Isomorphism: `molecular similarity to crystal structure similarity' in multicomponent forms of analgesic drugs tolfenamic and mefenamic acid

The non-steroidal anti-inflammatory drugs mefenamic acid (MFA) and tolfenamic acid (TFA) have a close resemblance in their molecular scaffold, whereby a methyl group in MFA is substituted by a chloro group in TFA. The present study demonstrates the isomorphous nature of these compounds in a series of their multicomponent solids. Furthermore, the unique nature of MFA and TFA has been demonstrated while excavating their alternate solid forms in that, by varying the drug (MFA or TFA) to coformer [4-di­methyl­amino­pyridine (DMAP)] stoichiometric ratio, both drugs have produced three different types of multicomponent crystals, viz. salt (1:1; API to coformer ratio), salt hydrate (1:1:1) and cocrystal salt (2:1). Interestingly, as anticipated from the close similarity of TFA and MFA structures, these multicomponent solids have shown an isomorphous relation. A thorough characterization and structural investigation of the new multicomponent forms of MFA and TFA revealed their similarity in terms of space group and structural packing with isomorphic nature among the pairs. Herein, the experimental results are generalized in a broader perspective for predictably identifying any possible new forms of comparable compounds by mapping their crystal structure landscapes. The utility of such an approach is evident from the identification of polymorph VI of TFA from hetero-seeding with isomorphous MFA form I from acetone–methanol (1:1) solution. That aside, a pseudopolymorph of TFA with di­methyl­formamide (DMF) was obtained, which also has some structural similarity to that of the solvate MFA:DMF. These new isostructural pairs are discussed in the context of solid form screening using structural landscape similarity.

1. Introduction

In crystal engineering, the aspects of isostructurality and polymorphism have always been intriguing for implications on the crystal packing and the potential impact on the properties of crystalline solids. Polymorphism is defined as the distinctive crystalline arrangements of a substance with the same chemical composition (Bernstein, 2002). On the other hand, two crystals are said to be isostructural if they have the same crystal structure but not necessarily the same cell dimensions nor the same chemical composition, whereas two crystalline solids are isomorphous if both have the same unit-cell dimensions and space group (Kálmán et al., 1993). It is perceived that the polymorphs discovered are often seren­dipitous, difficult to control and cause disadvantages over benefits (Llinàs & Goodman, 2008). Polymorphs may display very diverse properties (Bauer et al., 2001; Bag et al., 2012; Krishna et al., 2013; Saha & Desiraju, 2018a).

On the other hand, isostructurality has advantages such as reliable structure versus property knowledge transfer (Chennuru et al., 2017; Wood et al., 2012; Reddy et al., 2006; Krishna et al., 2016; Saha & Desiraju, 2017b), and formation of solid solutions for tuning physicochemical properties (Elgavi et al., 1973; Vangala et al., 2002; Pigge et al., 2006). In general, polymorphism and isostructurality are perceived as opposite phenomena. Coles et al. recently demonstrated a counter-intuitive case of two polymorphic forms with close structural resemblance which they called isostructural polymorphs (Coles et al., 2014; Fábián & Kálmán, 2004). This term has also been used in a different (rather unfitting) context to describe isostructural relationships between two forms of polymorphic analogous molecular pairs (Nath et al., 2008).

Methyl–chloro (Me, 19 ų; Cl, 21 ų) exchange is a well examined topic in isostructural studies (Ebenezer et al., 2011; Edwards et al., 2001). Kitaigorodskii stated that this exchange depends on volume and shape considerations rather than electronic factors (Kitaigorodskii, 1973). However, this interchange rule is broken when directional and/or electronic interactions are involved in the crystal packing (Desiraju & Sarma, 1986; Edwards et al., 2006). This means that, in some instances, the volume/shape considerations alone are inadequate and electronic factors must also be considered (SeethaLekshmi et al., 2014; Braga et al., 2009; Nath & Nangia, 2012; Reddy et al., 2006). There have been attempts to achieve forms with Cl/Me interchange. Braga et al. achieved a new polymorph of p-methyl­benzyl alcohol, which is isomorphous with the crystal of p-chloro­benzyl alcohol, by hetero-seeding with a small quantity of the latter (Romasanta et al., 2017). Although there have been several case studies on isostructurality consisting of single-component forms, only a few examples of multicomponent forms are reported in the literature (Cinčić et al., 2008a; Fandaruff et al., 2015; Clarke et al., 2012; Galcera & Molins, 2009).

In this study, we explored non-steroidal anti-inflammatory drugs tolfenamic (TFA) and mefenamic acids (MFA) to investigate the existence of isostructurality in their multicomponent solids. TFA and MFA are of interest in this study because, at the molecular level, there is a difference just in one position where the methyl group in MFA is replaced by the chloro group in TFA (Scheme 1). It has been reported that these two fenamates exist in several polymorphic forms owing to their conformational flexibility among the bridged amino group and carboxyl­ated phenyl group (SeethaLekshmi & Row, 2012; Bouanga Boudiombo & Jacobs, 2016; Wittering et al., 2015). TFA and MFA are known to exist in several polymorphic forms. Interestingly, crystal packing analyses reveal that amongst these, only form V of TFA is isomorphous to that of form II of MFA despite their ability to show Cl/Me interchange. From an isomorphous crystal point of view, a question arises as to whether one is likely to find some new forms for MFA that are isomorphous with that of known polymorphic forms of TFA and vice versa. One of the primary goals of this study is to unravel such hidden or new polymorphs of these active pharmaceutical ingredients (APIs) to expand the crystal structure landscape. This study allowed us to identify a new polymorph (VI) of TFA by hetero-seeding with the crystals of polymorph I of MFA from solution methods (Ranjan et al., 2017b). During the same period, Price and coworkers carried out an exhaustive study involving computational (crystal structure prediction) and experimental techniques on the single-component polymorphic forms of fenamates and successfully showed the effective use of this method by obtaining several new forms using the known isomorphous forms as templates in the sublimation method (Case et al., 2018).

Among the documented literature, the following two reports are of interest in this study. Fábián et al. have investigated the 1:2 (API to coformer ratio) co-crystal formation of all the fenamates with nicotinamide (Fábián et al., 2011; Utami et al., 2016). Later, Surov et al. described the similarity in crystal packing of 2:1 co-crystals of tolfenamic acid and mefenamic acid with 4,4′-bi­pyridine (Surov et al., 2015). However, in both cases, the authors have not explored the concept of isomorphism. The present work reports the structural studies of new multicomponent solids of TFA or MFA with 4-di­methyl­amino­pyridine (DMAP), which is known to form cocrystals/salts with APIs (Vangala et al., 2013; Ranjan et al., 2017a) in varying stoichiometric ratios. The concepts of solid-form screening, isostructurality, polymorphism and similarity in structural landscapes of related compounds are discussed.

2. Experimental

2.1. Materials

TFA, MFA, DMAP, DMF and other solvents were purchased from Sigma–Aldrich and were used without further purification.

2.2. Preparation of solid forms

The commercially available parent drugs TFA and MFA were separately ground with DMAP in different molar ratios, 1:1, 1:2 and 2:1 (drug to coformer ratio), with a few drops of methanol, which resulted in the 1:1 salt, 1:1:1 salt monohydrate and 2:1 co-crystal salt, respectively. The amounts of TFA and DMAP used in the synthesis of the salt, salt-monohydrate and cocrystal-salt were 50 and 23 mg, 50 and 46 mg, and 100 and 23 mg, respectively. Similarly, for the MFA–DMAP salt, salt monohydrate and cocrystal-salt, the amounts of MFA and DMAP used were 50 and 15 mg, 50 and 30 mg, and 100 and 15 mg, respectively. Single crystals were prepared by dissolving the respective ground powders in 10 ml acetone or an acetone–methanol solvent mixture (5 ml each) under ambient conditions and left undisturbed for 3 to 5 days. To get TFA–DMF in the solvated form, 50 mg of TFA was dissolved in 10 ml DMF under ambient conditions and was left undisturbed for 6–8 days. For TFA form VI preparation, 50 mg of TFA was dissolved in 10 ml of acetone:methanol (1:1) solvent mixture at 50 to 55°C to produce clear solution which was then allowed to cool without stirring. After cooling to 30°C, a couple of single crystals of MFA form I were added to the solution. Upon evaporation of the solvent, crystals of TFA form VI were obtained.

2.3. Single-crystal X-ray diffraction

Single-crystal X-ray diffraction (SCXRD) data were recorded on a SuperNova Eos diffractometer using monochromatic Mo Kα radiation (λ = 0.71073 Å) or Cu Kα radiation (λ = 1.54184 Å) at room temperature (293 K) or low temperature (100 K). Using Olex2 (Dolomanov et al., 2009), the structures were solved with SHELXT (Sheldrick, 2015a) using an intrinsic phasing algorithm and refined using SHELXL (Sheldrick, 2008, 2015b). Atomic displacement parameters (ADPs) were refined for all non-hydrogen atoms. The hydrogens attached to the carbons were placed in calculated positions with fixed geometries using the riding model with isotropic ADPs constrained, U_iso = 1.5 U_eq[C(sp³)] and U_iso = 1.2 U_eq[C(sp²)]. Hydrogens of the N—H and O—H groups were located using difference Fourier maps and refined with distance restraints d_N–H = 0.87 ± 0.02 Å, d_O–H = 0.82 ± 0.02 Å, and isotropic ADPs constraints U_iso = 1.2 U_eq(N), U_iso = 1.5 U_eq(O). The crystal packing diagrams were prepared using Mercury (version 3.8).

2.4. Powder X-ray diffraction

The bulk samples of all starting materials and new solid forms were characterized by powder X-ray diffraction (PXRD) analysis on a RigakuSmartLab using Cu Kα radiation (1.54056 Å). For all experiments, the tube voltage and amperage were set at 40 kV and 35 mA, respectively. Each sample was scanned between 5 and 50° 2θ with a step size of 0.02°.

2.5. Differential scanning calorimetry

Differential scanning calorimetry (DSC) was performed using a Mettler Toledo DSI1 STAR^e instrument with ∼5 mg of samples crimped in hermetic aluminium crucibles (40 ml) by ramping from 50 to 250°C at a heating rate of 10°C min⁻¹ under a dry nitro­gen atmosphere (flow rate 80 ml min⁻¹). The data were analysed using STAR^e software.

2.6. Thermogravimetric analysis

Thermogravimetric analysis (TGA) was carried out using a Perkin Elmer, Diamond TG/DTA analyser, operated under a nitro­gen atmosphere with a heating rate of 10°C min⁻¹ in the range 30−300°C.

3. Results and discussion

3.1. Powder X-ray diffraction analysis

Formation of a new solid phase and its purity were confirmed by PXRD analysis by matching the patterns with corresponding starting materials (see Figs. S13 and S14 of the supporting information). There is a good match between experimental and simulated PXRD patterns for all the multicomponent solids, except for two monohydrate salts. On the other hand, the mismatch between experimental and simulated PXRD patterns is not uncommon for hydrates or solvates (Clarke et al., 2010). The preferable orientation and different data collection temperatures for the experimental powder pattern compared with that of the simulated pattern, which was generated using SCXRD data, could have contributed to this difference. On the other hand, we have seen the close match between the PXRD patterns of the same molar ratio pairs of multicomponent solids of TFA and MFA (e.g. 1:1 salts of TFA and MFA).

3.2. Crystal structure analysis

3.2.1. Multicomponent isomorphic crystals of analogous fenamic acids

Cocrystallization of DMAP with fenamic acids is expected to yield a salt because of the ∼6 units of ΔpK_a between DMAP and the corresponding API (TFA and MFA, pK_a = 3.7; DMAP, pK_a = 9.7). Furthermore, it is well documented that the salt form of an API can significantly change its physicochemical properties such as crystallinity, solubility and stability and hence can be considered as an alternative route for drug delivery (Maddileti et al., 2014; Goud et al., 2013).

Notably, all the solids including parent APIs and the new multicomponent forms crystallized in the triclinic space group (Tables S1 and S2 of the supporting information). The 1:1 salt crystal structure possesses one molecule of TFA (or MFA) and DMAP each in the asymmetric unit, whereas the 1:1:1 salt monohydrate crystal structure (Ranjan et al., 2017b; Nechipadappu & Trivedi, 2017) contains a water molecule along with one TFA molecule (or MFA) and one DMAP molecule. Aside from this, the 2:1 co-crystal salt possesses two molecules of TFA (or MFA) and one molecule of DMAP in the asymmetric unit. The ORTEP representations of all the new solids are shown in Figs. S4–S11. Though the commercially available APIs TFA and MFA are not isomorphous (only isostructural), it is intriguing to perceive the isomorphic attribute in their multicomponent solids as their unit-cell parameters are near identical (Table 1). For further clarity, the isostructurality was quantitatively deciphered from the commonly used method which uses the unit-cell parameters of two crystal structures to calculate the unit-cell similarity index (Π) (Wood et al., 2012; Sarmah et al., 2017). If the compared structures are isostructural to a great extent, then Π should be close to zero, and if Π = 0, then they are isomorphous (Oliveira et al., 2008). In the present case of the multicomponent pairs of TFA and MFA, the Π value is zero (up to the first decimal place, see Table 1), confirming the isomorphous nature of the pairs. Furthermore, PXRD similarity index scores for each pair and the RMSDs (root-mean-square deviations) were calculated from the packing similarity overlay with 20 molecules by allowing molecular differences and keeping default tolerance values. PXRD similarity and RMSD values were derived from the program Mercury (CSD version 3.8). The quantitative numbers are given in Table 1. The results obtained from crystal packing similarity calculations showed that 20 out of 20 molecules were matched in the pairs of 1:1 salts and 1:1:1 salt monohydrates, whereas in case of the 2:1 co-crystal salt pairs, only 9 out of 20 molecules were matched despite the Π value being close to zero. The reason for the match of such fewer molecules could be due to the additional disorder of the symmetrically-independent molecules in the respective crystal structures. Therefore, the comparable PXRD similarity scores in all three cases suggest that these pairs possess identical intermolecular interactions and lead to the same crystal packing (Fig. 2). Furthermore, we have utilized the `Xpac' analysis to quantitatively measure the packing similarity between the TFA and MFA multicomponent series (Gelbrich & Hursthouse, 2006; Gelbrich et al., 2012). This analysis provides the dissimilarity index (x) value, which is a measure of the deviation of two structures from perfect geometrical similarity (Fábián & Kálmán, 1999). In the current study, the `x' values of the multicomponent solids of TFA and MFA are found to be 3.7 for 1:1 salts (Fig. S1), 1.0 for 1:1:1 salt monohydrates (Fig. S2) and 2.5 for 2:1 co-crystal salts (Fig. S3). Therefore, the `x' values of the corresponding multicomponent solid pairs of TFA and MFA signify that all pairs are isomorphous.

Table 1
Unit-cell parameters, root-mean-square deviation (RMSD), PXRD similarity and unit-cell similarity index (Π) for TFA and MFA multicomponent solids

The unit-cell parameters with estimated standard deviations are provided in the supporting information, see Tables S1 and S2.

	Unit-cell parameters (Å, °, Å^3)	RMSD (Å)	PXRD similarity	Unit-cell similarity index
TFA–DMAP (1:1)	a = 7.9299, b = 9.3219, c = 13.5862	0.219	0.987	0.010
	α = 87.768, β = 76.928, γ = 76.025
	V = 949.20
MFA–DMAP (1:1)	a = 7.7575, b = 9.4727, c = 13.3076
	α = 87.515, β = 78.596, γ = 74.174
	V = 922.20
TFA–DMAP–H2O (1:1:1)	a = 7.7631, b = 8.0250, c = 16.2297	0.088	0.989	0.001
	α = 101.784, β = 98.374, γ = 90.687
	V = 978.33
MFA–DMAP–H2O (1:1:1)	a = 7.7248, b = 8.0592, c = 16.2531
	α = 101.711, β = 98.743, γ = 90.160
	V = 978.68
TFA–DMAP (2:1)	a = 10.8864, b = 12.2705, c = 13.7811	0.872	0.982	0.011
	α = 106.966, β = 105.782, γ = 103.324
	V = 1595.92
MFA–DMAP (2:1)	a = 10.7678, b = 11.9673, c = 13.7860
	α = 106.151, β = 105.854, γ = 103.490
	V = 1546.4

In the structures of TFA and MFA multicomponent solids, some significant differences in the conformations were observed (see Table S3 for specifics). Although the torsion angles of the multicomponent solids deviate significantly from their parent API torsion angles, the torsion or dihedral angles among multicomponent solids for the same composition (e.g. 1:1 salts of TFA and MFA) are closely corroborated. In turn, the angles between the acid-holding aromatic ring of the API and DMAP pyridyl ring (θ) in the isomorphic pairs are quite close, which led to their identical close packing with nearly the same pattern of intermolecular interactions. As a result of such high twisting of rings, TFA and MFA molecules often show disorder in their structures.

In the crystal packing, both the parent APIs, TFA and MFA, form dimers and are close packed by several C—H⋯O and C—H⋯π interactions. However, in the new multicomponent solid forms of both APIs, the dimerization was disrupted either by a DMAP molecule (in the cases of 1:1 and 2:1) or a water molecule (in the case of 1:1:1). This is due to proton transfer from the acid (of API) to the DMAP molecule in all cases (Fig. 1). Furthermore, there were no noticeable Cl⋯Cl interactions observed in the parent TFA as well as in its multicomponent solids. If the Cl⋯Cl interactions have no effect on the packing of TFA crystals, then the methyl-substituted isostructural compound MFA would also display similar packing (Landenberger et al., 2013). As a result, we could expect the isostructural/isomorphous packing in both TFA and MFA multicomponent solids of the Cl and CH₃ groups to behave in a similar fashion in crystal packing for their comparable volumes, 19 and 24 ų, respectively (Desiraju & Sarma, 1986).

Figure 1 Synthons observed in crystal structures of parent APIs and multicomponent solids. (a) TFA form-I and (b) MFA form-I dimers (Andersen et al., 1989; Lee et al., 2006); (c) 1:1 TFA–DMAP and (d) MFA–DMAP salts; (e) 1:1:1 TFA–DMAP–H2O and (f) MFA–DMAP–H2O salt monohydrates; (g) 2:1 ratio of TFA–DMAP and (h) MFA–DMAP co-crystal salts.

In the 1:1 salt crystal packing, two molecules of TFA (or MFA) and two molecules of DMAP form a tetrameric synthon via N—H⋯O and C—H⋯O hydrogen bonds [Figs. 2(a) and 2(b)]. The adjacent tetrameric synthons are joined by moderately strong C—H⋯O interactions along the b direction. The motifs are further stacked by antiparallel π-stacking interactions between chlorinated (or methyl­ated in MFA) phenyl rings of TFA along []. Whereas in the case of the 1:1:1 salt hydrate, two molecules of TFA (or MFA) and two molecules of water form the tetrameric synthon with strong O—H⋯O hydrogen bonds [Figs. 1(e) and 1(f)]. These tetramers grow along the c direction in a 1D chain by edge-on (or T-shaped) C—H⋯π interactions between adjacent TFA (or MFA) molecules of the tetrameric synthon. Along the other two crystallographic directions a and b, the 1D chains are joined by DMAP molecules via strong N—H⋯O and weak C—H⋯O interactions [Figs. 2(c) and 2(d)]. In the third case, the 2:1 co-crystal salt, the alternative TFA (or MFA) and DMAP molecules form an infinite 1D chain (which resembles an open catemer) via strong O—H⋯O, N—H⋯O and C—H⋯O interactions. Furthermore, these 1D chains are interlocked by π-stacking interactions of TFA chlorinated (or MFA methyl­ated) phenyl rings along () as shown in Figs. 2(e) and 2(f). The geometrical parameters of hydrogen bonding in all the complexes are given in the Table S4.

Figure 2 Crystal packing in (a) 1:1 TFA–DMAP and (b) MFA–DMAP salts; (c) 1:1:1 TFA–DMAP–H2O and (d) MFA–DMAP–H2O salt monohydrates; (e) 2:1 TFA-DMAP and (f) MFA–DMAP co-crystal salts, respectively. For clarity, the pyridine molecules are shown in orange and C—H⋯π interactions have been omitted.

3.2.2. Polymorphism among analogous fenamic acids

Although our initial aim was to find the existence of isomorphism in multicomponent solids, we serendipitously discovered a new polymorph of TFA while co-crystallizing with DMAP, hereafter designated as TFA form VI (Ranjan et al., 2017b). This form was obtained by Price and co-workers in their study (Case et al., 2018). SCXRD data of this polymorph revealed that its cell parameters are identical to form I of MFA with unit-cell similarity index Π = 0.015. In addition, the high similarity index of PXRD (0.953) and low RMSD (0.132 Å) values suggest close structural similarity (see Table 2). Our attempts to reproduce form VI by the same co-crystallization procedure were unsuccessful. Even the co-crystallization attempts in different stoichiometric ratios or with different reaction conditions were also unsuccessful. However, interestingly, form VI could be obtained by the hetero-seeding crystallization method (Braga et al., 2009; Ebenezer et al., 2011) from its analogue isostructural form: form I of MFA from a 1:1 mixture of acetone and methanol solution by slow evaporation.

Table 2
Unit-cell parameters, root-mean-square deviatiom (RMSD), PXRD similarity and unit-cell similarity index (Π) for TFA and MFA polymorphs

	Unit-cell parameters (Å, °, Å^3)		RMSD (Å)	PXRD similarity	Unit-cell similarity index
TFA form-VI	a = 6.7049, b = 7.2778, c = 14.1630		0.132	0.953	0.015
(New form)	α = 77.167, β = 79.908, γ = 65.487
	V = 610.42
MFA form-I	a = 6.8144, b = 7.3256, c = 14.4196
(McConnell, 1976)	α = 76.648, β = 79.178, γ = 65.547
	V = 634.08
TFA form-V	a = 7.6488, b = 9.0160, c = 9.4184
(López-Mejías et al., 2009)	α = 107.385, β = 92.062, γ = 101.662		Could not be done due to heavy disorder of the molecules.		0.005
	V = 603.806
MFA form-II	a = 7.70630, b = 9.10160, c = 9.39700
(Lee et al., 2006)	α = 107.2850, β = 91.4080, γ = 101.8040
	V = 613.454

Nevertheless, the crystal packing of TFA form VI, which is isomorphous to MFA form I (McConnell, 1976), crystallizes in the triclinic space group with one molecule in the asymmetric unit. The TFA molecules form dimers. The alternate dimers along the b axis are held together by edge-to-face C—H⋯π (2.78 Å) interactions. Along the c direction, these dimer stacks are arranged in an anti-parallel fashion via C—H⋯π (2.71 Å) interactions. Therefore, the crystal structure view in the ac plane resembles the zipper-type interlocked packing of dimers [Fig. 3(a)]. The structural similarity between these isomorphous forms (MFA form I and TFA form VI) can be seen in Fig. 3.

Figure 3 Crystal packing of (a) TFA form-VI and (b) MFA-form-I in the ac plane.

3.2.3. Non-isomorphous pseudopolymorphs among analogous fenamic acids

To further demonstrate the viability of this concept, we attempted to obtain the other unknown forms for both fenamates. Consequently, we were able to obtain the new pseudopolymorph TFA–DMF solvate by crystallizing the TFA in DMF solvent (SeethaLekshmi & Row, 2012). However, the SCXRD data of this new solvate revealed that its cell parameters do not exactly match with its analogue, the MFA–DMF solvate. The unit-cell similarity index of this pair (∼0.149) is not close to zero and only 15 out of 20 molecules could be matched while calculating the packing similarity (Table 3). The deviation is caused by changes in the structural packing. Unlike MFA–DMF, which consists of one molecule each of MFA and DMF in the asymmetric unit, the TFA–DMF has two TFA and two DMF molecules in the asymmetric unit. As a result, the volume is roughly doubled to that of MFA–DMF. In both these pseudopolymorphs, the DMF molecule interrupts the acid dimer and forms TFA–DMF or MFA–DMF dimers through O—H⋯O and C—H⋯O hydrogen bonds. As shown in Figs. 4(a) and 4(b), the pseudopolymorphs have the same interactions (π⋯π and C—H⋯π) between the dimers, hence they have some structural similarity; however, these are non-isostructural. The difference in dihedral angle (∼9°, see Fig. S12) between symmetrically independent TFA molecules in TFA–DMF leads to significant changes in close packing compared with MFA–DMF [Figs. 4(c) and 4(d)], which in turn makes them non-isostructural or non-isomorphous pairs.

