···H2^ii	2.8300	H61···C14^iv	2.8700
C55···H37	2.9500	H61···C15^iv	2.7300
C56···H9^ix	2.9700	H61···C17^iv	2.9500
C56···H36	3.0600	H65···O8^xi	2.3200
C56···H37	2.8400	H65···H60	2.1500
C56···H10^ix	2.9600	H65···C60	2.7000
C57···H10^ix	3.0600	H66···O3^i	2.5800
C57···H37	2.8000	H66···H3O^i	2.5500
C57···H47^iii	3.0400	H66···H15^xi	2.5600
C57···H9^ix	2.6600	H67···C11^iv	3.0000
C58···H9^ix	2.6800	H67···H1^viii	2.3600
C58···H4^ix	2.9700	H68···C11^iv	3.0700
C58···H31	3.0700	H68···C15^iv	2.8400
C58···H37	2.8900	H68···C16^iv	2.8300
C59···H10^ix	2.9900	H68···C14^iv	3.0500
C59···H2O	2.7500	H68···C62	2.7600
C60···H65	2.7000	H68···H61	2.1800
C62···H68	2.7600
C55—O1—H1O	113.00	C6—C7—C8	120.4 (3)
C57—O2—H2O	113.00	N7—C8—C7	124.2 (3)
C28—N1—C32	116.1 (2)	C6—C9—C10	120.5 (3)
C35—N2—C36	116.1 (2)	N7—C10—C9	124.0 (3)
C39—O3—H3O	112.00	C2—C1—H1	122.00
C43—O4—H4O	110.00	N8—C1—H1	113.00
C18—N3—C22	116.0 (2)	C3—C2—H2	120.00
C25—N4—C26	115.2 (3)	C1—C2—H2	119.00
C50—O5—H5O	110.00	C5—C4—H4	120.00
C46—O6—H6O	110.00	C3—C4—H4	120.00
C59—N5—C63	116.2 (2)	N8—C5—H5	117.00
C66—N6—C67	116.2 (2)	C4—C5—H5	119.00
C12—O7—H7O	110.00	C6—C7—H7	121.00
C16—O8—H8O	111.00	C8—C7—H7	117.00
C8—N7—C10	115.4 (2)	C7—C8—H8	121.00
C1—N8—C5	115.4 (3)	N7—C8—H8	115.00
N1—C28—C29	124.0 (2)	C6—C9—H9	122.00
C28—C29—C30	119.8 (2)	C10—C9—H9	118.00
C29—C30—C33	121.6 (2)	N7—C10—H10	113.00
C29—C30—C31	116.6 (2)	C9—C10—H10	122.00
C31—C30—C33	121.8 (2)	C54—C53—C58	119.4 (2)
C30—C31—C32	119.7 (2)	C52—C53—C58	120.8 (2)
N1—C32—C31	123.8 (2)	C52—C53—C54	119.8 (2)
C30—C33—C34	121.8 (2)	C53—C54—C55	120.5 (2)
C34—C33—C37	116.8 (2)	O1—C55—C56	121.6 (2)
C30—C33—C37	121.4 (2)	O1—C55—C54	118.1 (2)
C33—C34—C35	119.2 (2)	C54—C55—C56	120.3 (2)
N2—C35—C34	124.4 (2)	C55—C56—C57	119.4 (2)
N2—C36—C37	123.9 (2)	C56—C57—C58	120.5 (2)
C33—C37—C36	119.6 (2)	O2—C57—C58	117.9 (2)
N1—C28—H28	117.00	O2—C57—C56	121.6 (2)
C29—C28—H28	119.00	C53—C58—C57	119.8 (2)
C28—C29—H29	120.00	C53—C52—H52B	115.00
C30—C29—H29	120.00	C53—C52—H52A	112.00
C32—C31—H31	117.00	C53—C52—H52C	111.00
C30—C31—H31	123.00	H52A—C52—H52B	103.00
N1—C32—H32	115.00	H52A—C52—H52C	108.00
C31—C32—H32	122.00	H52B—C52—H52C	108.00
C35—C34—H34	117.00	C55—C54—H54	120.00
C33—C34—H34	123.00	C53—C54—H54	120.00
N2—C35—H35	116.00	C55—C56—H56	122.00
C34—C35—H35	119.00	C57—C56—H56	119.00
N2—C36—H36	116.00	C53—C58—H58	121.00
C37—C36—H36	120.00	C57—C58—H58	120.00