Table 3
Unit-cell parameters, root-mean-square deviation (RMSD), PXRD similarity and unit-cell similarity index (Π) for TFA and MFA solvates

	Unit-cell parameters (Å, °, Å^3)		RMSD (Å)	PXRD similarity	Unit-cell similarity index
TFA–DMF	a = 10.4803, b = 11.8423, c = 13.3309		0.229	0.948	0.149
	α = 94.335, β = 95.884, γ = 102.871
	V = 1596.16
MFA–DMF	a = 7.4730, b = 9.559, c = 13.306
	α = 105.070, β = 103.780, γ = 103.410
	V = 846.512

Figure 4 Dimers in (a) TFA–DMF and (b) MFA–DMF, which interact via π⋯π and C—H⋯π interactions, show their structural similarity at the local level. Comparison of crystal packing of (c) TFA–DMF and (d) MFA–DMF solvates highlights differences when viewed from other directions. The DMF molecules are shown in ball and stick form for easy visualization of its interactions with fenamates.

3.3. Thermal analysis

Thermal behaviour of all the multicomponent solids and polymorphs was investigated by DSC and TGA, and the profiles are presented in Figs. S15 and S16. The melting points of TFA, MFA and DMAP are in the ranges 206.8–215.2, 230–231 and 110–113°C, respectively. All of the multicomponent solid forms exhibit distinct melting points to that of their respective starting materials, which is corroborated by PXRD and SCXRD results, suggesting the formation of new crystalline phases. The melting points of the TFA–DMAP (1:1) salt, the TFA–DMAP (2:1) co-crystal salt, the MFA–DMAP (1:1) salt and the MFA–DMAP (2:1) co-crystal salt were observed at 158, 178, 165 and 162°C, respectively. Negligible weight losses were observed in their respective TGA profiles, thus confirming that the endothermic peak is its melting temperature. The endothermic melting peaks of TFA–DMAP–H₂O (1:1:1) and MFA–DMAP–H₂O (1:1:1) were observed at 152 and 162°C, respectively. The TGA profiles of these solids established the stoichiometry of water in these hydrates (Du et al., 2009). Weight losses of 4.45 and 4.9% were observed in the temperature ranges 72–98 and 78–97°C in the TGA trace of TFA–DMAP–H₂O (1:1:1) and MFA–DMAP–H₂O (1:1:1), respectively, which correspond to the loss of one water molecule. This value is in accordance with the theoretical mass losses of 4.7 and 4.48% for desolvation of one mole of water from the respective crystal lattices and matching well with the calculated amount of water in the crystal structure. After the loss of water, TFA–DMAP–H₂O (1:1:1) was stable up to 142°C and then began to decompose upon further heating. Similarly, MFA–DMAP–H₂O (1:1:1) was stable up to 157°C.

Notably, the isomorphous pairs showed different melting points (physical properties) despite their similar structural packing. These results suggest that the properties of isostructural pairs can be directly correlated to chemical contribution from constituents, as mentioned by Jones and co-workers (Cinčić et al., 2008b).

We have also performed DSC experiments for TFA form VI and the TFA–DMF solvate and noticed melting endotherms at 221 and 209°C, respectively. In addition, we observed an additional endotherm that coud be ascribed to the solvent molecule in TFA–DMF. The observed weight loss of 17.6% in the temperature range 55–97°C for TFA–DMF corresponds to solvent evaporation. The remaining solids have shown no weight loss before their melting points, which confirms their purity and stability.

4. Hirshfeld surface analysis

Because it is difficult to quantify the short contacts present in a structure from either Mercury or other useful crystallography software, we used Hirshfeld surface analysis. Moreover, it is easy to plot and compare the interactions present in different polymorphic forms of a substance. Here, the newly obtained TFA polymorph VI is compared with the other five known polymorphs by plotting fingerprint plots (Fig. 5). The common interactions that participate in hydrogen bonding: O⋯H, N⋯H and other non-hydrogen bonding interactions are listed in the respective plots. From the overall interaction contribution, it is clear that the interactions in the new form are also in line with the reported polymorphs.

Figure 5 The fingerprint plots of polymorphs of TFA in ascending order from form I to form VI.

5. Discussion

5.1. Isostructurality and the relationship with crystal structural landscape

The investigation of crystal structural landscapes helps in understanding various dynamic events that occur during crystallization, including polymorphs, pseudopolymorphs and high-Z′ issues (Mukherjee et al., 2011). In principle, for a given molecule there exists a large number of virtual crystal structures within a narrow energy window. Many factors control a particular crystal structure formation. Accessing different structure types or, in other words, data points in a crystal structure landscape for a given system is a difficult task. This can be done experimentally (Chakraborty et al., 2018) or computationally through crystal structure prediction (CSP) (Thakur et al., 2015). However, CSP does not provide the information on the final experimental outcome under given crystallization conditions as it does not consider the kinetic issues associated with a crystallization event. By exploring the crystal structure landscape, one may find means to achieve a particular crystal structure with new synthons that are not readily accessible (Saha & Desiraju, 2018b). Obtaining such structures would be more useful when a specific structure type can only display a particular property (Saha & Desiraju, 2017a). Synthons encapsulate kinetic information regarding the process of crystallization. According to classical nucleation theory, synthons can be generated in solution and finally transfer into the crystal structure (Parveen et al., 2005; Davey et al., 2006). Understanding these events helps in structural profiling which, in turn, can guide us to develop crystal engineering strategies.

The present work considers experimental exploration of crystal structure landscapes for stoichiometric multicomponent fenamic acid drugs TFA and MFA. The only substitutional change is Cl/Me exchange on the basic fenamic acid molecular scaffold, i.e. the molecular similarity between TFA and MFA makes them ideal candidates to compare their individual crystal structural landscapes as a whole. In this regard, the multicomponent solids of TFA and MFA with DMAP and/or DMF are considered. A total of six binary structures for TFA were analysed in that three are different forms with DMAP. Analyses of crystal structures for MFA reveal the existence of identical or very similar crystal structures for each TFA type. Such a high degree of matching suggests that, by exploring the landscape for a model system, one can practically find possible crystal structures for other similar systems (Chennuru et al., 2017). Similarly, crystal structures of single-component TFA and MFA are analysed. We analyzed the six polymorphic forms of TFA (I–VI) with the three MFA forms (I–III) known thus far. However, crystal structures were matched for barely two pairs (TFA form V and MFA II; TFA form VI and MFA form I) (Fig. 6). Accordingly, one can assume that crystal structure pattern types for five pairs, which are placed in different energy data points in the landscape diagram, are known or experimentally accessed. It should also be mentioned that not only are the structural patterns of these polymorphs different, but also the major synthons differ significantly, indicating the possible influence of both geometrical and chemical factors. Such observation is uncommon (Dubey et al., 2014; Saha & Desiraju, 2018b). Here we see the existence of dimers and catemers for the same coformer DMAP. Dimers with multipoint recognition are generally known to be thermodynamically favoured, whereas single-point catemers are kinetically preferred. Such differences in structural patterns may lead to changes in physicochemical properties, such as solubility, stability, optical activity and nonlinear optical behaviour.

Figure 6 Isomorphous/isostructural pairs of multicomponent (top) and single-component (bottom) solids of TFA and MFA.

6. Conclusions

Existence of isomorphism in the multicomponent solids of TFA and MFA has been thoroughly investigated by considering the similarity of their crystal structure landscapes. The quantitative numbers of unit-cell similarity, PXRD similarity index and RMSD values suggest that the multicomponent crystals of TFA and MFA with DMAP and/or DMF in the same molar ratio are structurally very closely associated. In addition, the discovery of a new polymorph of TFA and a pseudopolymorph TFA–DMF solvate is in line with the concept of isomorphism. Hence, this study demonstrates that isomorphism will be a promising guiding principle for using crystal structure landscape similarity to uncover hidden unknown structures of closely resembling compounds, i.e. molecular similarities. Further work is ongoing in our laboratory to unravel the other hidden single-component forms of TFA and MFA.

It may be possible to use one model molecular system to explore the crystal structure landscape for other systems with molecular similarity (Chakraborty et al., 2018; Case et al., 2018). Such an approach can help to predict or compare properties of different structure types of analogous compounds in comparison with the model system (Krishna et al., 2016), without exploring each structure for individual compounds. If different forms are known for the model system, then measurements of their properties will reveal the suitability of targeted properties or applications (Saha et al., 2018). One can then target that particular structure type in an analogus compound to improve the property further (for example, by functional-group exchange) by using the knowledge of the isostructural behaviour of molecules.

Supporting information

Computing details

Data collection: CrysAlis PRO 1.171.38.41 (Rigaku OD, 2015) for tfa_dmap_1-1, tfa-dmap-H2O_1-1-1, mfa-dmap_1-1, mfa-dmap-H2O_1-1-1; CrysAlis PRO, Agilent Technologies, Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET) (compiled Apr 11 2014,15:12:41) for tfa-dmap_2-1; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for tfa_form-vi; CrysAlis PRO 1.171.38.43f (Rigaku OD, 2015) for tfa_dmf; CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) for mfa-dmap_2-1. Cell refinement: CrysAlis PRO 1.171.38.41 (Rigaku OD, 2015) for tfa_dmap_1-1, tfa-dmap-H2O_1-1-1, mfa-dmap_1-1, mfa-dmap-H2O_1-1-1; CrysAlis PRO, Agilent Technologies, Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET) (compiled Apr 11 2014,15:12:41) for tfa-dmap_2-1; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for tfa_form-vi; CrysAlis PRO 1.171.38.43f (Rigaku OD, 2015) for tfa_dmf; CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) for mfa-dmap_2-1. Data reduction: CrysAlis PRO 1.171.38.41 (Rigaku OD, 2015) for tfa_dmap_1-1, tfa-dmap-H2O_1-1-1, mfa-dmap_1-1, mfa-dmap-H2O_1-1-1; CrysAlis PRO, Agilent Technologies, Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET) (compiled Apr 11 2014,15:12:41) for tfa-dmap_2-1; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for tfa_form-vi; CrysAlis PRO 1.171.38.43f (Rigaku OD, 2015) for tfa_dmf; CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) for mfa-dmap_2-1. For all structures, program(s) used to solve structure: SHELXT 2014/4 (Sheldrick, 2014); program(s) used to refine structure: SHELXL 2018/3 (Sheldrick, 2015); molecular graphics: Olex2 1.3 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.3 (Dolomanov et al., 2009).

(tfa_dmap_1-1)

Crystal data

C14H11ClNO2·C7H11N2	Z = 2
Mr = 383.86	F(000) = 404
Triclinic, P1	Dx = 1.343 Mg m^−3
a = 7.9299 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3219 (4) Å	Cell parameters from 2867 reflections
c = 13.5862 (9) Å	θ = 2.2–26.3°
α = 87.768 (4)°	µ = 0.22 mm^−1
β = 76.928 (5)°	T = 291 K
γ = 76.025 (5)°	Block, colourless
V = 949.20 (10) Å^3	0.32 × 0.15 × 0.1 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	3841 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2799 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.022
Detector resolution: 7.9580 pixels mm^-1	θmax = 26.4°, θmin = 2.7°
ω scans	h = −9→9
Absorption correction: multi-scan CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −11→11
Tmin = 0.791, Tmax = 1.000	l = −16→15
6616 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.0595P)^2 + 0.3245P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3841 reflections	Δρmax = 0.16 e Å^−3
339 parameters	Δρmin = −0.26 e Å^−3
3 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.0273 (2)	0.37134 (15)	0.73327 (11)	0.0866 (6)	0.583 (3)
O1	0.4605 (2)	0.53164 (18)	0.22808 (14)	0.0712 (5)
O2	0.7060 (3)	0.44157 (19)	0.11431 (13)	0.0728 (5)
N3	0.3852 (3)	−0.2178 (2)	0.14091 (15)	0.0536 (5)
H3A	0.423 (3)	−0.309 (2)	0.1675 (18)	0.064*
N2	0.2291 (3)	0.20600 (19)	0.03897 (14)	0.0504 (5)
C15	0.2777 (3)	0.0688 (2)	0.07220 (15)	0.0420 (5)
C2	0.6260 (3)	0.2894 (2)	0.25145 (14)	0.0402 (5)
C1	0.5977 (3)	0.4311 (2)	0.19308 (16)	0.0456 (5)
C3	0.7847 (3)	0.1849 (2)	0.22048 (16)	0.0481 (5)
H3	0.871720	0.206687	0.165224	0.058*
C18	0.3148 (3)	−0.1945 (2)	0.05932 (19)	0.0536 (6)
H18	0.302513	−0.276959	0.025015	0.064*
C19	0.2605 (3)	−0.0568 (2)	0.02402 (17)	0.0505 (5)
H19	0.210312	−0.044758	−0.033842	0.061*
C16	0.3541 (3)	0.0387 (2)	0.15756 (16)	0.0546 (6)
H16	0.370078	0.117819	0.193696	0.066*
C7	0.4981 (3)	0.2571 (2)	0.33324 (18)	0.0565 (6)
C4	0.8215 (3)	0.0502 (2)	0.26680 (18)	0.0564 (6)
H4	0.932209	−0.019215	0.244356	0.068*
C17	0.4048 (3)	−0.1021 (3)	0.18816 (17)	0.0575 (6)
H17	0.456247	−0.119152	0.245540	0.069*
C5	0.6951 (3)	0.0185 (3)	0.34577 (18)	0.0584 (6)
H5	0.718192	−0.074270	0.377908	0.070*
C6	0.5366 (3)	0.1183 (3)	0.37896 (19)	0.0647 (7)
H6	0.450726	0.093891	0.433796	0.078*
C21	0.1480 (4)	0.2394 (3)	−0.0474 (2)	0.0672 (7)
H21A	0.192496	0.155908	−0.095502	0.101*
H21B	0.178564	0.328096	−0.080305	0.101*
H21C	0.018205	0.256910	−0.024784	0.101*
N1	0.3225 (6)	0.3383 (5)	0.3522 (4)	0.0524 (11)	0.583 (3)
H1	0.312 (6)	0.421 (3)	0.321 (3)	0.063*	0.5833
C20	0.2406 (5)	0.3357 (3)	0.0927 (2)	0.0761 (8)
H20A	0.140689	0.359127	0.151658	0.114*
H20B	0.235668	0.420222	0.047361	0.114*
H20C	0.353280	0.314223	0.114950	0.114*
C9	0.0572 (18)	0.2550 (15)	0.4140 (9)	0.059 (2)	0.583 (3)
H9	0.061531	0.229785	0.346266	0.071*	0.583 (3)
C13	0.1860 (6)	0.3517 (5)	0.5338 (4)	0.0433 (11)	0.583 (3)
C12	0.0437 (10)	0.3283 (6)	0.6081 (5)	0.0462 (13)	0.583 (3)
C14	0.3327 (11)	0.4090 (16)	0.5579 (11)	0.078 (3)	0.583 (3)
H14A	0.283976	0.508582	0.587669	0.116*	0.583 (3)
H14B	0.422712	0.412592	0.495736	0.116*	0.583 (3)
H14C	0.387579	0.343341	0.605994	0.116*	0.583 (3)
C11	−0.0868 (8)	0.2693 (6)	0.5873 (5)	0.0558 (17)	0.583 (3)
H11	−0.181610	0.254959	0.640581	0.067*	0.583 (3)
C8	0.1870 (7)	0.3141 (5)	0.4344 (3)	0.0426 (9)	0.583 (3)
C10	−0.0816 (6)	0.2311 (6)	0.4910 (4)	0.0743 (14)	0.583 (3)
H10	−0.171175	0.188836	0.476554	0.089*	0.583 (3)
N4	0.3631 (9)	0.3778 (7)	0.3895 (5)	0.0549 (17)	0.417 (3)
H4A	0.330 (8)	0.465 (4)	0.366 (5)	0.066*	0.4167
C24	0.1069 (10)	0.2921 (6)	0.4836 (6)	0.0526 (16)	0.417 (3)
C27	0.1438 (9)	0.4093 (7)	0.6625 (5)	0.0694 (18)	0.417 (3)
H27	0.158164	0.448031	0.722967	0.083*	0.417 (3)
C28	0.0079 (10)	0.3442 (7)	0.6636 (7)	0.055 (2)	0.417 (3)
H28	−0.076035	0.338424	0.724890	0.065*	0.417 (3)
C23	0.2431 (10)	0.3606 (7)	0.4826 (8)	0.0536 (19)	0.417 (3)
C26	0.2620 (14)	0.4180 (18)	0.5706 (14)	0.064 (3)	0.417 (3)
H26	0.357182	0.464246	0.568428	0.077*	0.417 (3)
C25	−0.0070 (12)	0.2886 (10)	0.5783 (8)	0.0481 (18)	0.417 (3)
Cl2	−0.1844 (3)	0.2020 (2)	0.58250 (16)	0.0878 (8)	0.417 (3)
C22	0.084 (3)	0.225 (3)	0.3893 (15)	0.080 (5)	0.417 (3)
H22A	0.138254	0.274468	0.329651	0.119*	0.417 (3)
H22B	−0.043310	0.238361	0.391789	0.119*	0.417 (3)
H22C	0.142225	0.119499	0.385187	0.119*	0.417 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1127 (12)	0.0841 (9)	0.0427 (9)	0.0103 (7)	−0.0109 (7)	−0.0055 (6)
O1	0.0717 (12)	0.0467 (9)	0.0738 (12)	0.0004 (8)	0.0075 (9)	0.0248 (8)
O2	0.0860 (13)	0.0586 (10)	0.0596 (11)	−0.0185 (9)	0.0110 (9)	0.0177 (8)
N3	0.0547 (11)	0.0389 (10)	0.0601 (12)	−0.0095 (8)	−0.0021 (9)	0.0143 (9)
N2	0.0605 (12)	0.0384 (9)	0.0503 (10)	−0.0133 (8)	−0.0077 (9)	0.0099 (8)
C15	0.0422 (11)	0.0373 (10)	0.0407 (10)	−0.0106 (8)	0.0025 (9)	0.0051 (8)
C2	0.0423 (11)	0.0387 (10)	0.0388 (10)	−0.0109 (9)	−0.0066 (9)	0.0038 (8)
C1	0.0544 (13)	0.0413 (11)	0.0423 (11)	−0.0177 (10)	−0.0072 (10)	0.0058 (9)
C3	0.0477 (12)	0.0488 (12)	0.0442 (11)	−0.0134 (10)	−0.0004 (9)	−0.0011 (9)
C18	0.0582 (14)	0.0393 (11)	0.0627 (14)	−0.0173 (10)	−0.0060 (11)	0.0010 (10)
C19	0.0541 (13)	0.0459 (12)	0.0537 (13)	−0.0175 (10)	−0.0116 (10)	0.0065 (10)
C16	0.0771 (16)	0.0467 (12)	0.0411 (11)	−0.0219 (11)	−0.0079 (11)	0.0030 (9)
C7	0.0479 (13)	0.0475 (12)	0.0565 (13)	0.0040 (10)	0.0046 (10)	0.0191 (10)
C4	0.0479 (13)	0.0475 (13)	0.0608 (14)	0.0047 (10)	−0.0031 (11)	0.0003 (10)
C17	0.0727 (16)	0.0549 (14)	0.0450 (12)	−0.0187 (12)	−0.0114 (11)	0.0126 (10)
C5	0.0628 (15)	0.0430 (12)	0.0587 (14)	0.0026 (11)	−0.0100 (12)	0.0126 (10)
C6	0.0554 (14)	0.0536 (14)	0.0640 (15)	0.0026 (11)	0.0083 (11)	0.0277 (12)
C21	0.0674 (16)	0.0586 (15)	0.0793 (18)	−0.0174 (12)	−0.0255 (14)	0.0256 (13)
N1	0.043 (2)	0.042 (2)	0.057 (3)	0.0029 (17)	0.0038 (18)	0.0196 (19)
C20	0.118 (2)	0.0394 (13)	0.0662 (16)	−0.0192 (14)	−0.0112 (16)	0.0033 (11)
C9	0.054 (4)	0.069 (5)	0.051 (6)	−0.012 (3)	−0.007 (4)	−0.008 (4)
C13	0.043 (3)	0.031 (2)	0.051 (3)	−0.0003 (18)	−0.010 (3)	0.004 (2)
C12	0.054 (4)	0.035 (3)	0.039 (4)	0.003 (2)	−0.007 (3)	0.004 (2)
C14	0.066 (6)	0.081 (5)	0.096 (6)	−0.028 (6)	−0.025 (6)	−0.005 (4)
C11	0.037 (3)	0.050 (3)	0.070 (3)	−0.016 (3)	0.013 (3)	0.008 (2)
C8	0.038 (2)	0.036 (2)	0.044 (2)	0.0017 (16)	0.000 (2)	0.0083 (19)
C10	0.054 (3)	0.086 (3)	0.085 (4)	−0.032 (2)	−0.002 (2)	−0.014 (3)
N4	0.054 (4)	0.035 (3)	0.057 (4)	0.000 (2)	0.011 (3)	0.019 (3)
C24	0.063 (4)	0.036 (3)	0.049 (4)	0.000 (3)	−0.006 (4)	0.004 (3)
C27	0.078 (5)	0.070 (4)	0.057 (4)	−0.019 (3)	−0.006 (3)	−0.005 (3)
C28	0.058 (4)	0.049 (4)	0.044 (5)	−0.001 (3)	0.001 (4)	0.004 (3)
C23	0.057 (4)	0.042 (3)	0.048 (4)	0.002 (3)	0.001 (4)	0.008 (3)
C26	0.054 (7)	0.057 (5)	0.081 (6)	−0.021 (6)	−0.008 (7)	0.004 (4)
C25	0.035 (5)	0.044 (4)	0.061 (6)	−0.013 (4)	0.001 (4)	0.015 (4)
Cl2	0.0759 (13)	0.0972 (15)	0.0901 (14)	−0.0384 (11)	0.0000 (10)	0.0041 (10)
C22	0.093 (12)	0.084 (10)	0.057 (9)	−0.015 (8)	−0.011 (7)	−0.006 (6)

Geometric parameters (Å, º)