C33—C37—H37	120.00	C39—C38—C43	119.1 (2)
C36—C37—H37	121.00	C38—C39—C40	120.4 (2)
N3—C18—C19	123.7 (2)	O3—C39—C40	118.2 (2)
C18—C19—C20	120.2 (2)	O3—C39—C38	121.4 (2)
C19—C20—C21	116.4 (2)	C39—C40—C41	120.3 (2)
C21—C20—C23	121.9 (2)	C40—C41—C44	119.4 (2)
C19—C20—C23	121.7 (2)	C42—C41—C44	120.9 (2)
C20—C21—C22	119.9 (3)	C40—C41—C42	119.6 (2)
N3—C22—C21	123.9 (3)	C41—C42—C43	119.9 (2)
C20—C23—C24	122.8 (2)	O4—C43—C38	121.7 (2)
C20—C23—C27	121.9 (3)	C38—C43—C42	120.7 (2)
C24—C23—C27	115.3 (3)	O4—C43—C42	117.6 (2)
C23—C24—C25	120.6 (3)	C39—C38—H38	122.00
N4—C25—C24	123.8 (3)	C43—C38—H38	119.00
N4—C26—C27	124.6 (3)	C39—C40—H40	117.00
C23—C27—C26	120.5 (3)	C41—C40—H40	122.00
N3—C18—H18	114.00	C43—C42—H42	117.00
C19—C18—H18	122.00	C41—C42—H42	123.00
C18—C19—H19	120.00	C41—C44—H44C	111.00
C20—C19—H19	120.00	C41—C44—H44B	110.00
C22—C21—H21	120.00	H44B—C44—H44C	108.00
C20—C21—H21	120.00	C41—C44—H44A	110.00
C21—C22—H22	120.00	H44A—C44—H44B	109.00
N3—C22—H22	116.00	H44A—C44—H44C	108.00
C23—C24—H24	122.00	C46—C45—C50	118.9 (2)
C25—C24—H24	118.00	O6—C46—C47	118.2 (2)
C24—C25—H25	121.00	C45—C46—C47	120.7 (2)
N4—C25—H25	115.00	O6—C46—C45	121.1 (2)
N4—C26—H26	114.00	C46—C47—C48	119.9 (2)
C27—C26—H26	122.00	C49—C48—C51	120.4 (2)
C26—C27—H27	118.00	C47—C48—C51	119.6 (2)
C23—C27—H27	122.00	C47—C48—C49	119.9 (2)
N5—C59—C60	124.1 (3)	C48—C49—C50	119.6 (2)
C59—C60—C61	119.4 (3)	C45—C50—C49	120.9 (2)
C62—C61—C64	121.6 (2)	O5—C50—C45	121.1 (2)
C60—C61—C64	121.6 (2)	O5—C50—C49	118.0 (2)
C60—C61—C62	116.8 (2)	C50—C45—H45	121.00
C61—C62—C63	120.1 (2)	C46—C45—H45	120.00
N5—C63—C62	123.5 (3)	C48—C47—H47	121.00
C65—C64—C68	117.1 (2)	C46—C47—H47	119.00
C61—C64—C65	121.7 (2)	C50—C49—H49	120.00
C61—C64—C68	121.3 (2)	C48—C49—H49	120.00
C64—C65—C66	119.5 (2)	C48—C51—H51C	111.00
N6—C66—C65	123.9 (3)	C48—C51—H51A	113.00
N6—C67—C68	124.1 (2)	C48—C51—H51B	112.00
C64—C68—C67	119.3 (2)	H51B—C51—H51C	107.00
N5—C59—H59	114.00	H51A—C51—H51C	107.00
C60—C59—H59	122.00	H51A—C51—H51B	107.00
C61—C60—H60	120.00	C12—C11—C16	119.0 (2)
C59—C60—H60	121.00	O7—C12—C11	121.0 (2)
C63—C62—H61	120.00	O7—C12—C13	118.5 (2)
C61—C62—H61	120.00	C11—C12—C13	120.6 (2)
C62—C63—H63	122.00	C12—C13—C14	120.2 (2)
N5—C63—H63	115.00	C15—C14—C17	120.2 (2)
C66—C65—H65	121.00	C13—C14—C15	119.8 (2)
C64—C65—H65	119.00	C13—C14—C17	120.1 (2)
C65—C66—H66	118.00	C14—C15—C16	119.5 (2)
N6—C66—H66	118.00	C11—C16—C15	120.9 (2)