Cl1—C12	1.732 (7)	N1—C8	1.418 (7)
O1—C1	1.264 (3)	C20—H20A	0.9800
O2—C1	1.228 (3)	C20—H20B	0.9800
N3—H3A	0.917 (16)	C20—H20C	0.9800
N3—C18	1.338 (3)	C9—H9	0.9500
N3—C17	1.333 (3)	C9—C8	1.361 (15)
N2—C15	1.336 (3)	C9—C10	1.392 (14)
N2—C21	1.450 (3)	C13—C12	1.387 (9)
N2—C20	1.468 (3)	C13—C14	1.494 (11)
C15—C19	1.412 (3)	C13—C8	1.406 (7)
C15—C16	1.415 (3)	C12—C11	1.368 (8)
C2—C1	1.510 (3)	C14—H14A	0.9800
C2—C3	1.382 (3)	C14—H14B	0.9800
C2—C7	1.402 (3)	C14—H14C	0.9800
C3—H3	0.9500	C11—H11	0.9500
C3—C4	1.380 (3)	C11—C10	1.358 (8)
C18—H18	0.9500	C10—H10	0.9500
C18—C19	1.357 (3)	N4—H4A	0.87 (2)
C19—H19	0.9500	N4—C23	1.430 (11)
C16—H16	0.9500	C24—C23	1.379 (11)
C16—C17	1.355 (3)	C24—C25	1.399 (13)
C7—C6	1.409 (3)	C24—C22	1.51 (2)
C7—N1	1.386 (5)	C27—H27	0.9500
C7—N4	1.453 (7)	C27—C28	1.356 (10)
C4—H4	0.9500	C27—C26	1.395 (16)
C4—C5	1.369 (3)	C28—H28	0.9500
C17—H17	0.9500	C28—C25	1.329 (12)
C5—H5	0.9500	C23—C26	1.38 (2)
C5—C6	1.364 (3)	C26—H26	0.9500
C6—H6	0.9500	C25—Cl2	1.773 (10)
C21—H21A	0.9800	C22—H22A	0.9800
C21—H21B	0.9800	C22—H22B	0.9800
C21—H21C	0.9800	C22—H22C	0.9800
N1—H1	0.860 (19)
C18—N3—H3A	124.8 (16)	N2—C20—H20C	109.5
C17—N3—H3A	116.3 (16)	H20A—C20—H20B	109.5
C17—N3—C18	118.92 (19)	H20A—C20—H20C	109.5
C15—N2—C21	122.9 (2)	H20B—C20—H20C	109.5
C15—N2—C20	122.0 (2)	C8—C9—H9	119.6
C21—N2—C20	114.9 (2)	C8—C9—C10	120.9 (9)
N2—C15—C19	122.9 (2)	C10—C9—H9	119.6
N2—C15—C16	122.1 (2)	C12—C13—C14	122.3 (7)
C19—C15—C16	115.08 (19)	C12—C13—C8	116.0 (6)
C3—C2—C1	117.91 (18)	C8—C13—C14	121.7 (7)
C3—C2—C7	118.61 (18)	C13—C12—Cl1	120.2 (6)
C7—C2—C1	123.46 (18)	C11—C12—Cl1	117.1 (5)
O1—C1—C2	117.24 (18)	C11—C12—C13	122.6 (6)
O2—C1—O1	123.9 (2)	C13—C14—H14A	109.5
O2—C1—C2	118.9 (2)	C13—C14—H14B	109.5
C2—C3—H3	118.8	C13—C14—H14C	109.5
C4—C3—C2	122.5 (2)	H14A—C14—H14B	109.5
C4—C3—H3	118.8	H14A—C14—H14C	109.5
N3—C18—H18	119.0	H14B—C14—H14C	109.5
N3—C18—C19	122.1 (2)	C12—C11—H11	119.8
C19—C18—H18	119.0	C10—C11—C12	120.5 (5)
C15—C19—H19	119.6	C10—C11—H11	119.8
C18—C19—C15	120.9 (2)	C9—C8—N1	118.0 (6)
C18—C19—H19	119.6	C9—C8—C13	121.2 (7)
C15—C16—H16	119.8	C13—C8—N1	120.8 (6)
C17—C16—C15	120.5 (2)	C9—C10—H10	120.6
C17—C16—H16	119.8	C11—C10—C9	118.8 (7)
C2—C7—C6	118.29 (19)	C11—C10—H10	120.6
C2—C7—N4	119.2 (3)	C7—N4—H4A	124 (4)
C6—C7—N4	119.2 (3)	C23—N4—C7	124.2 (5)
N1—C7—C2	121.2 (3)	C23—N4—H4A	110 (4)
N1—C7—C6	118.3 (3)	C23—C24—C25	114.9 (9)
C3—C4—H4	120.7	C23—C24—C22	122.3 (14)
C5—C4—C3	118.6 (2)	C25—C24—C22	122.9 (12)
C5—C4—H4	120.7	C28—C27—H27	120.8
N3—C17—C16	122.6 (2)	C28—C27—C26	118.4 (10)
N3—C17—H17	118.7	C26—C27—H27	120.8
C16—C17—H17	118.7	C27—C28—H28	120.3
C4—C5—H5	119.5	C25—C28—C27	119.5 (9)
C6—C5—C4	120.9 (2)	C25—C28—H28	120.3
C6—C5—H5	119.5	C24—C23—N4	120.1 (10)
C7—C6—H6	119.5	C24—C23—C26	120.7 (10)
C5—C6—C7	121.1 (2)	C26—C23—N4	119.1 (8)
C5—C6—H6	119.5	C27—C26—H26	119.4
N2—C21—H21A	109.5	C23—C26—C27	121.2 (11)
N2—C21—H21B	109.5	C23—C26—H26	119.4
N2—C21—H21C	109.5	C24—C25—Cl2	116.2 (9)
H21A—C21—H21B	109.5	C28—C25—C24	125.4 (10)
H21A—C21—H21C	109.5	C28—C25—Cl2	118.4 (6)
H21B—C21—H21C	109.5	C24—C22—H22A	109.5
C7—N1—H1	112 (3)	C24—C22—H22B	109.5
C7—N1—C8	124.3 (4)	C24—C22—H22C	109.5
C8—N1—H1	121 (3)	H22A—C22—H22B	109.5
N2—C20—H20A	109.5	H22A—C22—H22C	109.5
N2—C20—H20B	109.5	H22B—C22—H22C	109.5
Cl1—C12—C11—C10	−179.2 (4)	C21—N2—C15—C19	2.4 (3)
N3—C18—C19—C15	0.5 (3)	C21—N2—C15—C16	−179.0 (2)
N2—C15—C19—C18	178.7 (2)	N1—C7—C6—C5	164.3 (3)
N2—C15—C16—C17	−178.9 (2)	C20—N2—C15—C19	177.2 (2)
C15—C16—C17—N3	−0.3 (4)	C20—N2—C15—C16	−4.1 (3)
C2—C3—C4—C5	0.6 (4)	C13—C12—C11—C10	−0.1 (8)
C2—C7—C6—C5	1.0 (4)	C12—C13—C8—N1	177.8 (4)
C2—C7—N1—C8	−178.6 (4)	C12—C13—C8—C9	−1.5 (9)
C2—C7—N4—C23	−170.2 (7)	C12—C11—C10—C9	−0.9 (10)
C1—C2—C3—C4	−178.1 (2)	C14—C13—C12—Cl1	2.2 (8)
C1—C2—C7—C6	177.2 (2)	C14—C13—C12—C11	−176.8 (7)
C1—C2—C7—N1	14.4 (4)	C14—C13—C8—N1	−4.1 (8)
C1—C2—C7—N4	−23.5 (5)	C14—C13—C8—C9	176.7 (10)
C3—C2—C1—O1	−173.1 (2)	C8—C9—C10—C11	0.7 (16)
C3—C2—C1—O2	8.2 (3)	C8—C13—C12—Cl1	−179.7 (3)
C3—C2—C7—C6	−1.0 (4)	C8—C13—C12—C11	1.3 (7)
C3—C2—C7—N1	−163.8 (3)	C10—C9—C8—N1	−178.7 (8)
C3—C2—C7—N4	158.3 (4)	C10—C9—C8—C13	0.5 (15)
C3—C4—C5—C6	−0.7 (4)	N4—C7—C6—C5	−158.3 (4)
C18—N3—C17—C16	0.8 (4)	N4—C23—C26—C27	177.4 (9)
C19—C15—C16—C17	−0.1 (3)	C24—C23—C26—C27	−0.4 (16)
C16—C15—C19—C18	0.0 (3)	C27—C28—C25—C24	−0.8 (11)
C7—C2—C1—O1	8.7 (3)	C27—C28—C25—Cl2	179.2 (5)
C7—C2—C1—O2	−170.0 (2)	C28—C27—C26—C23	−0.7 (16)
C7—C2—C3—C4	0.2 (3)	C23—C24—C25—C28	−0.3 (10)
C7—N1—C8—C9	−109.3 (9)	C23—C24—C25—Cl2	179.8 (5)
C7—N1—C8—C13	71.4 (6)	C26—C27—C28—C25	1.2 (12)
C7—N4—C23—C24	−71.4 (9)	C25—C24—C23—N4	−176.9 (6)
C7—N4—C23—C26	110.8 (10)	C25—C24—C23—C26	0.9 (11)
C4—C5—C6—C7	−0.1 (4)	C22—C24—C23—N4	3.5 (14)
C17—N3—C18—C19	−0.9 (3)	C22—C24—C23—C26	−178.8 (14)
C6—C7—N1—C8	18.6 (7)	C22—C24—C25—C28	179.3 (13)
C6—C7—N4—C23	−11.1 (10)	C22—C24—C25—Cl2	−0.6 (14)

(tfa-dmap-H2O_1-1-1)

Crystal data

C14H11ClNO2·C7H11N2·H2O	Z = 2
Mr = 401.88	F(000) = 424
Triclinic, P1	Dx = 1.364 Mg m^−3
a = 7.7631 (6) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.0250 (6) Å	Cell parameters from 2768 reflections
c = 16.2297 (12) Å	θ = 5.6–65.9°
α = 101.784 (6)°	µ = 1.96 mm^−1
β = 98.374 (6)°	T = 100 K
γ = 90.687 (6)°	Block, colourless
V = 978.32 (13) Å^3	0.65 × 0.45 × 0.3 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	3366 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	2829 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.046
Detector resolution: 7.9580 pixels mm^-1	θmax = 66.2°, θmin = 2.8°
ω scans	h = −9→9
Absorption correction: multi-scan CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→8
Tmin = 0.747, Tmax = 1.000	l = −16→19
6172 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.155	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3366 reflections	Δρmax = 0.27 e Å^−3
265 parameters	Δρmin = −0.39 e Å^−3
2 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl1	0.71478 (8)	1.19551 (8)	0.09186 (4)	0.0382 (2)
O1	0.55610 (19)	0.50022 (19)	0.34168 (9)	0.0184 (3)
O2	0.2900 (2)	0.3879 (2)	0.33746 (9)	0.0235 (4)
N1	0.5891 (2)	0.6832 (2)	0.22370 (11)	0.0189 (4)
H1	0.632 (3)	0.644 (3)	0.2675 (13)	0.023*
C1	0.4003 (3)	0.4534 (3)	0.30404 (13)	0.0165 (4)
C2	0.3510 (3)	0.4762 (3)	0.21393 (12)	0.0158 (4)
C3	0.2057 (3)	0.3808 (3)	0.16440 (13)	0.0191 (5)
H3	0.138223	0.312301	0.190192	0.023*
C4	0.1577 (3)	0.3833 (3)	0.07941 (13)	0.0202 (5)
H4	0.059467	0.316841	0.046904	0.024*
C5	0.2558 (3)	0.4848 (3)	0.04242 (13)	0.0196 (5)
H5	0.224741	0.486961	−0.016158	0.024*
C6	0.3985 (3)	0.5832 (3)	0.08960 (13)	0.0187 (5)
H6	0.463255	0.652319	0.062928	0.022*
C7	0.4488 (3)	0.5822 (3)	0.17584 (12)	0.0164 (4)
C8	0.7048 (3)	0.7760 (3)	0.18860 (12)	0.0174 (4)
C9	0.6521 (3)	0.9261 (3)	0.16129 (13)	0.0192 (5)
C10	0.7739 (3)	1.0089 (3)	0.12682 (13)	0.0221 (5)
C11	0.9410 (3)	0.9541 (3)	0.12046 (13)	0.0235 (5)
H11	1.019648	1.014610	0.096356	0.028*
C12	0.9908 (3)	0.8089 (3)	0.15005 (13)	0.0239 (5)
H12	1.105763	0.770816	0.147895	0.029*
C13	0.8730 (3)	0.7196 (3)	0.18268 (13)	0.0211 (5)
H13	0.906808	0.618410	0.201333	0.025*
C14	0.4742 (3)	0.9944 (3)	0.17044 (15)	0.0260 (5)
H14A	0.399969	0.969990	0.114762	0.039*
H14B	0.485313	1.117807	0.192393	0.039*
H14C	0.421737	0.939728	0.210121	0.039*
N2	1.0721 (2)	−0.1642 (2)	0.39099 (11)	0.0182 (4)
N3	0.7483 (2)	0.2296 (2)	0.36356 (11)	0.0206 (4)
H3A	0.686 (3)	0.315 (3)	0.3581 (16)	0.025*
C15	0.9658 (3)	−0.0372 (3)	0.38155 (12)	0.0168 (5)
C16	0.7972 (3)	−0.0329 (3)	0.40652 (12)	0.0181 (5)
H16	0.755859	−0.123390	0.429126	0.022*
C17	0.6955 (3)	0.1016 (3)	0.39784 (13)	0.0210 (5)
H17	0.584757	0.105302	0.416360	0.025*
C18	0.9055 (3)	0.2286 (3)	0.33753 (13)	0.0203 (5)
H18	0.939643	0.319054	0.312840	0.024*
C19	1.0162 (3)	0.1009 (3)	0.34587 (12)	0.0194 (5)
H19	1.127176	0.103771	0.327922	0.023*
C20	1.0111 (3)	−0.3132 (3)	0.41870 (14)	0.0230 (5)
H20A	0.990128	−0.279973	0.477822	0.034*
H20B	1.099653	−0.399269	0.414717	0.034*
H20C	0.902533	−0.360411	0.382186	0.034*
C21	1.2516 (3)	−0.1569 (3)	0.37506 (14)	0.0236 (5)
H21A	1.253702	−0.184044	0.313554	0.035*
H21B	1.318579	−0.239604	0.401828	0.035*
H21C	1.303167	−0.042064	0.399092	0.035*
O3	0.3861 (2)	0.2898 (2)	0.49152 (9)	0.0242 (4)
H3B	0.369199	0.343147	0.449617	0.036*
H3C	0.402851	0.370491	0.537047	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0351 (4)	0.0322 (4)	0.0524 (4)	−0.0065 (3)	0.0007 (3)	0.0256 (3)
O1	0.0178 (7)	0.0182 (8)	0.0180 (7)	−0.0010 (6)	−0.0018 (6)	0.0044 (6)
O2	0.0238 (8)	0.0261 (9)	0.0217 (7)	−0.0067 (7)	0.0016 (6)	0.0090 (6)
N1	0.0191 (9)	0.0213 (10)	0.0147 (8)	−0.0067 (7)	−0.0034 (7)	0.0047 (7)
C1	0.0174 (10)	0.0136 (11)	0.0182 (10)	−0.0008 (8)	0.0028 (8)	0.0027 (8)
C2	0.0155 (10)	0.0124 (10)	0.0175 (10)	0.0006 (8)	0.0002 (8)	0.0002 (7)
C3	0.0159 (10)	0.0184 (11)	0.0215 (10)	−0.0022 (8)	0.0028 (8)	0.0009 (8)
C4	0.0162 (10)	0.0185 (11)	0.0224 (10)	−0.0036 (8)	−0.0017 (8)	−0.0001 (8)
C5	0.0213 (11)	0.0206 (12)	0.0148 (9)	0.0001 (9)	−0.0004 (8)	0.0011 (8)
C6	0.0167 (10)	0.0198 (11)	0.0190 (10)	−0.0019 (8)	0.0030 (8)	0.0026 (8)
C7	0.0137 (10)	0.0137 (11)	0.0201 (10)	0.0010 (8)	0.0017 (8)	−0.0001 (8)
C8	0.0177 (10)	0.0179 (11)	0.0147 (9)	−0.0046 (8)	−0.0012 (7)	0.0023 (8)
C9	0.0196 (11)	0.0181 (11)	0.0178 (10)	−0.0040 (9)	−0.0020 (8)	0.0023 (8)
C10	0.0242 (11)	0.0192 (12)	0.0214 (10)	−0.0078 (9)	−0.0012 (8)	0.0042 (8)
C11	0.0223 (11)	0.0277 (13)	0.0187 (10)	−0.0111 (9)	0.0024 (8)	0.0016 (9)
C12	0.0161 (10)	0.0296 (13)	0.0207 (10)	−0.0042 (9)	0.0000 (8)	−0.0050 (9)
C13	0.0191 (11)	0.0210 (12)	0.0191 (10)	−0.0010 (9)	−0.0021 (8)	−0.0015 (8)
C14	0.0202 (11)	0.0239 (13)	0.0319 (12)	0.0003 (9)	−0.0004 (9)	0.0046 (9)
N2	0.0152 (9)	0.0179 (10)	0.0201 (8)	−0.0014 (7)	0.0002 (7)	0.0030 (7)
N3	0.0188 (10)	0.0192 (10)	0.0218 (9)	0.0015 (8)	−0.0013 (7)	0.0025 (7)
C15	0.0162 (10)	0.0187 (11)	0.0118 (9)	−0.0029 (8)	−0.0017 (7)	−0.0026 (8)
C16	0.0163 (10)	0.0200 (11)	0.0155 (9)	−0.0053 (8)	−0.0007 (8)	0.0005 (8)
C17	0.0154 (10)	0.0223 (12)	0.0211 (10)	−0.0035 (9)	−0.0012 (8)	−0.0022 (8)
C18	0.0212 (11)	0.0200 (12)	0.0174 (10)	−0.0045 (9)	−0.0018 (8)	0.0027 (8)
C19	0.0185 (10)	0.0213 (12)	0.0165 (9)	−0.0038 (9)	0.0022 (8)	−0.0001 (8)
C20	0.0226 (11)	0.0192 (12)	0.0266 (11)	−0.0003 (9)	0.0018 (9)	0.0047 (9)
C21	0.0180 (11)	0.0242 (12)	0.0271 (11)	0.0010 (9)	0.0029 (9)	0.0022 (9)
O3	0.0318 (9)	0.0214 (9)	0.0193 (7)	0.0008 (7)	0.0029 (7)	0.0045 (6)

Geometric parameters (Å, º)

Cl1—C10	1.750 (2)	C13—H13	0.9500
O1—C1	1.288 (3)	C14—H14A	0.9800
O2—C1	1.242 (3)	C14—H14B	0.9800
N1—H1	0.860 (16)	C14—H14C	0.9800
N1—C7	1.386 (3)	N2—C15	1.338 (3)
N1—C8	1.412 (3)	N2—C20	1.457 (3)
C1—C2	1.506 (3)	N2—C21	1.456 (3)
C2—C3	1.403 (3)	N3—H3A	0.857 (17)
C2—C7	1.421 (3)	N3—C17	1.350 (3)
C3—H3	0.9500	N3—C18	1.348 (3)
C3—C4	1.380 (3)	C15—C16	1.424 (3)
C4—H4	0.9500	C15—C19	1.426 (3)
C4—C5	1.386 (3)	C16—H16	0.9500
C5—H5	0.9500	C16—C17	1.363 (3)
C5—C6	1.387 (3)	C17—H17	0.9500
C6—H6	0.9500	C18—H18	0.9500
C6—C7	1.399 (3)	C18—C19	1.361 (3)
C8—C9	1.411 (3)	C19—H19	0.9500
C8—C13	1.397 (3)	C20—H20A	0.9800
C9—C10	1.393 (3)	C20—H20B	0.9800
C9—C14	1.508 (3)	C20—H20C	0.9800
C10—C11	1.386 (3)	C21—H21A	0.9800
C11—H11	0.9500	C21—H21B	0.9800
C11—C12	1.387 (3)	C21—H21C	0.9800
C12—H12	0.9500	O3—H3B	0.8702
C12—C13	1.382 (3)	O3—H3C	0.8699
C7—N1—H1	111.7 (18)	C12—C13—H13	119.5
C7—N1—C8	123.71 (17)	C9—C14—H14A	109.5
C8—N1—H1	117.0 (18)	C9—C14—H14B	109.5
O1—C1—C2	117.89 (18)	C9—C14—H14C	109.5
O2—C1—O1	123.62 (18)	H14A—C14—H14B	109.5
O2—C1—C2	118.47 (18)	H14A—C14—H14C	109.5
C3—C2—C1	117.71 (19)	H14B—C14—H14C	109.5
C3—C2—C7	118.85 (18)	C15—N2—C20	120.55 (18)
C7—C2—C1	123.37 (18)	C15—N2—C21	121.24 (19)
C2—C3—H3	119.0	C21—N2—C20	118.20 (18)
C4—C3—C2	122.1 (2)	C17—N3—H3A	122.7 (18)
C4—C3—H3	119.0	C18—N3—H3A	116.7 (18)
C3—C4—H4	120.7	C18—N3—C17	120.54 (19)
C3—C4—C5	118.63 (19)	N2—C15—C16	121.8 (2)
C5—C4—H4	120.7	N2—C15—C19	121.48 (19)
C4—C5—H5	119.5	C16—C15—C19	116.7 (2)
C4—C5—C6	121.03 (19)	C15—C16—H16	120.1
C6—C5—H5	119.5	C17—C16—C15	119.7 (2)
C5—C6—H6	119.5	C17—C16—H16	120.1
C5—C6—C7	121.0 (2)	N3—C17—C16	121.6 (2)
C7—C6—H6	119.5	N3—C17—H17	119.2
N1—C7—C2	120.42 (18)	C16—C17—H17	119.2
N1—C7—C6	121.2 (2)	N3—C18—H18	119.3
C6—C7—C2	118.35 (19)	N3—C18—C19	121.4 (2)
C9—C8—N1	120.26 (19)	C19—C18—H18	119.3
C13—C8—N1	119.3 (2)	C15—C19—H19	120.0
C13—C8—C9	120.4 (2)	C18—C19—C15	120.0 (2)
C8—C9—C14	121.6 (2)	C18—C19—H19	120.0
C10—C9—C8	116.5 (2)	N2—C20—H20A	109.5
C10—C9—C14	121.9 (2)	N2—C20—H20B	109.5
C9—C10—Cl1	118.28 (17)	N2—C20—H20C	109.5
C11—C10—Cl1	118.06 (18)	H20A—C20—H20B	109.5
C11—C10—C9	123.6 (2)	H20A—C20—H20C	109.5
C10—C11—H11	120.7	H20B—C20—H20C	109.5
C10—C11—C12	118.6 (2)	N2—C21—H21A	109.5
C12—C11—H11	120.7	N2—C21—H21B	109.5
C11—C12—H12	120.0	N2—C21—H21C	109.5
C13—C12—C11	119.9 (2)	H21A—C21—H21B	109.5
C13—C12—H12	120.0	H21A—C21—H21C	109.5
C8—C13—H13	119.5	H21B—C21—H21C	109.5
C12—C13—C8	120.9 (2)	H3B—O3—H3C	104.5
Cl1—C10—C11—C12	178.31 (15)	C8—C9—C10—Cl1	179.93 (15)
O1—C1—C2—C3	160.81 (18)	C8—C9—C10—C11	−1.6 (3)
O1—C1—C2—C7	−16.0 (3)	C9—C8—C13—C12	0.0 (3)
O2—C1—C2—C3	−17.9 (3)	C9—C10—C11—C12	−0.1 (3)
O2—C1—C2—C7	165.26 (19)	C10—C11—C12—C13	1.9 (3)
N1—C8—C9—C10	−179.49 (17)	C11—C12—C13—C8	−1.8 (3)
N1—C8—C9—C14	1.5 (3)	C13—C8—C9—C10	1.7 (3)
N1—C8—C13—C12	−178.86 (17)	C13—C8—C9—C14	−177.27 (18)
C1—C2—C3—C4	−175.19 (19)	C14—C9—C10—Cl1	−1.1 (3)
C1—C2—C7—N1	−5.7 (3)	C14—C9—C10—C11	177.3 (2)
C1—C2—C7—C6	175.00 (18)	N2—C15—C16—C17	178.19 (18)
C2—C3—C4—C5	−0.6 (3)	N2—C15—C19—C18	−179.67 (18)
C3—C2—C7—N1	177.53 (18)	N3—C18—C19—C15	1.0 (3)
C3—C2—C7—C6	−1.8 (3)	C15—C16—C17—N3	2.0 (3)
C3—C4—C5—C6	−0.5 (3)	C16—C15—C19—C18	0.3 (3)
C4—C5—C6—C7	0.4 (3)	C17—N3—C18—C19	−0.9 (3)
C5—C6—C7—N1	−178.59 (19)	C18—N3—C17—C16	−0.7 (3)
C5—C6—C7—C2	0.7 (3)	C19—C15—C16—C17	−1.8 (3)
C7—N1—C8—C9	74.5 (3)	C20—N2—C15—C16	6.8 (3)
C7—N1—C8—C13	−106.7 (2)	C20—N2—C15—C19	−173.16 (17)
C7—C2—C3—C4	1.8 (3)	C21—N2—C15—C16	−172.37 (17)
C8—N1—C7—C2	172.20 (19)	C21—N2—C15—C19	7.6 (3)
C8—N1—C7—C6	−8.5 (3)

(tfa-dmap_2-1)

Crystal data

C14H12ClNO2·C14H11ClNO2·C7H11N2	Z = 2
Mr = 645.56	F(000) = 676
Triclinic, P1	Dx = 1.344 Mg m^−3
a = 10.8864 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.2705 (7) Å	Cell parameters from 2351 reflections
c = 13.7811 (10) Å	θ = 3.9–26.4°
α = 106.966 (6)°	µ = 0.25 mm^−1
β = 105.782 (6)°	T = 293 K
γ = 103.324 (5)°	Block, colourless
V = 1595.53 (19) Å^3	0.34 × 0.28 × 0.1 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	5577 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3784 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.022
Detector resolution: 7.9580 pixels mm^-1	θmax = 25.0°, θmin = 3.9°
ω scans	h = −12→12
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.33c (release 11-04-2014 CrysAlis171 .NET) (compiled Apr 11 2014,15:12:41) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −14→14
Tmin = 0.739, Tmax = 1.000	l = −16→16
8477 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.076	H-atom parameters constrained
wR(F^2) = 0.204	w = 1/[σ^2(Fo^2) + (0.0721P)^2 + 1.2105P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5577 reflections	Δρmax = 0.36 e Å^−3
582 parameters	Δρmin = −0.16 e Å^−3
6 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O3	0.7045 (3)	0.5557 (2)	0.3362 (2)	0.0732 (8)
H3	0.734 (4)	0.527 (4)	0.288 (3)	0.110*
O4	0.9145 (2)	0.6754 (2)	0.43924 (19)	0.0674 (8)
C15	0.7934 (3)	0.6449 (3)	0.4225 (2)	0.0440 (7)
C16	0.7347 (3)	0.7074 (3)	0.4980 (2)	0.0408 (7)
C17	0.5967 (3)	0.6647 (3)	0.4740 (3)	0.0596 (10)
H17	0.543534	0.596317	0.411450	0.071*
C18	0.5349 (4)	0.7191 (4)	0.5386 (3)	0.0704 (11)
H18	0.441618	0.688630	0.520008	0.084*
C19	0.6134 (4)	0.8193 (3)	0.6312 (3)	0.0612 (10)
H19	0.572905	0.856993	0.675923	0.073*
C20	0.7501 (3)	0.8643 (3)	0.6585 (3)	0.0556 (9)
H20	0.801141	0.932604	0.721705	0.067*
C21	0.8157 (3)	0.8099 (3)	0.5934 (2)	0.0461 (8)
Cl2	1.2336 (2)	1.09870 (18)	1.02376 (13)	0.0932 (7)	0.649 (3)
N2	0.9517 (15)	0.8672 (10)	0.6149 (11)	0.050 (2)	0.649 (3)
H2	0.984 (6)	0.830 (5)	0.569 (4)	0.060*	0.6493
C22	1.0366 (8)	0.9765 (10)	0.7025 (7)	0.0450 (18)	0.649 (3)
C23	1.0834 (8)	0.9790 (7)	0.8070 (9)	0.0486 (19)	0.649 (3)
C24	1.1683 (7)	1.0867 (7)	0.8890 (6)	0.0543 (18)	0.649 (3)
C25	1.2073 (9)	1.1928 (8)	0.8708 (7)	0.057 (2)	0.649 (3)
H25	1.264863	1.264789	0.928127	0.069*	0.649 (3)
C26	1.1597 (6)	1.1895 (5)	0.7672 (5)	0.0628 (15)	0.649 (3)
H26	1.185026	1.258885	0.752485	0.075*	0.649 (3)
C27	1.0728 (15)	1.0809 (14)	0.6842 (10)	0.062 (3)	0.649 (3)
H27	1.038083	1.078874	0.613906	0.074*	0.649 (3)
C28	1.0462 (18)	0.8689 (10)	0.8329 (15)	0.069 (3)	0.649 (3)
H28A	0.974486	0.869169	0.860902	0.104*	0.649 (3)
H28B	1.123780	0.868851	0.886598	0.104*	0.649 (3)
H28C	1.016298	0.797897	0.768018	0.104*	0.649 (3)
O1	0.5692 (3)	0.3446 (2)	0.0652 (2)	0.0746 (8)
O2	0.7762 (3)	0.4448 (2)	0.18603 (19)	0.0722 (8)
C1	0.6942 (3)	0.3682 (3)	0.0957 (2)	0.0456 (8)
C2	0.7517 (3)	0.3009 (3)	0.0204 (2)	0.0400 (7)
C3	0.8901 (3)	0.3405 (3)	0.0459 (3)	0.0546 (9)
H3A	0.943519	0.406808	0.110092	0.066*
C4	0.9531 (4)	0.2873 (3)	−0.0185 (3)	0.0628 (10)
H4	1.046539	0.317765	0.000686	0.075*
C5	0.8744 (3)	0.1877 (3)	−0.1122 (3)	0.0562 (9)
H5A	0.915225	0.149282	−0.156264	0.067*
C6	0.7378 (3)	0.1446 (3)	−0.1412 (3)	0.0562 (9)
H6	0.686560	0.077481	−0.205284	0.067*
C7	0.6718 (3)	0.1996 (3)	−0.0762 (3)	0.0498 (8)
Cl1	0.2722 (3)	−0.0683 (2)	−0.51096 (16)	0.1248 (10)	0.649 (3)
N1	0.5348 (11)	0.143 (3)	−0.099 (2)	0.057 (5)	0.67 (12)
H1	0.502 (6)	0.183 (5)	−0.056 (4)	0.068*	0.6702
C8	0.4504 (8)	0.0381 (11)	−0.1895 (7)	0.0464 (17)	0.649 (3)
C9	0.4091 (7)	0.0400 (7)	−0.2931 (10)	0.0509 (17)	0.649 (3)
C10	0.3240 (8)	−0.0671 (11)	−0.3766 (8)	0.059 (2)	0.649 (3)
C11	0.2774 (7)	−0.1731 (7)	−0.3673 (8)	0.067 (2)	0.649 (3)
H11	0.220110	−0.242313	−0.427795	0.081*	0.649 (3)
C12	0.3181 (6)	−0.1754 (5)	−0.2639 (6)	0.0698 (17)	0.649 (3)
H12	0.288415	−0.246412	−0.252574	0.084*	0.649 (3)
C13	0.4030 (14)	−0.0706 (13)	−0.1787 (10)	0.063 (3)	0.649 (3)
H13	0.430594	−0.072543	−0.109343	0.076*	0.649 (3)
C14	0.4575 (15)	0.1532 (12)	−0.3122 (14)	0.088 (4)	0.649 (3)
H14A	0.493414	0.221567	−0.244409	0.131*	0.649 (3)
H14B	0.383199	0.161804	−0.362363	0.131*	0.649 (3)
H14C	0.527145	0.149114	−0.342070	0.131*	0.649 (3)
N3	0.1498 (3)	0.5440 (3)	0.2998 (2)	0.0554 (8)
N4	0.4116 (3)	0.4344 (3)	0.1599 (2)	0.0587 (8)
H4A	0.473 (3)	0.424 (3)	0.130 (3)	0.070*
C29	0.2361 (3)	0.5067 (3)	0.2530 (2)	0.0424 (7)
C30	0.2875 (3)	0.4180 (3)	0.2729 (3)	0.0552 (9)
H30	0.262195	0.381732	0.318281	0.066*
C31	0.3756 (3)	0.3842 (3)	0.2253 (3)	0.0524 (8)
H31	0.410240	0.325487	0.239257	0.063*
C32	0.3635 (4)	0.5178 (3)	0.1367 (3)	0.0560 (9)
H32	0.390611	0.551484	0.090392	0.067*
C33	0.2739 (4)	0.5543 (3)	0.1810 (3)	0.0582 (9)
H33	0.238411	0.610882	0.162877	0.070*
C34	0.1056 (4)	0.4910 (3)	0.3696 (3)	0.0640 (10)
H34A	0.059159	0.405675	0.330065	0.096*
H34B	0.045221	0.527767	0.394500	0.096*
H34C	0.182746	0.503992	0.431143	0.096*
C35	0.1013 (4)	0.6377 (3)	0.2806 (3)	0.0649 (10)
H35A	0.176921	0.707554	0.297332	0.097*
H35B	0.050753	0.658695	0.326064	0.097*
H35C	0.043879	0.609566	0.205476	0.097*
Cl3	1.2458 (4)	1.2882 (3)	0.8528 (3)	0.0871 (12)	0.351 (3)
Cl4	0.2443 (4)	−0.2714 (3)	−0.3480 (3)	0.1012 (14)	0.351 (3)
N5	0.954 (3)	0.8354 (19)	0.6365 (19)	0.049 (4)	0.351 (3)
H5	0.988 (11)	0.797 (9)	0.592 (7)	0.059*	0.3507
N6	0.532 (2)	0.179 (6)	−0.127 (5)	0.052 (12)	0.33 (12)
H6A	0.490 (11)	0.211 (10)	−0.086 (8)	0.063*	0.3298
C43	1.1551 (15)	1.0061 (13)	0.9342 (10)	0.089 (4)	0.351 (3)
H43	1.172949	0.989972	0.997541	0.107*	0.351 (3)
C40	0.3973 (14)	−0.034 (2)	−0.2336 (10)	0.049 (3)	0.351 (3)
C42	1.0916 (13)	1.0504 (18)	0.7415 (9)	0.045 (3)	0.351 (3)
C46	1.0406 (15)	0.9357 (14)	0.7357 (16)	0.043 (3)	0.351 (3)
C41	0.3324 (16)	0.0183 (18)	−0.4205 (10)	0.099 (5)	0.351 (3)
H41	0.310808	0.035990	−0.482955	0.119*	0.351 (3)
C48	1.063 (4)	1.076 (3)	0.6420 (17)	0.076 (7)	0.351 (3)
H48A	0.985047	1.012306	0.585171	0.114*	0.351 (3)
H48B	1.139654	1.082513	0.619801	0.114*	0.351 (3)
H48C	1.044963	1.151407	0.655739	0.114*	0.351 (3)
C39	1.1789 (16)	1.1416 (14)	0.8410 (14)	0.053 (4)	0.351 (3)
C44	0.414 (3)	0.107 (3)	−0.3205 (19)	0.075 (7)	0.351 (3)
H44	0.447589	0.186411	−0.314167	0.090*	0.351 (3)
C36	1.074 (3)	0.920 (2)	0.8320 (19)	0.073 (8)	0.351 (3)
H36	1.037025	0.841944	0.828643	0.088*	0.351 (3)
C47	1.2068 (14)	1.1176 (13)	0.9321 (12)	0.057 (2)	0.351 (3)
H47	1.264522	1.180557	0.997449	0.069*	0.351 (3)
C37	0.433 (3)	−0.066 (3)	−0.1365 (17)	0.075 (6)	0.351 (3)
H37A	0.466180	−0.133027	−0.152005	0.112*	0.351 (3)
H37B	0.354531	−0.088417	−0.118328	0.112*	0.351 (3)
H37C	0.502571	0.002079	−0.076238	0.112*	0.351 (3)
C49	0.3114 (15)	−0.1272 (16)	−0.3334 (14)	0.059 (2)	0.351 (3)
C38	0.285 (2)	−0.094 (3)	−0.4246 (12)	0.074 (5)	0.351 (3)
H38	0.230488	−0.154689	−0.492300	0.089*	0.351 (3)
C45	0.4478 (15)	0.0779 (15)	−0.2287 (18)	0.047 (3)	0.351 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0574 (16)	0.0682 (17)	0.0547 (15)	0.0090 (13)	0.0184 (13)	−0.0193 (13)
O4	0.0502 (16)	0.0702 (17)	0.0564 (14)	0.0126 (12)	0.0238 (12)	−0.0090 (12)
C15	0.049 (2)	0.0402 (17)	0.0345 (16)	0.0141 (14)	0.0127 (14)	0.0053 (13)
C16	0.0419 (18)	0.0398 (16)	0.0365 (15)	0.0145 (13)	0.0133 (13)	0.0089 (13)
C17	0.045 (2)	0.054 (2)	0.0512 (19)	0.0083 (16)	0.0094 (16)	−0.0051 (16)
C18	0.040 (2)	0.074 (3)	0.072 (2)	0.0127 (18)	0.0216 (19)	−0.002 (2)
C19	0.052 (2)	0.059 (2)	0.064 (2)	0.0225 (17)	0.0259 (18)	0.0030 (18)
C20	0.047 (2)	0.0452 (19)	0.0540 (19)	0.0123 (15)	0.0161 (16)	−0.0048 (15)
C21	0.0420 (18)	0.0426 (17)	0.0439 (17)	0.0171 (14)	0.0127 (15)	0.0035 (14)
Cl2	0.1077 (15)	0.0915 (13)	0.0458 (9)	0.0215 (11)	−0.0012 (9)	0.0146 (8)
N2	0.042 (3)	0.039 (6)	0.050 (5)	0.009 (4)	0.016 (3)	−0.004 (3)
C22	0.034 (3)	0.043 (5)	0.045 (5)	0.010 (4)	0.009 (3)	0.005 (4)
C23	0.049 (4)	0.046 (5)	0.058 (6)	0.023 (4)	0.023 (4)	0.022 (5)
C24	0.046 (4)	0.048 (4)	0.045 (5)	0.008 (3)	0.005 (3)	0.000 (3)
C25	0.047 (4)	0.047 (5)	0.049 (5)	0.008 (4)	0.007 (3)	−0.004 (3)
C26	0.063 (4)	0.051 (3)	0.068 (4)	0.009 (3)	0.023 (3)	0.020 (3)
C27	0.064 (6)	0.059 (5)	0.051 (8)	0.017 (4)	0.023 (7)	0.006 (7)
C28	0.073 (8)	0.055 (7)	0.065 (5)	0.015 (6)	0.013 (5)	0.020 (6)
O1	0.0528 (16)	0.0800 (18)	0.0647 (16)	0.0222 (13)	0.0262 (13)	−0.0130 (13)
O2	0.0645 (16)	0.0676 (17)	0.0503 (14)	0.0125 (13)	0.0185 (13)	−0.0147 (13)
C1	0.053 (2)	0.0383 (17)	0.0390 (17)	0.0149 (15)	0.0186 (15)	0.0048 (14)
C2	0.0449 (18)	0.0373 (16)	0.0344 (15)	0.0181 (14)	0.0128 (13)	0.0071 (13)
C3	0.046 (2)	0.050 (2)	0.0425 (17)	0.0098 (15)	0.0085 (15)	−0.0049 (15)
C4	0.0395 (19)	0.068 (2)	0.060 (2)	0.0131 (17)	0.0161 (17)	0.0012 (18)
C5	0.050 (2)	0.056 (2)	0.055 (2)	0.0245 (17)	0.0227 (17)	0.0032 (17)
C6	0.046 (2)	0.0456 (19)	0.0514 (19)	0.0138 (15)	0.0112 (16)	−0.0104 (15)
C7	0.0437 (19)	0.0428 (18)	0.0489 (18)	0.0149 (15)	0.0151 (15)	−0.0005 (14)
Cl1	0.141 (2)	0.1242 (19)	0.0567 (12)	0.0256 (15)	−0.0151 (12)	0.0244 (12)
N1	0.043 (3)	0.048 (8)	0.054 (6)	0.009 (3)	0.017 (3)	−0.009 (6)
C8	0.035 (4)	0.045 (5)	0.047 (5)	0.009 (3)	0.018 (4)	0.002 (5)
C9	0.043 (4)	0.054 (5)	0.052 (5)	0.018 (3)	0.009 (4)	0.021 (5)
C10	0.049 (4)	0.058 (6)	0.048 (6)	0.018 (4)	0.004 (4)	0.004 (4)
C11	0.042 (4)	0.060 (5)	0.063 (5)	0.005 (3)	0.010 (4)	−0.010 (4)
C12	0.070 (4)	0.047 (4)	0.082 (5)	0.005 (3)	0.028 (4)	0.020 (4)
C13	0.063 (7)	0.064 (5)	0.054 (8)	0.014 (5)	0.021 (6)	0.013 (7)
C14	0.083 (10)	0.064 (7)	0.097 (7)	0.018 (6)	0.004 (7)	0.037 (5)
N3	0.0531 (17)	0.0505 (17)	0.0565 (17)	0.0168 (14)	0.0235 (14)	0.0093 (14)
N4	0.0522 (18)	0.0561 (18)	0.0548 (17)	0.0172 (15)	0.0227 (15)	0.0009 (15)
C29	0.0411 (17)	0.0367 (16)	0.0375 (16)	0.0074 (13)	0.0135 (14)	0.0028 (13)
C30	0.056 (2)	0.053 (2)	0.0528 (19)	0.0171 (17)	0.0201 (17)	0.0147 (16)
C31	0.054 (2)	0.0478 (19)	0.0488 (19)	0.0162 (16)	0.0195 (17)	0.0100 (16)
C32	0.064 (2)	0.051 (2)	0.054 (2)	0.0182 (18)	0.0279 (18)	0.0149 (16)
C33	0.067 (2)	0.047 (2)	0.064 (2)	0.0207 (17)	0.0300 (19)	0.0167 (17)
C34	0.071 (3)	0.066 (2)	0.059 (2)	0.0196 (19)	0.038 (2)	0.0179 (19)
C35	0.070 (2)	0.050 (2)	0.078 (3)	0.0269 (19)	0.036 (2)	0.0143 (19)
Cl3	0.093 (2)	0.0461 (18)	0.091 (2)	0.0047 (15)	0.0193 (19)	0.0107 (16)
Cl4	0.096 (3)	0.048 (2)	0.129 (3)	0.0006 (17)	0.042 (2)	0.0084 (19)
N5	0.047 (6)	0.031 (9)	0.049 (10)	0.007 (7)	0.013 (7)	−0.006 (5)
N6	0.036 (6)	0.042 (14)	0.052 (13)	0.004 (6)	0.016 (7)	−0.012 (10)
C43	0.118 (12)	0.102 (11)	0.054 (7)	0.030 (9)	0.035 (8)	0.042 (8)
C40	0.047 (7)	0.066 (10)	0.040 (7)	0.023 (7)	0.021 (6)	0.023 (9)
C42	0.042 (7)	0.058 (9)	0.028 (6)	0.019 (7)	0.010 (5)	0.009 (7)
C46	0.042 (7)	0.048 (9)	0.030 (8)	0.014 (6)	0.014 (6)	0.001 (7)
C41	0.116 (12)	0.145 (15)	0.042 (8)	0.056 (12)	0.015 (8)	0.045 (9)
C48	0.083 (11)	0.072 (11)	0.056 (14)	0.011 (8)	0.022 (12)	0.015 (13)
C39	0.048 (8)	0.048 (11)	0.045 (10)	0.016 (8)	0.016 (7)	−0.007 (7)
C44	0.067 (14)	0.10 (2)	0.058 (11)	0.025 (14)	0.022 (10)	0.034 (14)
C36	0.063 (13)	0.08 (2)	0.047 (10)	0.017 (16)	0.000 (8)	0.001 (15)
C47	0.047 (4)	0.047 (5)	0.049 (5)	0.008 (4)	0.007 (3)	−0.004 (3)
C37	0.078 (16)	0.075 (11)	0.055 (12)	0.003 (9)	0.017 (10)	0.026 (11)
C49	0.049 (4)	0.058 (6)	0.048 (6)	0.018 (4)	0.004 (4)	0.004 (4)
C38	0.085 (13)	0.077 (13)	0.038 (11)	0.028 (12)	0.011 (8)	0.002 (10)
C45	0.036 (7)	0.056 (10)	0.033 (9)	0.008 (6)	0.008 (6)	0.004 (8)

Geometric parameters (Å, º)