N6—C67—H67	116.00	O8—C16—C11	120.9 (2)
C68—C67—H67	119.00	O8—C16—C15	118.2 (2)
C64—C68—H68	123.00	C12—C11—H11	120.00
C67—C68—H68	117.00	C16—C11—H11	121.00
N8—C1—C2	124.1 (3)	C12—C13—H13	118.00
C1—C2—C3	120.6 (3)	C14—C13—H13	122.00
C4—C3—C6	121.7 (3)	C14—C15—H15	121.00
C2—C3—C6	122.6 (3)	C16—C15—H15	119.00
C2—C3—C4	115.6 (3)	C14—C17—H17A	113.00
C3—C4—C5	120.4 (3)	C14—C17—H17B	111.00
N8—C5—C4	123.9 (3)	C14—C17—H17C	109.00
C3—C6—C7	122.6 (2)	H17A—C17—H17B	108.00
C3—C6—C9	121.9 (3)	H17A—C17—H17C	109.00
C7—C6—C9	115.5 (2)	H17B—C17—H17C	106.00
C32—N1—C28—C29	−1.5 (4)	N8—C1—C2—C3	−0.1 (5)
C28—N1—C32—C31	1.2 (4)	C1—C2—C3—C4	0.4 (5)
C36—N2—C35—C34	0.0 (4)	C1—C2—C3—C6	177.5 (3)
C35—N2—C36—C37	0.7 (4)	C2—C3—C4—C5	0.1 (5)
C22—N3—C18—C19	−0.4 (4)	C6—C3—C4—C5	−177.0 (3)
C18—N3—C22—C21	0.4 (4)	C2—C3—C6—C7	−6.3 (4)
C26—N4—C25—C24	−1.6 (5)	C2—C3—C6—C9	174.9 (3)
C25—N4—C26—C27	0.9 (5)	C4—C3—C6—C7	170.6 (3)
C59—N5—C63—C62	−0.8 (4)	C4—C3—C6—C9	−8.2 (4)
C63—N5—C59—C60	−0.3 (4)	C3—C4—C5—N8	−1.0 (6)
C67—N6—C66—C65	0.1 (4)	C3—C6—C7—C8	−177.4 (3)
C66—N6—C67—C68	0.1 (4)	C9—C6—C7—C8	1.5 (4)
C10—N7—C8—C7	−1.0 (5)	C3—C6—C9—C10	176.5 (3)
C8—N7—C10—C9	0.0 (5)	C7—C6—C9—C10	−2.4 (4)
C5—N8—C1—C2	−0.8 (5)	C6—C7—C8—N7	0.3 (5)
C1—N8—C5—C4	1.3 (5)	C6—C9—C10—N7	1.8 (5)
N1—C28—C29—C30	−0.3 (4)	C52—C53—C54—C55	−179.3 (2)
C28—C29—C30—C31	2.3 (4)	C58—C53—C54—C55	0.4 (4)
C28—C29—C30—C33	−176.7 (2)	C52—C53—C58—C57	−178.7 (2)
C29—C30—C33—C37	159.2 (2)	C54—C53—C58—C57	1.6 (4)
C31—C30—C33—C37	−19.7 (4)	C53—C54—C55—O1	177.9 (2)
C29—C30—C33—C34	−18.9 (4)	C53—C54—C55—C56	−2.2 (4)
C29—C30—C31—C32	−2.5 (4)	O1—C55—C56—C57	−178.1 (2)
C33—C30—C31—C32	176.4 (2)	C54—C55—C56—C57	2.0 (4)
C31—C30—C33—C34	162.2 (2)	C55—C56—C57—O2	−179.5 (2)
C30—C31—C32—N1	0.8 (4)	C55—C56—C57—C58	0.0 (4)
C30—C33—C34—C35	179.3 (2)	O2—C57—C58—C53	177.7 (2)
C30—C33—C37—C36	−178.6 (2)	C56—C57—C58—C53	−1.8 (4)
C34—C33—C37—C36	−0.4 (4)	C43—C38—C39—O3	−179.7 (2)
C37—C33—C34—C35	1.0 (4)	C43—C38—C39—C40	0.2 (4)
C33—C34—C35—N2	−0.9 (4)	C39—C38—C43—O4	−177.7 (2)
N2—C36—C37—C33	−0.5 (4)	C39—C38—C43—C42	1.4 (4)
N3—C18—C19—C20	0.4 (4)	O3—C39—C40—C41	177.9 (2)
C18—C19—C20—C21	−0.3 (4)	C38—C39—C40—C41	−2.0 (4)
C18—C19—C20—C23	179.8 (2)	C39—C40—C41—C42	2.3 (4)
C19—C20—C21—C22	0.3 (4)	C39—C40—C41—C44	−175.8 (2)
C23—C20—C21—C22	−179.8 (3)	C40—C41—C42—C43	−0.7 (4)
C21—C20—C23—C27	−13.0 (4)	C44—C41—C42—C43	177.4 (2)
C19—C20—C23—C24	−13.2 (4)	C41—C42—C43—O4	178.0 (2)