O3—H3	0.84 (2)	C12—C13	1.366 (15)
O3—C15	1.294 (4)	C13—H13	0.9300
O4—C15	1.220 (4)	C14—H14A	0.9600
C15—C16	1.483 (4)	C14—H14B	0.9600
C16—C17	1.381 (4)	C14—H14C	0.9600
C16—C21	1.408 (4)	N3—C29	1.366 (4)
C17—H17	0.9300	N3—C34	1.434 (4)
C17—C18	1.369 (5)	N3—C35	1.431 (4)
C18—H18	0.9300	N4—H4A	0.884 (19)
C18—C19	1.370 (5)	N4—C31	1.323 (5)
C19—H19	0.9300	N4—C32	1.331 (5)
C19—C20	1.362 (5)	C29—C30	1.394 (4)
C20—H20	0.9300	C29—C33	1.395 (4)
C20—C21	1.408 (4)	C30—H30	0.9300
C21—N2	1.390 (15)	C30—C31	1.374 (5)
C21—N5	1.39 (3)	C31—H31	0.9300
Cl2—C24	1.746 (7)	C32—H32	0.9300
N2—H2	0.87 (2)	C32—C33	1.375 (5)
N2—C22	1.410 (17)	C33—H33	0.9300
C22—C23	1.378 (12)	C34—H34A	0.9600
C22—C27	1.367 (18)	C34—H34B	0.9600
C23—C24	1.370 (13)	C34—H34C	0.9600
C23—C28	1.491 (12)	C35—H35A	0.9600
C24—C25	1.390 (16)	C35—H35B	0.9600
C25—H25	0.9300	C35—H35C	0.9600
C25—C26	1.365 (12)	Cl3—C39	1.719 (18)
C26—H26	0.9300	Cl4—C49	1.68 (2)
C26—C27	1.385 (16)	N5—H5	0.87 (2)
C27—H27	0.9300	N5—C46	1.43 (3)
C28—H28A	0.9600	N6—H6A	0.87 (2)
C28—H28B	0.9600	N6—C45	1.46 (3)
C28—H28C	0.9600	C43—H43	0.9300
O1—C1	1.245 (4)	C43—C36	1.38 (3)
O2—C1	1.248 (4)	C43—C47	1.37 (2)
C1—C2	1.496 (4)	C40—C37	1.48 (2)
C2—C3	1.380 (4)	C40—C49	1.40 (2)
C2—C7	1.408 (4)	C40—C45	1.33 (2)
C3—H3A	0.9300	C42—C46	1.36 (2)
C3—C4	1.373 (5)	C42—C48	1.47 (2)
C4—H4	0.9300	C42—C39	1.39 (2)
C4—C5	1.375 (4)	C46—C36	1.36 (3)
C5—H5A	0.9300	C41—H41	0.9300
C5—C6	1.357 (4)	C41—C44	1.37 (3)
C6—H6	0.9300	C41—C38	1.34 (3)
C6—C7	1.412 (4)	C48—H48A	0.9600
C7—N1	1.395 (18)	C48—H48B	0.9600
C7—N6	1.42 (4)	C48—H48C	0.9600
Cl1—C10	1.778 (12)	C39—C47	1.34 (3)
N1—H1	0.86 (2)	C44—H44	0.9300
N1—C8	1.398 (16)	C44—C45	1.39 (3)
C8—C9	1.383 (12)	C36—H36	0.9300
C8—C13	1.382 (18)	C47—H47	0.9300
C9—C10	1.374 (13)	C37—H37A	0.9600
C9—C14	1.493 (15)	C37—H37B	0.9600
C10—C11	1.34 (2)	C37—H37C	0.9600
C11—H11	0.9300	C49—C38	1.41 (4)
C11—C12	1.383 (13)	C38—H38	0.9300
C12—H12	0.9300
C15—O3—H3	115 (3)	C12—C13—H13	118.1
O3—C15—C16	114.0 (3)	C9—C14—H14A	109.5
O4—C15—O3	122.7 (3)	C9—C14—H14B	109.5
O4—C15—C16	123.2 (3)	C9—C14—H14C	109.5
C17—C16—C15	119.3 (3)	H14A—C14—H14B	109.5
C17—C16—C21	118.8 (3)	H14A—C14—H14C	109.5
C21—C16—C15	121.8 (3)	H14B—C14—H14C	109.5
C16—C17—H17	118.7	C29—N3—C34	121.0 (3)
C18—C17—C16	122.7 (3)	C29—N3—C35	120.8 (3)
C18—C17—H17	118.7	C35—N3—C34	118.2 (3)
C17—C18—H18	120.7	C31—N4—H4A	127 (3)
C17—C18—C19	118.6 (3)	C31—N4—C32	121.8 (3)
C19—C18—H18	120.7	C32—N4—H4A	111 (3)
C18—C19—H19	119.6	N3—C29—C30	121.8 (3)
C20—C19—C18	120.9 (3)	N3—C29—C33	120.9 (3)
C20—C19—H19	119.6	C30—C29—C33	117.3 (3)
C19—C20—H20	119.3	C29—C30—H30	120.0
C19—C20—C21	121.5 (3)	C31—C30—C29	119.9 (3)
C21—C20—H20	119.3	C31—C30—H30	120.0
C16—C21—C20	117.5 (3)	N4—C31—C30	120.7 (3)
N2—C21—C16	121.7 (6)	N4—C31—H31	119.7
N2—C21—C20	120.1 (6)	C30—C31—H31	119.7
N5—C21—C16	120.3 (10)	N4—C32—H32	119.9
N5—C21—C20	119.8 (11)	N4—C32—C33	120.2 (3)
C21—N2—H2	115 (5)	C33—C32—H32	119.9
C21—N2—C22	125.4 (11)	C29—C33—H33	120.0
C22—N2—H2	120 (5)	C32—C33—C29	120.1 (3)
C23—C22—N2	120.4 (10)	C32—C33—H33	120.0
C27—C22—N2	120.0 (9)	N3—C34—H34A	109.5
C27—C22—C23	119.6 (11)	N3—C34—H34B	109.5
C22—C23—C28	122.4 (13)	N3—C34—H34C	109.5
C24—C23—C22	118.2 (7)	H34A—C34—H34B	109.5
C24—C23—C28	119.4 (12)	H34A—C34—H34C	109.5
C23—C24—Cl2	121.6 (7)	H34B—C34—H34C	109.5
C23—C24—C25	122.5 (8)	N3—C35—H35A	109.5
C25—C24—Cl2	115.9 (5)	N3—C35—H35B	109.5
C24—C25—H25	120.6	N3—C35—H35C	109.5
C26—C25—C24	118.8 (7)	H35A—C35—H35B	109.5
C26—C25—H25	120.6	H35A—C35—H35C	109.5
C25—C26—H26	120.6	H35B—C35—H35C	109.5
C25—C26—C27	118.8 (9)	C21—N5—H5	115 (8)
C27—C26—H26	120.6	C21—N5—C46	122 (2)
C22—C27—C26	122.0 (11)	C46—N5—H5	121 (9)
C22—C27—H27	119.0	C7—N6—H6A	118 (9)
C26—C27—H27	119.0	C7—N6—C45	122 (2)
C23—C28—H28A	109.5	C45—N6—H6A	117 (9)
C23—C28—H28B	109.5	C36—C43—H43	123.7
C23—C28—H28C	109.5	C47—C43—H43	123.7
H28A—C28—H28B	109.5	C47—C43—C36	112.6 (16)
H28A—C28—H28C	109.5	C49—C40—C37	118 (2)
H28B—C28—H28C	109.5	C45—C40—C37	122 (2)
O1—C1—O2	124.1 (3)	C45—C40—C49	120.3 (16)
O1—C1—C2	118.8 (3)	C46—C42—C48	120 (2)
O2—C1—C2	117.1 (3)	C46—C42—C39	119.9 (14)
C3—C2—C1	118.7 (3)	C39—C42—C48	120 (2)
C3—C2—C7	117.9 (3)	C42—C46—N5	123.8 (18)
C7—C2—C1	123.4 (3)	C42—C46—C36	115.9 (19)
C2—C3—H3A	118.2	C36—C46—N5	120.3 (16)
C4—C3—C2	123.5 (3)	C44—C41—H41	121.3
C4—C3—H3A	118.2	C38—C41—H41	121.3
C3—C4—H4	120.9	C38—C41—C44	117.3 (17)
C3—C4—C5	118.2 (3)	C42—C48—H48A	109.5
C5—C4—H4	120.9	C42—C48—H48B	109.5
C4—C5—H5A	119.6	C42—C48—H48C	109.5
C6—C5—C4	120.9 (3)	H48A—C48—H48B	109.5
C6—C5—H5A	119.6	H48A—C48—H48C	109.5
C5—C6—H6	119.3	H48B—C48—H48C	109.5
C5—C6—C7	121.4 (3)	C42—C39—Cl3	121.7 (17)
C7—C6—H6	119.3	C47—C39—Cl3	118.1 (10)
C2—C7—C6	118.2 (3)	C47—C39—C42	120.1 (18)
C2—C7—N6	120.4 (10)	C41—C44—H44	119.8
C6—C7—N6	117.9 (13)	C41—C44—C45	120 (2)
N1—C7—C2	121.0 (5)	C45—C44—H44	119.8
N1—C7—C6	120.0 (5)	C43—C36—H36	116.2
C7—N1—H1	114 (5)	C46—C36—C43	128 (2)
C7—N1—C8	124.7 (10)	C46—C36—H36	116.2
C8—N1—H1	121 (5)	C43—C47—H47	118.1
C9—C8—N1	121 (3)	C39—C47—C43	123.7 (13)
C13—C8—N1	121 (2)	C39—C47—H47	118.1
C13—C8—C9	117.6 (11)	C40—C37—H37A	109.5
C8—C9—C14	121.0 (11)	C40—C37—H37B	109.5
C10—C9—C8	116.8 (9)	C40—C37—H37C	109.5
C10—C9—C14	122.1 (12)	H37A—C37—H37B	109.5
C9—C10—Cl1	117.9 (11)	H37A—C37—H37C	109.5
C11—C10—Cl1	115.9 (6)	H37B—C37—H37C	109.5
C11—C10—C9	126.2 (13)	C40—C49—Cl4	123.8 (18)
C10—C11—H11	121.4	C40—C49—C38	116 (2)
C10—C11—C12	117.2 (7)	C38—C49—Cl4	120.3 (13)
C12—C11—H11	121.4	C41—C38—C49	124.4 (16)
C11—C12—H12	120.8	C41—C38—H38	117.8
C13—C12—C11	118.3 (8)	C49—C38—H38	117.8
C13—C12—H12	120.8	C40—C45—N6	123 (5)
C8—C13—H13	118.1	C40—C45—C44	122 (2)
C12—C13—C8	123.9 (11)	C44—C45—N6	116 (5)
O3—C15—C16—C17	2.6 (5)	C6—C7—N6—C45	19 (10)
O3—C15—C16—C21	−176.9 (3)	C7—C2—C3—C4	0.8 (5)
O4—C15—C16—C17	−178.3 (3)	C7—N1—C8—C9	−71 (5)
O4—C15—C16—C21	2.2 (5)	C7—N1—C8—C13	110 (4)
C15—C16—C17—C18	−178.7 (4)	C7—N6—C45—C40	80 (7)
C15—C16—C21—C20	178.7 (3)	C7—N6—C45—C44	−105 (8)
C15—C16—C21—N2	8.3 (6)	Cl1—C10—C11—C12	178.9 (5)
C15—C16—C21—N5	−18.7 (10)	N1—C8—C9—C10	−178.7 (8)
C16—C17—C18—C19	−0.5 (7)	N1—C8—C9—C14	2.3 (14)
C16—C21—N2—C22	173.5 (8)	N1—C8—C13—C12	178.6 (10)
C16—C21—N5—C46	−177.4 (13)	C8—C9—C10—Cl1	−178.7 (5)
C17—C16—C21—C20	−0.8 (5)	C8—C9—C10—C11	−0.1 (13)
C17—C16—C21—N2	−171.2 (5)	C9—C8—C13—C12	−0.2 (15)
C17—C16—C21—N5	161.8 (9)	C9—C10—C11—C12	0.3 (14)
C17—C18—C19—C20	0.2 (6)	C10—C11—C12—C13	−0.4 (12)
C18—C19—C20—C21	−0.2 (6)	C11—C12—C13—C8	0.4 (15)
C19—C20—C21—C16	0.5 (5)	C13—C8—C9—C10	0.0 (11)
C19—C20—C21—N2	171.1 (5)	C13—C8—C9—C14	−178.9 (11)
C19—C20—C21—N5	−162.2 (8)	C14—C9—C10—Cl1	0.3 (13)
C20—C21—N2—C22	3.3 (12)	C14—C9—C10—C11	178.9 (11)
C20—C21—N5—C46	−15.2 (19)	N3—C29—C30—C31	−179.1 (3)
C21—C16—C17—C18	0.8 (6)	N3—C29—C33—C32	178.4 (3)
C21—N2—C22—C23	74.1 (11)	N4—C32—C33—C29	1.9 (5)
C21—N2—C22—C27	−105.8 (12)	C29—C30—C31—N4	−0.5 (5)
C21—N5—C46—C42	−84 (2)	C30—C29—C33—C32	−3.0 (5)
C21—N5—C46—C36	95 (2)	C31—N4—C32—C33	0.0 (5)
Cl2—C24—C25—C26	−180.0 (5)	C32—N4—C31—C30	−0.7 (5)
N2—C22—C23—C24	178.4 (9)	C33—C29—C30—C31	2.4 (5)
N2—C22—C23—C28	−0.8 (17)	C34—N3—C29—C30	−1.5 (5)
N2—C22—C27—C26	−177.8 (11)	C34—N3—C29—C33	176.9 (3)
C22—C23—C24—Cl2	−179.6 (6)	C35—N3—C29—C30	178.2 (3)
C22—C23—C24—C25	0.6 (12)	C35—N3—C29—C33	−3.3 (4)
C23—C22—C27—C26	2.3 (16)	Cl3—C39—C47—C43	177.1 (11)
C23—C24—C25—C26	−0.2 (14)	Cl4—C49—C38—C41	179.2 (14)
C24—C25—C26—C27	0.8 (13)	N5—C46—C36—C43	180 (2)
C25—C26—C27—C22	−1.9 (16)	C40—C49—C38—C41	−2 (3)
C27—C22—C23—C24	−1.7 (12)	C42—C46—C36—C43	−2 (3)
C27—C22—C23—C28	179.1 (13)	C42—C39—C47—C43	1 (3)
C28—C23—C24—Cl2	−0.3 (15)	C46—C42—C39—Cl3	−179.8 (10)
C28—C23—C24—C25	179.9 (12)	C46—C42—C39—C47	−4 (2)
O1—C1—C2—C3	169.2 (3)	C41—C44—C45—N6	−178.3 (19)
O1—C1—C2—C7	−10.0 (5)	C41—C44—C45—C40	−3 (3)
O2—C1—C2—C3	−11.0 (5)	C48—C42—C46—N5	−2 (3)
O2—C1—C2—C7	169.8 (3)	C48—C42—C46—C36	179 (2)
C1—C2—C3—C4	−178.5 (4)	C48—C42—C39—Cl3	5 (2)
C1—C2—C7—C6	179.3 (3)	C48—C42—C39—C47	−179 (2)
C1—C2—C7—N1	−11 (3)	C39—C42—C46—N5	−177.5 (17)
C1—C2—C7—N6	21 (5)	C39—C42—C46—C36	4 (2)
C2—C3—C4—C5	−1.4 (6)	C44—C41—C38—C49	1 (3)
C2—C7—N1—C8	−176 (3)	C36—C43—C47—C39	1 (3)
C2—C7—N6—C45	178 (5)	C47—C43—C36—C46	−1 (3)
C3—C2—C7—C6	0.0 (5)	C37—C40—C49—Cl4	2 (2)
C3—C2—C7—N1	170 (3)	C37—C40—C49—C38	−177 (2)
C3—C2—C7—N6	−158 (5)	C37—C40—C45—N6	−6 (3)
C3—C4—C5—C6	1.2 (6)	C37—C40—C45—C44	179 (2)
C4—C5—C6—C7	−0.5 (6)	C49—C40—C45—N6	176.9 (17)
C5—C6—C7—C2	−0.1 (6)	C49—C40—C45—C44	2 (2)
C5—C6—C7—N1	−170 (3)	C38—C41—C44—C45	1 (3)
C5—C6—C7—N6	159 (5)	C45—C40—C49—Cl4	179.2 (11)
C6—C7—N1—C8	−6 (6)	C45—C40—C49—C38	0 (2)

(tfa_form-vi)

Crystal data

C14H12ClNO2	Z = 2
Mr = 261.70	F(000) = 272
Triclinic, P1	Dx = 1.424 Mg m^−3
a = 6.7049 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2778 (3) Å	Cell parameters from 6423 reflections
c = 14.1630 (6) Å	θ = 2.9–26.4°
α = 77.167 (4)°	µ = 0.31 mm^−1
β = 79.908 (3)°	T = 100 K
γ = 65.487 (4)°	Plate, colourless
V = 610.42 (5) Å^3	0.6 × 0.3 × 0.2 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	2133 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	1931 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.031
Detector resolution: 7.9580 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −7→7
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→8
Tmin = 0.376, Tmax = 1.000	l = −16→16
11414 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.079	H-atom parameters constrained
wR(F^2) = 0.220	w = 1/[σ^2(Fo^2) + (0.1132P)^2 + 1.7122P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2133 reflections	Δρmax = 0.41 e Å^−3
168 parameters	Δρmin = −1.39 e Å^−3
1 restraint

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl1	0.1897 (3)	1.2652 (3)	0.48462 (10)	0.0931 (8)
O1	0.2753 (3)	0.2912 (3)	1.00433 (16)	0.0187 (6)
H1	0.146287	0.323866	1.026784	0.028*
O2	0.1345 (3)	0.6017 (3)	0.91569 (16)	0.0179 (5)
N1	0.4029 (4)	0.7444 (4)	0.7946 (2)	0.0186 (6)
H1A	0.273 (4)	0.750 (6)	0.817 (3)	0.022*
C1	0.2961 (5)	0.4426 (4)	0.9383 (2)	0.0146 (7)
C2	0.5208 (5)	0.4083 (4)	0.8940 (2)	0.0142 (7)
C3	0.6931 (5)	0.2194 (5)	0.9220 (2)	0.0168 (7)
H3	0.662320	0.119839	0.968388	0.020*
C4	0.9064 (5)	0.1795 (5)	0.8819 (2)	0.0195 (7)
H4	1.018891	0.054134	0.900907	0.023*
C5	0.9512 (5)	0.3287 (5)	0.8127 (2)	0.0176 (7)
H5	1.095154	0.302015	0.785483	0.021*
C6	0.7874 (5)	0.5154 (5)	0.7835 (2)	0.0164 (7)
H6	0.821793	0.612520	0.736797	0.020*
C7	0.5674 (5)	0.5607 (5)	0.8239 (2)	0.0145 (7)
C8	0.4256 (5)	0.9128 (5)	0.7288 (2)	0.0169 (7)
C9	0.3088 (5)	0.9868 (5)	0.6464 (2)	0.0233 (8)
C10	0.3221 (7)	1.1611 (5)	0.5862 (3)	0.0327 (9)
C11	0.4458 (7)	1.2553 (5)	0.6060 (3)	0.0399 (11)
H11	0.451334	1.371880	0.564411	0.048*
C12	0.5627 (7)	1.1789 (5)	0.6873 (3)	0.0326 (9)
H12	0.647623	1.242863	0.699809	0.039*
C13	0.5522 (5)	1.0067 (5)	0.7497 (2)	0.0226 (7)
H13	0.628654	0.954618	0.804919	0.027*
C14	0.1795 (6)	0.8792 (6)	0.6236 (3)	0.0343 (9)
H14A	0.233774	0.739617	0.656296	0.051*
H14B	0.194903	0.881956	0.554676	0.051*
H14C	0.027015	0.946879	0.645243	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1010 (13)	0.0718 (11)	0.0403 (8)	0.0316 (9)	−0.0107 (8)	−0.0076 (7)
O1	0.0124 (11)	0.0165 (11)	0.0231 (12)	−0.0045 (9)	0.0008 (9)	0.0002 (9)
O2	0.0122 (11)	0.0157 (11)	0.0228 (12)	−0.0039 (9)	−0.0014 (9)	−0.0008 (9)
N1	0.0107 (13)	0.0140 (13)	0.0257 (15)	−0.0029 (11)	0.0012 (11)	0.0010 (11)
C1	0.0156 (15)	0.0141 (15)	0.0157 (15)	−0.0057 (13)	−0.0035 (12)	−0.0041 (12)
C2	0.0135 (15)	0.0128 (14)	0.0167 (15)	−0.0040 (12)	−0.0024 (12)	−0.0048 (12)
C3	0.0173 (16)	0.0145 (15)	0.0156 (15)	−0.0032 (12)	−0.0023 (12)	−0.0023 (11)
C4	0.0141 (15)	0.0164 (15)	0.0218 (16)	0.0015 (12)	−0.0035 (12)	−0.0043 (12)
C5	0.0120 (15)	0.0223 (16)	0.0183 (16)	−0.0049 (13)	0.0008 (12)	−0.0080 (12)
C6	0.0155 (15)	0.0161 (15)	0.0177 (15)	−0.0065 (13)	0.0010 (12)	−0.0045 (12)
C7	0.0147 (15)	0.0131 (15)	0.0160 (15)	−0.0039 (12)	−0.0022 (12)	−0.0053 (11)
C8	0.0152 (15)	0.0122 (14)	0.0175 (15)	−0.0011 (12)	0.0051 (12)	−0.0050 (12)
C9	0.0179 (16)	0.0199 (16)	0.0193 (16)	0.0058 (13)	0.0013 (13)	−0.0068 (13)
C10	0.037 (2)	0.0175 (17)	0.0223 (18)	0.0069 (15)	0.0096 (15)	−0.0063 (14)
C11	0.052 (3)	0.0134 (17)	0.030 (2)	−0.0004 (17)	0.0247 (19)	−0.0025 (15)
C12	0.037 (2)	0.0190 (17)	0.041 (2)	−0.0145 (16)	0.0198 (17)	−0.0150 (16)
C13	0.0211 (17)	0.0198 (16)	0.0245 (17)	−0.0061 (14)	0.0056 (13)	−0.0086 (13)
C14	0.0228 (19)	0.041 (2)	0.034 (2)	−0.0004 (17)	−0.0089 (16)	−0.0145 (17)

Geometric parameters (Å, º)

Cl1—C10	1.684 (4)	C6—H6	0.9300
O1—H1	0.8200	C6—C7	1.412 (4)
O1—C1	1.316 (4)	C8—C9	1.400 (5)
O2—C1	1.238 (4)	C8—C13	1.391 (5)
N1—H1A	0.860 (19)	C9—C10	1.389 (5)
N1—C7	1.366 (4)	C9—C14	1.498 (5)
N1—C8	1.411 (4)	C10—C11	1.369 (7)
C1—C2	1.467 (4)	C11—H11	0.9300
C2—C3	1.407 (4)	C11—C12	1.385 (6)
C2—C7	1.416 (4)	C12—H12	0.9300
C3—H3	0.9300	C12—C13	1.384 (5)
C3—C4	1.377 (5)	C13—H13	0.9300
C4—H4	0.9300	C14—H14A	0.9600
C4—C5	1.387 (5)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600
C5—C6	1.377 (5)
C1—O1—H1	109.5	C9—C8—N1	118.2 (3)
C7—N1—H1A	114 (3)	C13—C8—N1	119.8 (3)
C7—N1—C8	127.0 (3)	C13—C8—C9	122.0 (3)
C8—N1—H1A	119 (3)	C8—C9—C14	121.0 (3)
O1—C1—C2	115.5 (3)	C10—C9—C8	117.1 (3)
O2—C1—O1	121.3 (3)	C10—C9—C14	121.9 (3)
O2—C1—C2	123.2 (3)	C9—C10—Cl1	121.7 (3)
C3—C2—C1	119.1 (3)	C11—C10—Cl1	116.7 (3)
C3—C2—C7	119.5 (3)	C11—C10—C9	121.5 (4)
C7—C2—C1	121.4 (3)	C10—C11—H11	119.6
C2—C3—H3	119.4	C10—C11—C12	120.8 (3)
C4—C3—C2	121.2 (3)	C12—C11—H11	119.6
C4—C3—H3	119.4	C11—C12—H12	120.2
C3—C4—H4	120.4	C13—C12—C11	119.6 (4)
C3—C4—C5	119.1 (3)	C13—C12—H12	120.2
C5—C4—H4	120.4	C8—C13—H13	120.5
C4—C5—H5	119.3	C12—C13—C8	119.1 (3)
C6—C5—C4	121.4 (3)	C12—C13—H13	120.5
C6—C5—H5	119.3	C9—C14—H14A	109.5
C5—C6—H6	119.7	C9—C14—H14B	109.5
C5—C6—C7	120.6 (3)	C9—C14—H14C	109.5
C7—C6—H6	119.7	H14A—C14—H14B	109.5
N1—C7—C2	120.7 (3)	H14A—C14—H14C	109.5
N1—C7—C6	121.1 (3)	H14B—C14—H14C	109.5
C6—C7—C2	118.1 (3)
Cl1—C10—C11—C12	−179.2 (3)	C5—C6—C7—C2	−0.7 (4)
O1—C1—C2—C3	1.8 (4)	C7—N1—C8—C9	122.8 (3)
O1—C1—C2—C7	−178.3 (2)	C7—N1—C8—C13	−60.6 (4)
O2—C1—C2—C3	−177.8 (3)	C7—C2—C3—C4	−0.4 (4)
O2—C1—C2—C7	2.1 (5)	C8—N1—C7—C2	177.2 (3)
N1—C8—C9—C10	175.8 (3)	C8—N1—C7—C6	−4.3 (5)
N1—C8—C9—C14	−5.5 (4)	C8—C9—C10—Cl1	179.9 (2)
N1—C8—C13—C12	−176.3 (3)	C8—C9—C10—C11	0.7 (5)
C1—C2—C3—C4	179.5 (3)	C9—C8—C13—C12	0.2 (5)
C1—C2—C7—N1	−0.6 (4)	C9—C10—C11—C12	0.1 (5)
C1—C2—C7—C6	−179.2 (3)	C10—C11—C12—C13	−0.8 (5)
C2—C3—C4—C5	0.0 (5)	C11—C12—C13—C8	0.6 (5)
C3—C2—C7—N1	179.3 (3)	C13—C8—C9—C10	−0.8 (5)
C3—C2—C7—C6	0.7 (4)	C13—C8—C9—C14	178.0 (3)
C3—C4—C5—C6	0.1 (5)	C14—C9—C10—Cl1	1.1 (5)
C4—C5—C6—C7	0.3 (5)	C14—C9—C10—C11	−178.1 (3)
C5—C6—C7—N1	−179.2 (3)

(tfa_dmf)

Crystal data

2(C7H6Cl0.5N0.5O)·2(C1.5H3.5N0.5O0.5)	Z = 4
Mr = 334.79	F(000) = 704
Triclinic, P1	Dx = 1.393 Mg m^−3
a = 10.4803 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.8423 (9) Å	Cell parameters from 3883 reflections
c = 13.3309 (8) Å	θ = 2.3–27.9°
α = 94.335 (5)°	µ = 0.26 mm^−1
β = 95.883 (5)°	T = 100 K
γ = 102.871 (6)°	Plate, colourless
V = 1596.16 (18) Å^3	0.56 × 0.29 × 0.18 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	6498 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	4756 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.044
Detector resolution: 7.9580 pixels mm^-1	θmax = 26.4°, θmin = 1.8°
ω scans	h = −13→12
Absorption correction: multi-scan CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −14→14
Tmin = 0.582, Tmax = 1.000	l = −16→16
15902 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 0.5428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
6498 reflections	Δρmax = 0.38 e Å^−3
423 parameters	Δρmin = −0.37 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl2	0.19883 (6)	0.46175 (5)	0.32126 (4)	0.02544 (16)
Cl1	−0.70131 (6)	0.03877 (5)	−0.07515 (4)	0.02676 (16)
O1	−0.42217 (16)	0.32812 (15)	0.58448 (11)	0.0214 (4)
H1	−0.474369	0.351946	0.617531	0.032*
O3	−0.07342 (16)	0.19504 (15)	−0.33062 (11)	0.0224 (4)
H3	−0.016315	0.177986	−0.362490	0.034*
O4	0.06794 (16)	0.17536 (15)	−0.20033 (11)	0.0229 (4)
O2	−0.56101 (18)	0.35602 (16)	0.45556 (12)	0.0284 (4)
O6	0.40913 (17)	0.39622 (15)	−0.30638 (12)	0.0254 (4)
O5	−0.10675 (18)	−0.14166 (16)	0.43380 (12)	0.0275 (4)
N1	−0.52881 (19)	0.28374 (17)	0.26980 (13)	0.0187 (4)
H1A	−0.579624	0.305308	0.310343	0.022*
N2	0.00786 (19)	0.20524 (18)	−0.01434 (13)	0.0194 (5)
H2	0.058513	0.181246	−0.053694	0.023*
N4	0.2125 (2)	0.44894 (17)	−0.32228 (14)	0.0207 (5)
N3	−0.2985 (2)	−0.08168 (17)	0.42500 (14)	0.0196 (4)
C9	−0.6113 (2)	0.1674 (2)	0.10577 (16)	0.0162 (5)
C17	−0.2503 (2)	0.2496 (2)	−0.20765 (17)	0.0186 (5)
H17	−0.268075	0.246012	−0.277767	0.022*
C7	−0.4143 (2)	0.26016 (19)	0.31231 (16)	0.0165 (5)
C16	−0.1322 (2)	0.2265 (2)	−0.16578 (17)	0.0167 (5)
C12	−0.6218 (2)	0.3754 (2)	0.01964 (17)	0.0180 (5)
H12	−0.627715	0.444122	−0.007998	0.022*
C27	0.0488 (2)	0.1149 (2)	0.13864 (16)	0.0178 (5)
H27	0.020257	0.042699	0.100736	0.021*
C23	0.0912 (2)	0.3255 (2)	0.14616 (17)	0.0173 (5)
C24	0.1350 (2)	0.3283 (2)	0.25005 (17)	0.0174 (5)
C21	−0.1046 (2)	0.2306 (2)	−0.05871 (17)	0.0168 (5)
C8	−0.5707 (2)	0.2754 (2)	0.16388 (16)	0.0166 (5)
C3	−0.2597 (2)	0.2533 (2)	0.46004 (17)	0.0185 (5)
H3A	−0.236032	0.265560	0.529849	0.022*
C2	−0.3769 (2)	0.27896 (19)	0.41925 (16)	0.0162 (5)
C6	−0.3291 (2)	0.2168 (2)	0.25219 (17)	0.0177 (5)
H6	−0.350890	0.204205	0.182204	0.021*
C13	−0.5773 (2)	0.3784 (2)	0.12143 (17)	0.0185 (5)
H13	−0.551752	0.449253	0.161621	0.022*
C15	−0.0367 (2)	0.1973 (2)	−0.23182 (16)	0.0173 (5)
C20	−0.1984 (2)	0.2595 (2)	0.00051 (17)	0.0178 (5)
H20	−0.182292	0.263331	0.070746	0.021*
C11	−0.6573 (2)	0.2711 (2)	−0.04100 (17)	0.0176 (5)
H11	−0.684570	0.268815	−0.109900	0.021*
C5	−0.2143 (2)	0.1927 (2)	0.29555 (17)	0.0194 (5)
H5	−0.159788	0.164098	0.254335	0.023*
C25	0.1355 (2)	0.2282 (2)	0.29769 (17)	0.0197 (5)
H25	0.164544	0.233222	0.366536	0.024*
C19	−0.3135 (2)	0.2822 (2)	−0.04319 (17)	0.0195 (5)
H19	−0.373900	0.301047	−0.002166	0.023*
C18	−0.3409 (2)	0.2774 (2)	−0.14869 (17)	0.0201 (5)
H18	−0.418827	0.292751	−0.178114	0.024*
C1	−0.4619 (2)	0.3250 (2)	0.48622 (17)	0.0175 (5)
C10	−0.6516 (2)	0.1699 (2)	0.00287 (17)	0.0175 (5)
C22	0.0477 (2)	0.2156 (2)	0.09256 (16)	0.0168 (5)
C4	−0.1784 (2)	0.2105 (2)	0.40033 (17)	0.0204 (5)
H4	−0.100922	0.193739	0.429136	0.024*
C26	0.0925 (2)	0.1213 (2)	0.24160 (17)	0.0201 (5)
H26	0.092556	0.053436	0.272491	0.024*
C32	0.3110 (2)	0.4131 (2)	−0.35837 (18)	0.0222 (6)
H32	0.306555	0.399448	−0.428400	0.027*
C30	−0.4135 (2)	−0.0647 (2)	0.36281 (18)	0.0246 (6)
H30A	−0.491664	−0.113236	0.382012	0.037*
H30B	−0.407029	−0.085188	0.292760	0.037*
H30C	−0.417929	0.015386	0.372573	0.037*
C14	−0.6153 (2)	0.0547 (2)	0.15166 (18)	0.0227 (6)
H14A	−0.610817	0.068189	0.223993	0.034*
H14B	−0.541639	0.024377	0.134863	0.034*
H14C	−0.695918	−0.000393	0.125418	0.034*
C28	0.0943 (2)	0.4354 (2)	0.09668 (18)	0.0212 (5)
H28A	0.020619	0.466276	0.112299	0.032*
H28B	0.089519	0.418930	0.024579	0.032*
H28C	0.174899	0.491358	0.121445	0.032*
C29	−0.2060 (2)	−0.1230 (2)	0.38524 (18)	0.0226 (6)
H29	−0.215983	−0.139374	0.315161	0.027*
C33	0.2119 (3)	0.4755 (2)	−0.21391 (17)	0.0256 (6)
H33A	0.296726	0.475725	−0.178837	0.038*
H33B	0.145513	0.417583	−0.190076	0.038*
H33C	0.193223	0.550696	−0.201350	0.038*
C31	−0.2866 (3)	−0.0488 (2)	0.53404 (17)	0.0252 (6)
H31A	−0.346760	−0.105985	0.564246	0.038*
H31B	−0.307317	0.025769	0.545771	0.038*
H31C	−0.198042	−0.044414	0.563733	0.038*
C34	0.0997 (3)	0.4633 (2)	−0.3891 (2)	0.0304 (6)
H34A	0.020864	0.412885	−0.372867	0.046*
H34B	0.111449	0.443670	−0.458185	0.046*
H34C	0.092328	0.542663	−0.380229	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl2	0.0295 (4)	0.0223 (3)	0.0209 (3)	0.0043 (3)	−0.0050 (3)	−0.0043 (2)
Cl1	0.0276 (4)	0.0239 (3)	0.0241 (3)	0.0039 (3)	−0.0059 (3)	−0.0084 (3)
O1	0.0226 (10)	0.0299 (10)	0.0120 (8)	0.0091 (8)	−0.0011 (7)	−0.0017 (7)
O3	0.0239 (10)	0.0333 (11)	0.0111 (8)	0.0113 (8)	0.0001 (7)	−0.0004 (7)
O4	0.0199 (10)	0.0359 (11)	0.0138 (8)	0.0106 (8)	−0.0017 (7)	0.0005 (7)
O2	0.0284 (11)	0.0467 (12)	0.0150 (8)	0.0219 (9)	−0.0010 (8)	−0.0008 (8)
O6	0.0262 (10)	0.0328 (11)	0.0170 (8)	0.0096 (8)	−0.0007 (8)	−0.0017 (7)
O5	0.0286 (11)	0.0374 (11)	0.0191 (9)	0.0156 (9)	−0.0001 (8)	−0.0006 (8)
N1	0.0176 (11)	0.0287 (12)	0.0109 (9)	0.0092 (9)	−0.0011 (8)	0.0001 (8)
N2	0.0171 (11)	0.0306 (12)	0.0116 (9)	0.0091 (9)	0.0001 (8)	0.0005 (8)
N4	0.0225 (12)	0.0219 (11)	0.0184 (10)	0.0070 (9)	0.0024 (9)	0.0014 (8)
N3	0.0220 (11)	0.0214 (11)	0.0147 (10)	0.0058 (9)	−0.0007 (8)	0.0003 (8)
C9	0.0118 (12)	0.0198 (13)	0.0166 (11)	0.0036 (10)	0.0018 (9)	0.0007 (10)
C17	0.0184 (13)	0.0190 (13)	0.0148 (11)	−0.0012 (10)	−0.0034 (10)	0.0017 (10)
C7	0.0175 (13)	0.0137 (12)	0.0174 (11)	0.0020 (10)	0.0005 (10)	0.0033 (9)
C16	0.0158 (13)	0.0145 (12)	0.0177 (12)	0.0007 (10)	−0.0013 (10)	0.0008 (9)
C12	0.0158 (13)	0.0201 (13)	0.0178 (11)	0.0036 (10)	−0.0005 (10)	0.0055 (10)
C27	0.0169 (13)	0.0180 (13)	0.0163 (11)	0.0030 (10)	−0.0019 (10)	−0.0034 (10)
C23	0.0116 (12)	0.0231 (13)	0.0177 (11)	0.0047 (10)	0.0015 (9)	0.0025 (10)
C24	0.0124 (12)	0.0222 (13)	0.0167 (11)	0.0040 (10)	−0.0002 (9)	−0.0010 (10)
C21	0.0149 (12)	0.0149 (12)	0.0181 (12)	0.0003 (10)	−0.0021 (9)	0.0012 (9)
C8	0.0134 (12)	0.0238 (13)	0.0128 (11)	0.0048 (10)	0.0006 (9)	0.0023 (10)
C3	0.0173 (13)	0.0207 (13)	0.0150 (11)	0.0005 (10)	−0.0020 (10)	0.0035 (10)
C2	0.0182 (13)	0.0140 (12)	0.0148 (11)	0.0013 (10)	0.0003 (9)	0.0013 (9)
C6	0.0176 (13)	0.0203 (13)	0.0131 (11)	0.0013 (10)	−0.0003 (9)	0.0014 (9)
C13	0.0137 (12)	0.0204 (13)	0.0190 (12)	0.0015 (10)	−0.0004 (10)	−0.0028 (10)
C15	0.0191 (13)	0.0143 (12)	0.0150 (11)	−0.0011 (10)	−0.0027 (10)	0.0009 (9)
C20	0.0169 (13)	0.0231 (13)	0.0119 (11)	0.0025 (10)	−0.0002 (9)	0.0013 (10)
C11	0.0124 (12)	0.0260 (14)	0.0137 (11)	0.0029 (10)	0.0005 (9)	0.0026 (10)
C5	0.0146 (13)	0.0240 (14)	0.0193 (12)	0.0035 (10)	0.0030 (10)	0.0027 (10)
C25	0.0166 (13)	0.0277 (14)	0.0141 (11)	0.0057 (11)	−0.0009 (10)	−0.0011 (10)
C19	0.0155 (13)	0.0206 (13)	0.0213 (12)	0.0022 (10)	0.0021 (10)	0.0014 (10)
C18	0.0147 (13)	0.0232 (13)	0.0209 (12)	0.0033 (10)	−0.0038 (10)	0.0043 (10)
C1	0.0187 (13)	0.0168 (13)	0.0145 (11)	0.0009 (10)	−0.0023 (10)	0.0005 (9)
C10	0.0127 (12)	0.0203 (13)	0.0173 (11)	0.0021 (10)	0.0000 (9)	−0.0034 (10)
C22	0.0119 (12)	0.0240 (13)	0.0150 (11)	0.0051 (10)	0.0018 (9)	0.0018 (10)
C4	0.0139 (13)	0.0245 (14)	0.0219 (12)	0.0042 (11)	−0.0019 (10)	0.0040 (10)
C26	0.0201 (13)	0.0194 (13)	0.0205 (12)	0.0045 (11)	−0.0006 (10)	0.0058 (10)
C32	0.0268 (15)	0.0211 (14)	0.0172 (12)	0.0051 (11)	0.0005 (11)	−0.0033 (10)
C30	0.0225 (14)	0.0267 (15)	0.0230 (13)	0.0039 (12)	0.0000 (11)	0.0013 (11)
C14	0.0225 (14)	0.0199 (13)	0.0235 (13)	0.0028 (11)	−0.0022 (10)	0.0013 (10)
C28	0.0197 (13)	0.0193 (13)	0.0237 (13)	0.0035 (10)	0.0007 (10)	0.0022 (10)
C29	0.0278 (15)	0.0239 (14)	0.0150 (12)	0.0050 (12)	0.0017 (11)	−0.0015 (10)
C33	0.0281 (15)	0.0274 (15)	0.0228 (13)	0.0081 (12)	0.0082 (11)	0.0000 (11)
C31	0.0340 (16)	0.0254 (14)	0.0178 (12)	0.0102 (12)	0.0048 (11)	0.0004 (10)
C34	0.0260 (15)	0.0351 (16)	0.0306 (14)	0.0084 (13)	0.0011 (12)	0.0057 (12)

Geometric parameters (Å, º)

Cl2—C24	1.737 (2)	C21—C20	1.405 (3)
Cl1—C10	1.746 (2)	C8—C13	1.395 (3)
O1—H1	0.8200	C3—H3A	0.9300
O1—C1	1.328 (3)	C3—C2	1.397 (3)
O3—H3	0.8200	C3—C4	1.374 (3)
O3—C15	1.331 (3)	C2—C1	1.482 (3)
O4—C15	1.222 (3)	C6—H6	0.9300
O2—C1	1.219 (3)	C6—C5	1.378 (3)
O6—C32	1.243 (3)	C13—H13	0.9300
O5—C29	1.239 (3)	C20—H20	0.9300
N1—H1A	0.8600	C20—C19	1.375 (3)
N1—C7	1.369 (3)	C11—H11	0.9300
N1—C8	1.424 (3)	C11—C10	1.383 (3)
N2—H2	0.8600	C5—H5	0.9300
N2—C21	1.368 (3)	C5—C4	1.396 (3)
N2—C22	1.432 (3)	C25—H25	0.9300
N4—C32	1.320 (3)	C25—C26	1.379 (3)
N4—C33	1.456 (3)	C19—H19	0.9300
N4—C34	1.455 (3)	C19—C18	1.400 (3)
N3—C30	1.452 (3)	C18—H18	0.9300
N3—C29	1.318 (3)	C4—H4	0.9300
N3—C31	1.462 (3)	C26—H26	0.9300
C9—C8	1.399 (3)	C32—H32	0.9300
C9—C10	1.398 (3)	C30—H30A	0.9600
C9—C14	1.504 (3)	C30—H30B	0.9600
C17—H17	0.9300	C30—H30C	0.9600
C17—C16	1.396 (3)	C14—H14A	0.9600
C17—C18	1.372 (3)	C14—H14B	0.9600
C7—C2	1.426 (3)	C14—H14C	0.9600
C7—C6	1.411 (3)	C28—H28A	0.9600
C16—C21	1.422 (3)	C28—H28B	0.9600
C16—C15	1.479 (3)	C28—H28C	0.9600
C12—H12	0.9300	C29—H29	0.9300
C12—C13	1.384 (3)	C33—H33A	0.9600
C12—C11	1.379 (3)	C33—H33B	0.9600
C27—H27	0.9300	C33—H33C	0.9600
C27—C22	1.384 (3)	C31—H31A	0.9600
C27—C26	1.393 (3)	C31—H31B	0.9600
C23—C24	1.409 (3)	C31—H31C	0.9600
C23—C22	1.393 (3)	C34—H34A	0.9600
C23—C28	1.498 (3)	C34—H34B	0.9600
C24—C25	1.387 (3)	C34—H34C	0.9600
C1—O1—H1	109.5	C4—C5—H5	119.5
C15—O3—H3	109.5	C24—C25—H25	120.5
C7—N1—H1A	117.4	C26—C25—C24	119.1 (2)
C7—N1—C8	125.30 (19)	C26—C25—H25	120.5
C8—N1—H1A	117.4	C20—C19—H19	119.6
C21—N2—H2	117.5	C20—C19—C18	120.8 (2)
C21—N2—C22	125.04 (19)	C18—C19—H19	119.6
C22—N2—H2	117.5	C17—C18—C19	118.5 (2)
C32—N4—C33	121.5 (2)	C17—C18—H18	120.7
C32—N4—C34	121.4 (2)	C19—C18—H18	120.7
C34—N4—C33	117.1 (2)	O1—C1—C2	114.0 (2)
C30—N3—C31	117.63 (19)	O2—C1—O1	122.0 (2)
C29—N3—C30	121.8 (2)	O2—C1—C2	124.0 (2)
C29—N3—C31	120.6 (2)	C9—C10—Cl1	118.99 (18)
C8—C9—C14	122.1 (2)	C11—C10—Cl1	117.50 (18)
C10—C9—C8	116.2 (2)	C11—C10—C9	123.5 (2)
C10—C9—C14	121.7 (2)	C27—C22—N2	118.3 (2)
C16—C17—H17	118.9	C27—C22—C23	121.8 (2)
C18—C17—H17	118.9	C23—C22—N2	119.8 (2)
C18—C17—C16	122.1 (2)	C3—C4—C5	118.7 (2)
N1—C7—C2	120.9 (2)	C3—C4—H4	120.7
N1—C7—C6	121.4 (2)	C5—C4—H4	120.7
C6—C7—C2	117.7 (2)	C27—C26—H26	120.0
C17—C16—C21	119.4 (2)	C25—C26—C27	119.9 (2)
C17—C16—C15	120.6 (2)	C25—C26—H26	120.0
C21—C16—C15	120.0 (2)	O6—C32—N4	125.3 (2)
C13—C12—H12	119.8	O6—C32—H32	117.3
C11—C12—H12	119.8	N4—C32—H32	117.3
C11—C12—C13	120.3 (2)	N3—C30—H30A	109.5
C22—C27—H27	119.9	N3—C30—H30B	109.5
C22—C27—C26	120.2 (2)	N3—C30—H30C	109.5
C26—C27—H27	119.9	H30A—C30—H30B	109.5
C24—C23—C28	121.3 (2)	H30A—C30—H30C	109.5
C22—C23—C24	116.3 (2)	H30B—C30—H30C	109.5
C22—C23—C28	122.4 (2)	C9—C14—H14A	109.5
C23—C24—Cl2	119.35 (18)	C9—C14—H14B	109.5
C25—C24—Cl2	117.87 (18)	C9—C14—H14C	109.5
C25—C24—C23	122.7 (2)	H14A—C14—H14B	109.5
N2—C21—C16	121.6 (2)	H14A—C14—H14C	109.5
N2—C21—C20	120.8 (2)	H14B—C14—H14C	109.5
C20—C21—C16	117.7 (2)	C23—C28—H28A	109.5
C9—C8—N1	121.2 (2)	C23—C28—H28B	109.5
C13—C8—N1	117.5 (2)	C23—C28—H28C	109.5
C13—C8—C9	121.1 (2)	H28A—C28—H28B	109.5
C2—C3—H3A	118.9	H28A—C28—H28C	109.5
C4—C3—H3A	118.9	H28B—C28—H28C	109.5
C4—C3—C2	122.1 (2)	O5—C29—N3	125.2 (2)
C7—C2—C1	120.2 (2)	O5—C29—H29	117.4
C3—C2—C7	119.3 (2)	N3—C29—H29	117.4
C3—C2—C1	120.5 (2)	N4—C33—H33A	109.5
C7—C6—H6	119.5	N4—C33—H33B	109.5
C5—C6—C7	121.0 (2)	N4—C33—H33C	109.5
C5—C6—H6	119.5	H33A—C33—H33B	109.5
C12—C13—C8	120.1 (2)	H33A—C33—H33C	109.5
C12—C13—H13	119.9	H33B—C33—H33C	109.5
C8—C13—H13	119.9	N3—C31—H31A	109.5
O3—C15—C16	114.7 (2)	N3—C31—H31B	109.5
O4—C15—O3	121.3 (2)	N3—C31—H31C	109.5
O4—C15—C16	124.0 (2)	H31A—C31—H31B	109.5
C21—C20—H20	119.3	H31A—C31—H31C	109.5
C19—C20—C21	121.4 (2)	H31B—C31—H31C	109.5
C19—C20—H20	119.3	N4—C34—H34A	109.5
C12—C11—H11	120.7	N4—C34—H34B	109.5
C12—C11—C10	118.5 (2)	N4—C34—H34C	109.5
C10—C11—H11	120.7	H34A—C34—H34B	109.5
C6—C5—H5	119.5	H34A—C34—H34C	109.5
C6—C5—C4	121.1 (2)	H34B—C34—H34C	109.5
Cl2—C24—C25—C26	−176.32 (18)	C2—C7—C6—C5	0.4 (3)
N1—C7—C2—C3	179.6 (2)	C2—C3—C4—C5	0.2 (4)
N1—C7—C2—C1	−0.2 (3)	C6—C7—C2—C3	−0.5 (3)
N1—C7—C6—C5	−179.7 (2)	C6—C7—C2—C1	179.7 (2)
N1—C8—C13—C12	−177.7 (2)	C6—C5—C4—C3	−0.3 (4)
N2—C21—C20—C19	−178.3 (2)	C13—C12—C11—C10	2.1 (3)
C9—C8—C13—C12	−1.5 (3)	C15—C16—C21—N2	−1.6 (3)
C17—C16—C21—N2	178.0 (2)	C15—C16—C21—C20	179.6 (2)
C17—C16—C21—C20	−0.8 (3)	C20—C19—C18—C17	−0.1 (4)
C17—C16—C15—O3	−0.2 (3)	C11—C12—C13—C8	−1.3 (3)
C17—C16—C15—O4	−179.5 (2)	C18—C17—C16—C21	0.6 (3)
C7—N1—C8—C9	70.1 (3)	C18—C17—C16—C15	−179.7 (2)
C7—N1—C8—C13	−113.7 (3)	C10—C9—C8—N1	179.3 (2)
C7—C2—C1—O1	174.0 (2)	C10—C9—C8—C13	3.3 (3)
C7—C2—C1—O2	−4.8 (4)	C22—N2—C21—C16	175.1 (2)
C7—C6—C5—C4	0.0 (4)	C22—N2—C21—C20	−6.1 (4)
C16—C17—C18—C19	−0.2 (3)	C22—C27—C26—C25	−0.4 (3)
C16—C21—C20—C19	0.5 (3)	C22—C23—C24—Cl2	176.70 (17)
C12—C11—C10—Cl1	178.38 (17)	C22—C23—C24—C25	0.0 (3)
C12—C11—C10—C9	−0.1 (3)	C4—C3—C2—C7	0.2 (3)
C23—C24—C25—C26	0.4 (3)	C4—C3—C2—C1	−180.0 (2)
C24—C23—C22—N2	−176.91 (19)	C26—C27—C22—N2	177.2 (2)
C24—C23—C22—C27	−0.6 (3)	C26—C27—C22—C23	0.8 (3)
C24—C25—C26—C27	−0.2 (3)	C30—N3—C29—O5	−178.6 (2)
C21—N2—C22—C27	112.6 (3)	C14—C9—C8—N1	1.0 (3)
C21—N2—C22—C23	−71.0 (3)	C14—C9—C8—C13	−175.0 (2)
C21—C16—C15—O3	179.4 (2)	C14—C9—C10—Cl1	−2.7 (3)
C21—C16—C15—O4	0.1 (3)	C14—C9—C10—C11	175.8 (2)
C21—C20—C19—C18	−0.1 (4)	C28—C23—C24—Cl2	−2.1 (3)
C8—N1—C7—C2	175.6 (2)	C28—C23—C24—C25	−178.8 (2)
C8—N1—C7—C6	−4.3 (4)	C28—C23—C22—N2	1.9 (3)
C8—C9—C10—Cl1	179.00 (17)	C28—C23—C22—C27	178.2 (2)
C8—C9—C10—C11	−2.5 (3)	C33—N4—C32—O6	1.6 (4)
C3—C2—C1—O1	−5.8 (3)	C31—N3—C29—O5	2.8 (4)
C3—C2—C1—O2	175.3 (2)	C34—N4—C32—O6	−178.3 (2)