C19—C20—C23—C27	166.9 (3)	C41—C42—C43—C38	−1.1 (4)
C21—C20—C23—C24	166.9 (3)	C50—C45—C46—O6	179.3 (2)
C20—C21—C22—N3	−0.3 (5)	C50—C45—C46—C47	0.3 (4)
C24—C23—C27—C26	−1.6 (5)	C46—C45—C50—O5	−179.7 (2)
C27—C23—C24—C25	1.0 (4)	C46—C45—C50—C49	0.7 (4)
C20—C23—C27—C26	178.3 (3)	O6—C46—C47—C48	179.3 (2)
C20—C23—C24—C25	−178.9 (3)	C45—C46—C47—C48	−1.8 (4)
C23—C24—C25—N4	0.7 (5)	C46—C47—C48—C49	2.2 (4)
N4—C26—C27—C23	0.7 (6)	C46—C47—C48—C51	−177.1 (2)
N5—C59—C60—C61	1.1 (4)	C47—C48—C49—C50	−1.2 (4)
C59—C60—C61—C62	−0.8 (4)	C51—C48—C49—C50	178.1 (2)
C59—C60—C61—C64	179.7 (2)	C48—C49—C50—O5	−179.9 (2)
C60—C61—C64—C65	25.1 (4)	C48—C49—C50—C45	−0.3 (4)
C62—C61—C64—C68	25.8 (4)	C16—C11—C12—O7	−179.0 (2)
C60—C61—C64—C68	−154.8 (2)	C16—C11—C12—C13	1.1 (4)
C62—C61—C64—C65	−154.4 (3)	C12—C11—C16—O8	−179.2 (2)
C60—C61—C62—C63	−0.1 (4)	C12—C11—C16—C15	0.5 (4)
C64—C61—C62—C63	179.4 (3)	O7—C12—C13—C14	178.7 (2)
C61—C62—C63—N5	0.9 (5)	C11—C12—C13—C14	−1.4 (4)
C61—C64—C65—C66	179.2 (2)	C12—C13—C14—C15	0.1 (4)
C68—C64—C65—C66	−1.0 (4)	C12—C13—C14—C17	179.8 (2)
C65—C64—C68—C67	1.2 (4)	C13—C14—C15—C16	1.5 (4)
C61—C64—C68—C67	−178.9 (2)	C17—C14—C15—C16	−178.2 (2)
C64—C65—C66—N6	0.3 (4)	C14—C15—C16—O8	177.9 (2)
N6—C67—C68—C64	−0.8 (4)	C14—C15—C16—C11	−1.8 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y+1/2, z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) −x, −y+1, −z+1; (viii) x+1, −y+3/2, z−1/2; (ix) x, −y+1/2, z−1/2; (x) −x+1, −y+2, −z; (xi) x, −y+3/2, z−1/2; (xii) x−1, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N6^i	0.9900	1.8000	2.785 (3)	173.00
O2—H2O···N5	0.9900	1.7600	2.755 (3)	179.00
O3—H3O···N2	0.9900	1.7500	2.745 (3)	176.00
O4—H4O···N4	0.9900	1.8100	2.791 (3)	169.00
O5—H5O···N1	0.9900	1.7900	2.776 (3)	173.00
O6—H6O···N3	0.9900	1.7900	2.784 (3)	175.00
O7—H7O···N7	0.9900	1.7800	2.773 (3)	175.00
C7—H7···O2^ii	1.0800	2.5600	3.294 (3)	124.00
C8—H8···O6	1.0800	2.5900	3.381 (3)	130.00
C11—H11···N7	1.0800	2.5300	3.322 (3)	129.00
C15—H15···O3^iv	1.0800	2.5100	3.436 (3)	143.00
C19—H19···O5^iii	1.0800	2.4700	3.332 (3)	135.00
C34—H34···O4^vi	1.0800	2.4300	3.189 (3)	126.00
C44—H44B···O7^iv	1.0800	2.5600	3.565 (3)	156.00
C47—H47···O2^ii	1.0800	2.4000	3.386 (3)	151.00
C65—H65···O8^xi	1.0800	2.3200	3.336 (3)	155.00
C66—H66···O3^i	1.0800	2.5800	3.393 (3)	132.00

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2; (xi) x, −y+3/2, z−1/2.