(mfa-dmap_1-1)

Crystal data

C15H14NO2·C7H11N2	Z = 2
Mr = 363.45	F(000) = 388
Triclinic, P1	Dx = 1.309 Mg m^−3
a = 7.7575 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4727 (7) Å	Cell parameters from 2026 reflections
c = 13.3076 (13) Å	θ = 2.7–26.3°
α = 87.515 (7)°	µ = 0.09 mm^−1
β = 78.596 (8)°	T = 100 K
γ = 74.174 (8)°	Block, colourless
V = 922.20 (15) Å^3	0.34 × 0.25 × 0.13 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	3361 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	2670 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.026
Detector resolution: 7.9580 pixels mm^-1	θmax = 25.4°, θmin = 2.2°
ω scans	h = −6→9
Absorption correction: multi-scan CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→11
Tmin = 0.846, Tmax = 1.000	l = −14→16
5455 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 0.692P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3361 reflections	Δρmax = 0.21 e Å^−3
341 parameters	Δρmin = −0.19 e Å^−3
3 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.4679 (2)	0.53199 (18)	0.22864 (13)	0.0296 (4)
O2	0.7171 (2)	0.43478 (19)	0.11148 (12)	0.0296 (4)
C1	0.6077 (3)	0.4264 (3)	0.19231 (18)	0.0230 (5)
C2	0.6369 (3)	0.2859 (3)	0.25118 (17)	0.0219 (5)
C3	0.5126 (4)	0.2595 (3)	0.3388 (2)	0.0407 (7)
C4	0.5514 (4)	0.1204 (3)	0.3842 (2)	0.0400 (7)
H4	0.469269	0.101023	0.440540	0.048*
C5	0.7071 (3)	0.0130 (3)	0.34758 (18)	0.0271 (6)
H5	0.728883	−0.078298	0.378744	0.032*
C6	0.8325 (3)	0.0394 (3)	0.26428 (18)	0.0259 (5)
H6	0.940019	−0.032442	0.240168	0.031*
C7	0.7948 (3)	0.1742 (3)	0.21794 (17)	0.0235 (5)
H7	0.878786	0.191460	0.161781	0.028*
N1	0.3736 (5)	0.3768 (4)	0.3920 (3)	0.0280 (9)	0.657 (6)
H1	0.354 (6)	0.456 (3)	0.358 (3)	0.034*	0.6575
C8	0.2511 (6)	0.3613 (5)	0.4844 (5)	0.0253 (12)	0.657 (6)
C9	0.1074 (6)	0.2968 (4)	0.4828 (4)	0.0232 (11)	0.657 (6)
C10	−0.0148 (8)	0.2938 (8)	0.5755 (6)	0.0243 (13)	0.657 (6)
C11	0.0052 (7)	0.3495 (5)	0.6638 (6)	0.0248 (13)	0.657 (6)
H11	−0.079288	0.347876	0.723764	0.030*	0.657 (6)
C12	0.1492 (5)	0.4085 (4)	0.6657 (3)	0.0281 (11)	0.657 (6)
H12	0.163719	0.444396	0.726593	0.034*	0.657 (6)
C13	0.2715 (10)	0.4131 (13)	0.5750 (9)	0.0271 (18)	0.657 (6)
H13	0.369229	0.452040	0.575512	0.033*	0.657 (6)
C14	0.083 (2)	0.2320 (14)	0.3852 (8)	0.033 (2)	0.657 (6)
H14A	0.124096	0.126848	0.387289	0.050*	0.657 (6)
H14B	0.154173	0.266620	0.326779	0.050*	0.657 (6)
H14C	−0.043188	0.261645	0.380193	0.050*	0.657 (6)
C15	−0.1719 (7)	0.2254 (6)	0.5759 (3)	0.0340 (12)	0.657 (6)
H15A	−0.123925	0.121897	0.562314	0.051*	0.657 (6)
H15B	−0.238566	0.269998	0.523892	0.051*	0.657 (6)
H15C	−0.252072	0.241208	0.641722	0.051*	0.657 (6)
N3	0.3943 (3)	−0.2178 (2)	0.14055 (15)	0.0248 (5)
H3	0.427 (3)	−0.311 (2)	0.1666 (19)	0.030*
N2	0.2383 (3)	0.2100 (2)	0.03916 (15)	0.0254 (5)
C16	0.2853 (3)	0.0719 (3)	0.07312 (17)	0.0225 (5)
C17	0.2552 (3)	−0.0479 (3)	0.02493 (18)	0.0247 (5)
H17	0.196122	−0.030998	−0.030556	0.030*
C18	0.3122 (3)	−0.1872 (3)	0.05918 (18)	0.0246 (5)
H18	0.293633	−0.263899	0.025117	0.030*
C19	0.4234 (3)	−0.1069 (3)	0.18912 (18)	0.0276 (6)
H19	0.480706	−0.128303	0.245237	0.033*
C20	0.3723 (3)	0.0349 (3)	0.15917 (18)	0.0274 (6)
H20	0.394264	0.108225	0.195038	0.033*
C21	0.2573 (4)	0.3341 (3)	0.0946 (2)	0.0360 (7)
H21A	0.151611	0.367551	0.147774	0.054*
H21B	0.268316	0.412602	0.047779	0.054*
H21C	0.364404	0.303267	0.124458	0.054*
C22	0.1421 (3)	0.2513 (3)	−0.0459 (2)	0.0317 (6)
H22A	0.181352	0.172713	−0.095481	0.048*
H22B	0.168597	0.338014	−0.077493	0.048*
H22C	0.012992	0.270358	−0.020748	0.048*
N1A	0.3255 (9)	0.3393 (7)	0.3499 (5)	0.0199 (16)	0.343 (6)
H1A	0.295 (10)	0.425 (4)	0.324 (5)	0.024*	0.3425
C23	−0.0871 (18)	0.2743 (11)	0.5855 (9)	0.019 (3)	0.343 (6)
H23	−0.180879	0.260950	0.637292	0.023*	0.343 (6)
C24	0.069 (3)	0.255 (2)	0.4121 (13)	0.023 (4)	0.343 (6)
H24	0.081439	0.224454	0.344878	0.028*	0.343 (6)
C25	0.331 (2)	0.413 (3)	0.5601 (17)	0.030 (4)	0.343 (6)
H25A	0.277603	0.510754	0.586975	0.045*	0.343 (6)
H25B	0.421788	0.413854	0.499841	0.045*	0.343 (6)
H25C	0.386336	0.351525	0.610817	0.045*	0.343 (6)
C26	0.0291 (12)	0.3756 (10)	0.7203 (8)	0.031 (2)	0.343 (6)
H26A	0.139819	0.323067	0.742058	0.047*	0.343 (6)
H26B	−0.072854	0.350464	0.763226	0.047*	0.343 (6)
H26C	0.014154	0.479215	0.725428	0.047*	0.343 (6)
C27	0.0390 (15)	0.3352 (11)	0.6113 (9)	0.018 (2)	0.343 (6)
C28	0.1842 (14)	0.3532 (8)	0.5331 (8)	0.023 (2)	0.343 (6)
C29	0.1862 (14)	0.3139 (8)	0.4334 (7)	0.0198 (19)	0.343 (6)
C30	−0.0839 (10)	0.2317 (9)	0.4881 (6)	0.033 (2)	0.343 (6)
H30	−0.171796	0.191552	0.471741	0.039*	0.343 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0274 (9)	0.0224 (10)	0.0308 (9)	−0.0021 (7)	0.0064 (7)	0.0015 (7)
O2	0.0317 (10)	0.0266 (10)	0.0248 (9)	−0.0086 (8)	0.0086 (7)	−0.0008 (7)
C1	0.0238 (12)	0.0235 (13)	0.0229 (12)	−0.0102 (10)	−0.0013 (10)	−0.0032 (10)
C2	0.0205 (12)	0.0250 (13)	0.0202 (12)	−0.0087 (10)	0.0000 (9)	−0.0019 (10)
C3	0.0282 (14)	0.0310 (16)	0.0436 (16)	0.0068 (12)	0.0155 (12)	0.0094 (13)
C4	0.0292 (14)	0.0332 (16)	0.0403 (16)	0.0027 (12)	0.0149 (12)	0.0138 (13)
C5	0.0271 (13)	0.0217 (13)	0.0284 (13)	−0.0029 (10)	−0.0017 (11)	0.0027 (10)
C6	0.0215 (12)	0.0241 (14)	0.0271 (13)	−0.0022 (10)	0.0026 (10)	−0.0062 (10)
C7	0.0223 (12)	0.0279 (14)	0.0199 (12)	−0.0096 (10)	0.0014 (10)	−0.0039 (10)
N1	0.0264 (19)	0.022 (2)	0.025 (2)	0.0009 (15)	0.0094 (16)	0.0000 (16)
C8	0.019 (2)	0.020 (2)	0.029 (3)	0.0002 (18)	0.006 (2)	0.000 (2)
C9	0.024 (2)	0.020 (2)	0.023 (3)	−0.0027 (17)	0.001 (2)	−0.002 (2)
C10	0.016 (3)	0.021 (3)	0.032 (4)	−0.004 (3)	0.002 (3)	0.002 (2)
C11	0.023 (2)	0.025 (3)	0.021 (3)	−0.0014 (18)	0.004 (3)	−0.004 (3)
C12	0.025 (2)	0.028 (2)	0.030 (2)	−0.0065 (17)	−0.0012 (18)	−0.0043 (17)
C13	0.018 (4)	0.024 (3)	0.038 (4)	−0.008 (3)	0.002 (3)	−0.003 (2)
C14	0.040 (4)	0.037 (4)	0.025 (5)	−0.013 (3)	−0.005 (3)	−0.014 (3)
C15	0.028 (2)	0.038 (3)	0.033 (3)	−0.011 (2)	0.0044 (19)	−0.008 (2)
N3	0.0238 (11)	0.0191 (11)	0.0280 (11)	−0.0063 (9)	0.0046 (9)	−0.0008 (9)
N2	0.0270 (11)	0.0209 (11)	0.0263 (11)	−0.0087 (9)	0.0031 (9)	−0.0008 (9)
C16	0.0178 (11)	0.0232 (13)	0.0220 (12)	−0.0067 (10)	0.0088 (9)	−0.0020 (10)
C17	0.0186 (12)	0.0280 (14)	0.0270 (13)	−0.0091 (10)	0.0010 (10)	−0.0009 (11)
C18	0.0213 (12)	0.0243 (14)	0.0275 (13)	−0.0097 (10)	0.0034 (10)	−0.0048 (10)
C19	0.0291 (13)	0.0294 (15)	0.0221 (12)	−0.0100 (11)	0.0035 (10)	−0.0030 (11)
C20	0.0327 (14)	0.0234 (14)	0.0244 (13)	−0.0114 (11)	0.0052 (11)	−0.0051 (10)
C21	0.0515 (17)	0.0218 (14)	0.0314 (14)	−0.0110 (12)	0.0020 (13)	−0.0026 (11)
C22	0.0265 (13)	0.0300 (15)	0.0372 (15)	−0.0092 (11)	−0.0011 (11)	0.0028 (12)
N1A	0.029 (4)	0.013 (3)	0.013 (3)	−0.001 (3)	−0.001 (3)	0.010 (3)
C23	0.024 (7)	0.015 (5)	0.019 (4)	−0.011 (5)	0.003 (6)	0.002 (3)
C24	0.042 (7)	0.017 (7)	0.010 (9)	−0.004 (5)	−0.008 (6)	−0.005 (6)
C25	0.033 (10)	0.035 (6)	0.029 (8)	−0.022 (9)	−0.004 (7)	0.001 (6)
C26	0.037 (5)	0.027 (5)	0.025 (5)	−0.007 (4)	0.000 (4)	0.007 (4)
C27	0.027 (6)	0.014 (4)	0.008 (6)	0.001 (4)	−0.003 (5)	−0.003 (4)
C28	0.029 (5)	0.007 (4)	0.030 (5)	−0.003 (3)	−0.004 (5)	0.004 (4)
C29	0.028 (5)	0.009 (4)	0.022 (5)	−0.005 (3)	−0.007 (4)	0.006 (3)
C30	0.030 (4)	0.038 (5)	0.031 (5)	−0.013 (4)	−0.002 (3)	−0.002 (3)

Geometric parameters (Å, º)

O1—C1	1.286 (3)	N2—C16	1.342 (3)
O2—C1	1.246 (3)	N2—C21	1.470 (3)
C1—C2	1.501 (3)	N2—C22	1.459 (3)
C2—C3	1.419 (3)	C16—C17	1.422 (3)
C2—C7	1.391 (3)	C16—C20	1.426 (3)
C3—C4	1.406 (4)	C17—H17	0.9300
C3—N1	1.418 (4)	C17—C18	1.362 (3)
C3—N1A	1.423 (7)	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C4—C5	1.368 (3)	C19—C20	1.358 (3)
C5—H5	0.9300	C20—H20	0.9300
C5—C6	1.386 (3)	C21—H21A	0.9600
C6—H6	0.9300	C21—H21B	0.9600
C6—C7	1.377 (3)	C21—H21C	0.9600
C7—H7	0.9300	C22—H22A	0.9600
N1—H1	0.858 (19)	C22—H22B	0.9600
N1—C8	1.426 (7)	C22—H22C	0.9600
C8—C9	1.414 (7)	N1A—H1A	0.86 (2)
C8—C13	1.375 (15)	N1A—C29	1.451 (13)
C9—C10	1.403 (9)	C23—H23	0.9300
C9—C14	1.525 (11)	C23—C27	1.366 (15)
C10—C11	1.362 (10)	C23—C30	1.367 (14)
C10—C15	1.527 (7)	C24—H24	0.9300
C11—H11	0.9300	C24—C29	1.27 (3)
C11—C12	1.384 (7)	C24—C30	1.46 (2)
C12—H12	0.9300	C25—H25A	0.9600
C12—C13	1.387 (10)	C25—H25B	0.9600
C13—H13	0.9300	C25—H25C	0.9600
C14—H14A	0.9600	C25—C28	1.51 (2)
C14—H14B	0.9600	C26—H26A	0.9600
C14—H14C	0.9600	C26—H26B	0.9600
C15—H15A	0.9600	C26—H26C	0.9600
C15—H15B	0.9600	C26—C27	1.498 (13)
C15—H15C	0.9600	C27—C28	1.417 (17)
N3—H3	0.921 (17)	C28—C29	1.390 (13)
N3—C18	1.344 (3)	C30—H30	0.9300
N3—C19	1.348 (3)
O1—C1—C2	117.2 (2)	C22—N2—C21	114.7 (2)
O2—C1—O1	123.6 (2)	N2—C16—C17	122.6 (2)
O2—C1—C2	119.2 (2)	N2—C16—C20	122.1 (2)
C3—C2—C1	123.9 (2)	C17—C16—C20	115.3 (2)
C7—C2—C1	118.3 (2)	C16—C17—H17	119.7
C7—C2—C3	117.8 (2)	C18—C17—C16	120.7 (2)
C2—C3—N1A	118.2 (3)	C18—C17—H17	119.7
C4—C3—C2	118.4 (2)	N3—C18—C17	122.3 (2)
C4—C3—N1	119.5 (3)	N3—C18—H18	118.9
C4—C3—N1A	117.2 (3)	C17—C18—H18	118.9
N1—C3—C2	120.9 (3)	N3—C19—H19	118.8
C3—C4—H4	119.2	N3—C19—C20	122.5 (2)
C5—C4—C3	121.6 (2)	C20—C19—H19	118.8
C5—C4—H4	119.2	C16—C20—H20	119.8
C4—C5—H5	119.8	C19—C20—C16	120.4 (2)
C4—C5—C6	120.4 (2)	C19—C20—H20	119.8
C6—C5—H5	119.8	N2—C21—H21A	109.5
C5—C6—H6	120.7	N2—C21—H21B	109.5
C7—C6—C5	118.6 (2)	N2—C21—H21C	109.5
C7—C6—H6	120.7	H21A—C21—H21B	109.5
C2—C7—H7	118.5	H21A—C21—H21C	109.5
C6—C7—C2	123.1 (2)	H21B—C21—H21C	109.5
C6—C7—H7	118.5	N2—C22—H22A	109.5
C3—N1—H1	114 (3)	N2—C22—H22B	109.5
C3—N1—C8	124.5 (3)	N2—C22—H22C	109.5
C8—N1—H1	121 (3)	H22A—C22—H22B	109.5
C9—C8—N1	120.6 (6)	H22A—C22—H22C	109.5
C13—C8—N1	119.2 (5)	H22B—C22—H22C	109.5
C13—C8—C9	120.1 (7)	C3—N1A—H1A	121 (5)
C8—C9—C14	122.2 (8)	C3—N1A—C29	122.4 (5)
C10—C9—C8	117.5 (6)	C29—N1A—H1A	113 (5)
C10—C9—C14	120.3 (7)	C27—C23—H23	118.0
C9—C10—C15	118.6 (7)	C27—C23—C30	124.0 (11)
C11—C10—C9	121.3 (7)	C30—C23—H23	118.0
C11—C10—C15	120.1 (5)	C29—C24—H24	118.4
C10—C11—H11	119.4	C29—C24—C30	123.1 (13)
C10—C11—C12	121.1 (6)	C30—C24—H24	118.4
C12—C11—H11	119.4	H25A—C25—H25B	109.5
C11—C12—H12	120.7	H25A—C25—H25C	109.5
C11—C12—C13	118.6 (7)	H25B—C25—H25C	109.5
C13—C12—H12	120.7	C28—C25—H25A	109.5
C8—C13—C12	121.3 (7)	C28—C25—H25B	109.5
C8—C13—H13	119.4	C28—C25—H25C	109.5
C12—C13—H13	119.4	H26A—C26—H26B	109.5
C9—C14—H14A	109.5	H26A—C26—H26C	109.5
C9—C14—H14B	109.5	H26B—C26—H26C	109.5
C9—C14—H14C	109.5	C27—C26—H26A	109.5
H14A—C14—H14B	109.5	C27—C26—H26B	109.5
H14A—C14—H14C	109.5	C27—C26—H26C	109.5
H14B—C14—H14C	109.5	C23—C27—C26	120.9 (9)
C10—C15—H15A	109.5	C23—C27—C28	118.3 (11)
C10—C15—H15B	109.5	C28—C27—C26	120.7 (11)
C10—C15—H15C	109.5	C27—C28—C25	119.5 (11)
H15A—C15—H15B	109.5	C29—C28—C25	122.3 (14)
H15A—C15—H15C	109.5	C29—C28—C27	118.2 (11)
H15B—C15—H15C	109.5	C24—C29—N1A	118.0 (10)
C18—N3—H3	122.6 (16)	C24—C29—C28	122.0 (13)
C18—N3—C19	118.9 (2)	C28—C29—N1A	120.0 (11)
C19—N3—H3	118.4 (16)	C23—C30—C24	114.3 (12)
C16—N2—C21	121.8 (2)	C23—C30—H30	122.8
C16—N2—C22	123.0 (2)	C24—C30—H30	122.8
O1—C1—C2—C3	5.3 (4)	C11—C12—C13—C8	0.4 (12)
O1—C1—C2—C7	−174.9 (2)	C13—C8—C9—C10	2.5 (8)
O2—C1—C2—C3	−174.2 (2)	C13—C8—C9—C14	−177.4 (9)
O2—C1—C2—C7	5.6 (3)	C14—C9—C10—C11	179.3 (7)
C1—C2—C3—C4	176.9 (3)	C14—C9—C10—C15	−0.4 (9)
C1—C2—C3—N1	−15.7 (5)	C15—C10—C11—C12	178.3 (4)
C1—C2—C3—N1A	25.3 (6)	N3—C19—C20—C16	−0.4 (4)
C1—C2—C7—C6	−177.9 (2)	N2—C16—C17—C18	177.1 (2)
C2—C3—C4—C5	1.8 (5)	N2—C16—C20—C19	−177.7 (2)
C2—C3—N1—C8	−175.6 (4)	C16—C17—C18—N3	1.7 (3)
C2—C3—N1A—C29	176.2 (6)	C17—C16—C20—C19	1.1 (3)
C3—C2—C7—C6	1.9 (4)	C18—N3—C19—C20	0.2 (3)
C3—C4—C5—C6	0.5 (5)	C19—N3—C18—C17	−0.9 (3)
C3—N1—C8—C9	−73.6 (6)	C20—C16—C17—C18	−1.7 (3)
C3—N1—C8—C13	107.9 (7)	C21—N2—C16—C17	175.2 (2)
C3—N1A—C29—C24	−110.6 (14)	C21—N2—C16—C20	−6.1 (3)
C3—N1A—C29—C28	69.0 (10)	C22—N2—C16—C17	4.0 (3)
C4—C3—N1—C8	−8.4 (7)	C22—N2—C16—C20	−177.3 (2)
C4—C3—N1A—C29	24.2 (10)	N1A—C3—C4—C5	153.7 (5)
C4—C5—C6—C7	−1.6 (4)	C23—C27—C28—C25	−176.8 (13)
C5—C6—C7—C2	0.4 (4)	C23—C27—C28—C29	2.8 (12)
C7—C2—C3—C4	−2.9 (4)	C25—C28—C29—N1A	−4.4 (15)
C7—C2—C3—N1	164.5 (3)	C25—C28—C29—C24	175.2 (16)
C7—C2—C3—N1A	−154.5 (5)	C26—C27—C28—C25	0.4 (16)
N1—C3—C4—C5	−165.8 (4)	C26—C27—C28—C29	−180.0 (7)
N1—C8—C9—C10	−176.0 (4)	C27—C23—C30—C24	0.9 (16)
N1—C8—C9—C14	4.1 (9)	C27—C28—C29—N1A	176.0 (6)
N1—C8—C13—C12	176.1 (6)	C27—C28—C29—C24	−4.4 (15)
C8—C9—C10—C11	−0.7 (7)	C29—C24—C30—C23	−2 (2)
C8—C9—C10—C15	179.7 (4)	C30—C23—C27—C26	−178.4 (9)
C9—C8—C13—C12	−2.4 (12)	C30—C23—C27—C28	−1.2 (15)
C9—C10—C11—C12	−1.3 (8)	C30—C24—C29—N1A	−176.1 (12)
C10—C11—C12—C13	1.5 (8)	C30—C24—C29—C28	4 (2)

(mfa-dmap-H2O_1-1-1)

Crystal data

C15H14NO2·H2O·C7H11N2	Z = 2
Mr = 381.46	F(000) = 408
Triclinic, P1	Dx = 1.294 Mg m^−3
a = 7.7248 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0592 (3) Å	Cell parameters from 10891 reflections
c = 16.2531 (7) Å	θ = 2.6–28.1°
α = 101.711 (4)°	µ = 0.09 mm^−1
β = 98.743 (4)°	T = 100 K
γ = 90.160 (3)°	Block, colourless
V = 978.68 (7) Å^3	0.44 × 0.34 × 0.2 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	3976 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	3605 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.031
Detector resolution: 7.9580 pixels mm^-1	θmax = 26.4°, θmin = 2.6°
ω scans	h = −9→9
Absorption correction: multi-scan CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −10→10
Tmin = 0.817, Tmax = 1.000	l = −20→20
20122 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.5896P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3976 reflections	Δρmax = 0.28 e Å^−3
266 parameters	Δρmin = −0.22 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.44608 (12)	0.49854 (11)	0.65769 (6)	0.0171 (2)
O2	0.71182 (12)	0.61232 (12)	0.66294 (6)	0.0216 (2)
N1	0.41509 (15)	0.31551 (14)	0.77509 (7)	0.0178 (2)
H1	0.374 (2)	0.348 (2)	0.7270 (11)	0.021*
C1	0.60181 (16)	0.54579 (15)	0.69584 (8)	0.0150 (3)
C2	0.65082 (16)	0.52369 (15)	0.78601 (8)	0.0141 (3)
C3	0.79294 (17)	0.62072 (16)	0.83616 (8)	0.0167 (3)
H3	0.858048	0.688743	0.811404	0.020*
C4	0.83998 (17)	0.61897 (17)	0.92137 (8)	0.0186 (3)
H4	0.934614	0.685515	0.953716	0.022*
C5	0.74331 (17)	0.51592 (17)	0.95796 (8)	0.0178 (3)
H5	0.773014	0.514403	1.015431	0.021*
C6	0.60389 (17)	0.41592 (16)	0.91000 (8)	0.0166 (3)
H6	0.541885	0.346609	0.935442	0.020*
C7	0.55403 (16)	0.41712 (16)	0.82329 (8)	0.0143 (3)
C8	0.30256 (17)	0.21908 (16)	0.81067 (8)	0.0164 (3)
C9	0.36041 (17)	0.07121 (17)	0.83699 (8)	0.0180 (3)
C10	0.24726 (18)	−0.01869 (18)	0.87397 (9)	0.0213 (3)
C11	0.07958 (18)	0.03846 (18)	0.88094 (9)	0.0224 (3)
H11	0.004991	−0.020744	0.905515	0.027*
C12	0.02127 (18)	0.18180 (18)	0.85205 (9)	0.0214 (3)
H12	−0.092445	0.216558	0.855888	0.026*
C13	0.13299 (17)	0.27312 (17)	0.81743 (8)	0.0182 (3)
H13	0.095027	0.370435	0.798688	0.022*
C14	0.53948 (18)	0.00707 (18)	0.82556 (9)	0.0228 (3)
H14A	0.587473	0.064472	0.787394	0.034*
H14B	0.530790	−0.112627	0.802348	0.034*
H14C	0.614586	0.028394	0.879630	0.034*
C15	0.3074 (2)	−0.1766 (2)	0.90431 (11)	0.0340 (4)
H15A	0.320333	−0.264526	0.856270	0.051*
H15B	0.222213	−0.212925	0.934816	0.051*
H15C	0.417894	−0.152916	0.941178	0.051*
O3	0.61612 (13)	0.70949 (12)	0.50865 (6)	0.0216 (2)
H3B	0.643701	0.660657	0.550246	0.032*
H3C	0.593588	0.628753	0.465487	0.032*
N2	−0.07084 (14)	1.16488 (14)	0.60892 (7)	0.0167 (2)
N3	0.25312 (15)	0.76866 (15)	0.63474 (7)	0.0194 (2)
H3A	0.324 (2)	0.679 (2)	0.6396 (10)	0.023*
C16	0.03549 (16)	1.03708 (16)	0.61844 (8)	0.0153 (3)
C17	0.20371 (17)	1.03095 (16)	0.59280 (8)	0.0169 (3)
H17	0.243789	1.118711	0.570475	0.020*
C18	0.30570 (17)	0.89642 (17)	0.60105 (8)	0.0186 (3)
H18	0.414521	0.892318	0.583003	0.022*
C19	0.09535 (18)	0.77189 (17)	0.66103 (8)	0.0191 (3)
H19	0.061570	0.683926	0.685029	0.023*
C20	−0.01486 (17)	0.90002 (16)	0.65331 (8)	0.0173 (3)
H20	−0.123793	0.898191	0.670904	0.021*
C21	−0.00940 (18)	1.31341 (17)	0.58161 (9)	0.0206 (3)
H21A	0.097905	1.358014	0.617407	0.031*
H21B	−0.096336	1.398340	0.585757	0.031*
H21C	0.010621	1.281545	0.523721	0.031*
C22	−0.25061 (17)	1.15961 (18)	0.62570 (9)	0.0217 (3)
H22A	−0.301544	1.047792	0.603102	0.033*
H22B	−0.317608	1.239955	0.599094	0.033*
H22C	−0.251088	1.187632	0.685963	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0170 (5)	0.0177 (5)	0.0165 (4)	0.0010 (4)	0.0004 (3)	0.0054 (4)
O2	0.0237 (5)	0.0247 (5)	0.0183 (5)	−0.0042 (4)	0.0041 (4)	0.0082 (4)
N1	0.0189 (6)	0.0203 (6)	0.0141 (5)	−0.0050 (4)	0.0000 (4)	0.0056 (4)
C1	0.0184 (6)	0.0101 (6)	0.0167 (6)	0.0021 (5)	0.0043 (5)	0.0021 (5)
C2	0.0151 (6)	0.0125 (6)	0.0148 (6)	0.0036 (5)	0.0038 (5)	0.0018 (5)
C3	0.0164 (6)	0.0149 (6)	0.0194 (6)	−0.0003 (5)	0.0051 (5)	0.0034 (5)
C4	0.0166 (6)	0.0175 (6)	0.0192 (6)	−0.0028 (5)	0.0001 (5)	−0.0003 (5)
C5	0.0194 (6)	0.0202 (7)	0.0130 (6)	0.0028 (5)	0.0015 (5)	0.0022 (5)
C6	0.0179 (6)	0.0169 (6)	0.0162 (6)	0.0002 (5)	0.0055 (5)	0.0043 (5)
C7	0.0140 (6)	0.0131 (6)	0.0158 (6)	0.0025 (5)	0.0038 (5)	0.0016 (5)
C8	0.0174 (6)	0.0178 (6)	0.0120 (6)	−0.0041 (5)	0.0007 (5)	−0.0005 (5)
C9	0.0182 (6)	0.0179 (6)	0.0166 (6)	−0.0025 (5)	0.0015 (5)	0.0016 (5)
C10	0.0233 (7)	0.0201 (7)	0.0198 (7)	−0.0054 (5)	0.0025 (5)	0.0031 (5)
C11	0.0238 (7)	0.0239 (7)	0.0186 (7)	−0.0085 (6)	0.0058 (5)	0.0011 (5)
C12	0.0153 (6)	0.0249 (7)	0.0203 (7)	−0.0014 (5)	0.0032 (5)	−0.0041 (5)
C13	0.0190 (6)	0.0169 (6)	0.0163 (6)	0.0001 (5)	−0.0001 (5)	−0.0002 (5)
C14	0.0205 (7)	0.0205 (7)	0.0286 (7)	0.0012 (5)	0.0042 (6)	0.0073 (6)
C15	0.0336 (9)	0.0294 (8)	0.0443 (10)	−0.0039 (7)	0.0074 (7)	0.0190 (7)
O3	0.0291 (5)	0.0199 (5)	0.0167 (5)	0.0023 (4)	0.0045 (4)	0.0053 (4)
N2	0.0163 (5)	0.0161 (5)	0.0176 (5)	0.0012 (4)	0.0033 (4)	0.0024 (4)
N3	0.0189 (6)	0.0168 (6)	0.0205 (6)	0.0032 (5)	0.0002 (4)	0.0015 (4)
C16	0.0167 (6)	0.0158 (6)	0.0111 (6)	−0.0010 (5)	0.0002 (5)	−0.0012 (5)
C17	0.0172 (6)	0.0170 (6)	0.0155 (6)	−0.0025 (5)	0.0029 (5)	0.0011 (5)
C18	0.0156 (6)	0.0210 (7)	0.0171 (6)	−0.0003 (5)	0.0018 (5)	−0.0003 (5)
C19	0.0232 (7)	0.0171 (6)	0.0165 (6)	−0.0022 (5)	0.0024 (5)	0.0028 (5)
C20	0.0165 (6)	0.0186 (7)	0.0160 (6)	−0.0012 (5)	0.0039 (5)	0.0010 (5)
C21	0.0224 (7)	0.0156 (6)	0.0234 (7)	0.0014 (5)	0.0030 (5)	0.0038 (5)
C22	0.0168 (6)	0.0208 (7)	0.0276 (7)	0.0033 (5)	0.0053 (5)	0.0035 (6)

Geometric parameters (Å, º)

O1—C1	1.2851 (16)	C14—H14B	0.9600
O2—C1	1.2441 (15)	C14—H14C	0.9600
N1—H1	0.887 (17)	C15—H15A	0.9600
N1—C7	1.3839 (17)	C15—H15B	0.9600
N1—C8	1.4231 (16)	C15—H15C	0.9600
C1—C2	1.5034 (17)	O3—H3B	0.8498
C2—C3	1.3948 (18)	O3—H3C	0.8501
C2—C7	1.4175 (17)	N2—C16	1.3380 (17)
C3—H3	0.9300	N2—C21	1.4601 (17)
C3—C4	1.3803 (18)	N2—C22	1.4575 (16)
C4—H4	0.9300	N3—H3A	0.916 (17)
C4—C5	1.3904 (19)	N3—C18	1.3488 (18)
C5—H5	0.9300	N3—C19	1.3500 (18)
C5—C6	1.3791 (18)	C16—C17	1.4217 (18)
C6—H6	0.9300	C16—C20	1.4182 (18)
C6—C7	1.4053 (18)	C17—H17	0.9300
C8—C9	1.3981 (19)	C17—C18	1.3586 (19)
C8—C13	1.3947 (18)	C18—H18	0.9300
C9—C10	1.4082 (18)	C19—H19	0.9300
C9—C14	1.5028 (19)	C19—C20	1.3535 (19)
C10—C11	1.389 (2)	C20—H20	0.9300
C10—C15	1.505 (2)	C21—H21A	0.9600
C11—H11	0.9300	C21—H21B	0.9600
C11—C12	1.384 (2)	C21—H21C	0.9600
C12—H12	0.9300	C22—H22A	0.9600
C12—C13	1.3840 (19)	C22—H22B	0.9600
C13—H13	0.9300	C22—H22C	0.9600
C14—H14A	0.9600
C7—N1—H1	113.4 (10)	C9—C14—H14C	109.5
C7—N1—C8	123.09 (11)	H14A—C14—H14B	109.5
C8—N1—H1	118.7 (10)	H14A—C14—H14C	109.5
O1—C1—C2	117.83 (11)	H14B—C14—H14C	109.5
O2—C1—O1	123.56 (12)	C10—C15—H15A	109.5
O2—C1—C2	118.59 (11)	C10—C15—H15B	109.5
C3—C2—C1	117.74 (11)	C10—C15—H15C	109.5
C3—C2—C7	118.94 (11)	H15A—C15—H15B	109.5
C7—C2—C1	123.22 (11)	H15A—C15—H15C	109.5
C2—C3—H3	119.0	H15B—C15—H15C	109.5
C4—C3—C2	122.08 (12)	H3B—O3—H3C	104.5
C4—C3—H3	119.0	C16—N2—C21	120.76 (11)
C3—C4—H4	120.6	C16—N2—C22	120.91 (11)
C3—C4—C5	118.79 (12)	C22—N2—C21	118.32 (11)
C5—C4—H4	120.6	C18—N3—H3A	120.3 (10)
C4—C5—H5	119.6	C18—N3—C19	120.09 (12)
C6—C5—C4	120.76 (12)	C19—N3—H3A	119.6 (10)
C6—C5—H5	119.6	N2—C16—C17	121.49 (12)
C5—C6—H6	119.5	N2—C16—C20	121.76 (12)
C5—C6—C7	121.04 (12)	C20—C16—C17	116.75 (12)
C7—C6—H6	119.5	C16—C17—H17	120.1
N1—C7—C2	120.67 (11)	C18—C17—C16	119.76 (12)
N1—C7—C6	120.95 (11)	C18—C17—H17	120.1
C6—C7—C2	118.38 (11)	N3—C18—C17	121.67 (12)
C9—C8—N1	120.43 (12)	N3—C18—H18	119.2
C13—C8—N1	118.85 (12)	C17—C18—H18	119.2
C13—C8—C9	120.71 (12)	N3—C19—H19	119.2
C8—C9—C10	118.93 (12)	N3—C19—C20	121.60 (12)
C8—C9—C14	121.01 (12)	C20—C19—H19	119.2
C10—C9—C14	120.06 (12)	C16—C20—H20	119.9
C9—C10—C15	120.03 (13)	C19—C20—C16	120.12 (12)
C11—C10—C9	119.36 (13)	C19—C20—H20	119.9
C11—C10—C15	120.60 (13)	N2—C21—H21A	109.5
C10—C11—H11	119.3	N2—C21—H21B	109.5
C12—C11—C10	121.32 (13)	N2—C21—H21C	109.5
C12—C11—H11	119.3	H21A—C21—H21B	109.5
C11—C12—H12	120.2	H21A—C21—H21C	109.5
C13—C12—C11	119.69 (13)	H21B—C21—H21C	109.5
C13—C12—H12	120.2	N2—C22—H22A	109.5
C8—C13—H13	120.0	N2—C22—H22B	109.5
C12—C13—C8	119.94 (13)	N2—C22—H22C	109.5
C12—C13—H13	120.0	H22A—C22—H22B	109.5
C9—C14—H14A	109.5	H22A—C22—H22C	109.5
C9—C14—H14B	109.5	H22B—C22—H22C	109.5
O1—C1—C2—C3	−159.79 (11)	C8—C9—C10—C15	−178.90 (13)
O1—C1—C2—C7	16.51 (18)	C9—C8—C13—C12	1.28 (19)
O2—C1—C2—C3	18.44 (17)	C9—C10—C11—C12	0.2 (2)
O2—C1—C2—C7	−165.25 (12)	C10—C11—C12—C13	−1.7 (2)
N1—C8—C9—C10	178.35 (11)	C11—C12—C13—C8	0.94 (19)
N1—C8—C9—C14	−2.24 (19)	C13—C8—C9—C10	−2.75 (19)
N1—C8—C13—C12	−179.80 (12)	C13—C8—C9—C14	176.66 (12)
C1—C2—C3—C4	175.06 (12)	C14—C9—C10—C11	−177.41 (13)
C1—C2—C7—N1	5.47 (18)	C14—C9—C10—C15	1.7 (2)
C1—C2—C7—C6	−175.22 (11)	C15—C10—C11—C12	−178.90 (13)
C2—C3—C4—C5	0.6 (2)	N2—C16—C17—C18	−177.95 (12)
C3—C2—C7—N1	−178.26 (11)	N2—C16—C20—C19	179.20 (12)
C3—C2—C7—C6	1.05 (18)	N3—C19—C20—C16	−1.2 (2)
C3—C4—C5—C6	0.6 (2)	C16—C17—C18—N3	−1.35 (19)
C4—C5—C6—C7	−0.9 (2)	C17—C16—C20—C19	0.13 (18)
C5—C6—C7—N1	179.40 (12)	C18—N3—C19—C20	1.08 (19)
C5—C6—C7—C2	0.09 (19)	C19—N3—C18—C17	0.24 (19)
C7—N1—C8—C9	−74.57 (17)	C20—C16—C17—C18	1.13 (18)
C7—N1—C8—C13	106.50 (15)	C21—N2—C16—C17	−7.69 (18)
C7—C2—C3—C4	−1.41 (19)	C21—N2—C16—C20	173.28 (12)
C8—N1—C7—C2	−173.52 (12)	C22—N2—C16—C17	172.45 (12)
C8—N1—C7—C6	7.18 (19)	C22—N2—C16—C20	−6.58 (18)
C8—C9—C10—C11	2.01 (19)

(mfa-dmap_2-1)

Crystal data

C15H14NO2·C15H15NO2·C7H11N2	Z = 2
Mr = 604.73	F(000) = 644
Triclinic, P1	Dx = 1.298 Mg m^−3
a = 10.7678 (8) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.9673 (10) Å	Cell parameters from 1757 reflections
c = 13.7860 (11) Å	θ = 3.6–50.8°
α = 106.152 (7)°	µ = 0.68 mm^−1
β = 105.842 (7)°	T = 100 K
γ = 103.490 (7)°	Needle, colourless
V = 1546.9 (2) Å^3	0.44 × 0.35 × 0.2 mm

Data collection

SuperNova, Dual, Cu at zero, Eos diffractometer	3203 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	2494 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.052
Detector resolution: 7.9580 pixels mm^-1	θmax = 50.9°, θmin = 3.6°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −10→12
Tmin = 0.942, Tmax = 1.000	l = −13→13
4616 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.186	w = 1/[σ^2(Fo^2) + (0.1036P)^2 + 0.6853P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.003
3203 reflections	Δρmax = 0.26 e Å^−3
525 parameters	Δρmin = −0.25 e Å^−3
6 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O2	0.2148 (2)	0.5569 (2)	0.81108 (19)	0.0353 (7)
O3	0.2942 (2)	0.4457 (2)	0.6661 (2)	0.0379 (8)
H3	0.265 (4)	0.479 (3)	0.714 (2)	0.057*
O4	0.0801 (2)	0.3289 (2)	0.55678 (19)	0.0355 (7)
O1	0.4257 (2)	0.6504 (2)	0.93647 (19)	0.0357 (7)
N4	0.5828 (3)	0.5642 (3)	0.8395 (2)	0.0347 (9)
H4A	0.521 (3)	0.581 (3)	0.871 (3)	0.042*
N3	0.8486 (3)	0.4567 (3)	0.7000 (2)	0.0304 (8)
N2	0.0480 (17)	0.1592 (15)	0.3637 (12)	0.031 (2)	0.587 (5)
H2	0.001 (6)	0.186 (6)	0.402 (5)	0.037*	0.5873
N1	0.4583 (16)	0.8308 (14)	1.1222 (11)	0.031 (2)	0.587 (5)
H1	0.503 (6)	0.803 (6)	1.082 (5)	0.037*	0.587 (5)
C1	0.2982 (4)	0.6315 (3)	0.9033 (3)	0.0270 (9)
C2	0.2406 (3)	0.6996 (3)	0.9790 (3)	0.0259 (9)
C16	0.2025 (4)	0.3561 (3)	0.5768 (3)	0.0252 (9)
C17	0.2652 (3)	0.2939 (3)	0.5038 (3)	0.0247 (9)
C21	0.2517 (3)	0.1371 (3)	0.3430 (3)	0.0321 (10)
H21	0.199436	0.069854	0.276350	0.039*
C33	0.6329 (3)	0.4778 (3)	0.8619 (3)	0.0296 (9)
H33	0.604943	0.440999	0.908670	0.036*
C22	0.1831 (3)	0.1919 (3)	0.4061 (3)	0.0308 (10)
C31	0.7634 (3)	0.4938 (3)	0.7467 (3)	0.0261 (10)
C7	0.3227 (3)	0.7990 (3)	1.0779 (3)	0.0304 (10)
C4	0.0366 (4)	0.7175 (3)	1.0151 (3)	0.0369 (11)
H4	−0.060256	0.688481	0.993915	0.044*
C6	0.2554 (4)	0.8545 (3)	1.1420 (3)	0.0327 (10)
H6	0.308490	0.921124	1.208806	0.039*
C32	0.7232 (3)	0.4421 (3)	0.8185 (3)	0.0321 (10)
H32	0.759234	0.382151	0.836429	0.039*
C5	0.1164 (3)	0.8149 (3)	1.1102 (3)	0.0302 (10)
H5	0.074033	0.855187	1.154417	0.036*
C34	0.6195 (3)	0.6166 (3)	0.7730 (3)	0.0309 (10)
H34	0.582246	0.677132	0.757967	0.037*
C20	0.3908 (4)	0.1779 (3)	0.3750 (3)	0.0349 (10)
H20	0.433903	0.137009	0.331932	0.042*
C35	0.7091 (3)	0.5852 (3)	0.7262 (3)	0.0328 (10)
H35	0.734757	0.624457	0.680119	0.039*
C3	0.1005 (4)	0.6629 (3)	0.9512 (3)	0.0342 (10)
H3A	0.045129	0.596616	0.884576	0.041*
C36	0.8994 (4)	0.3602 (3)	0.7209 (3)	0.0364 (10)
H36A	0.955131	0.388247	0.797956	0.055*
H36B	0.955429	0.341458	0.677415	0.055*
H36C	0.821824	0.285798	0.701529	0.055*
C37	0.8944 (4)	0.5146 (3)	0.6303 (3)	0.0344 (10)
H37A	0.816241	0.495397	0.564474	0.052*
H37B	0.963874	0.483178	0.610591	0.052*
H37C	0.933799	0.604237	0.668757	0.052*
C18	0.4056 (4)	0.3329 (3)	0.5320 (3)	0.0378 (11)
H18	0.460357	0.400652	0.597772	0.045*
C19	0.4693 (4)	0.2777 (3)	0.4689 (3)	0.0405 (11)
H19	0.566142	0.307946	0.489683	0.049*
C25	−0.1889 (15)	−0.1476 (13)	0.1579 (13)	0.0304 (18)	0.587 (5)
C12	0.6943 (15)	1.1321 (14)	1.3389 (17)	0.0339 (16)	0.587 (5)
C28	−0.0723 (14)	0.0916 (15)	0.1731 (12)	0.0399 (19)	0.587 (5)
H28	−0.036414	0.173807	0.176879	0.048*	0.587 (5)
C26	−0.2179 (11)	−0.1178 (12)	0.0690 (9)	0.037 (4)	0.587 (5)
H26	−0.281551	−0.178757	0.001888	0.045*	0.587 (5)
C8	0.5453 (13)	0.9230 (12)	1.2217 (12)	0.031 (4)	0.587 (5)
C29	−0.0583 (13)	−0.0888 (14)	0.3587 (8)	0.049 (3)	0.587 (5)
H29A	−0.039970	−0.167027	0.341231	0.074*	0.587 (5)
H29B	−0.133117	−0.096228	0.386703	0.074*	0.587 (5)
H29C	0.024263	−0.022831	0.413707	0.074*	0.587 (5)
C15	0.5641 (16)	1.0875 (17)	1.1419 (14)	0.038 (4)	0.587 (5)
H15A	0.556563	1.169804	1.167635	0.057*	0.587 (5)
H15B	0.475803	1.029302	1.087739	0.057*	0.587 (5)
H15C	0.634372	1.090731	1.109180	0.057*	0.587 (5)
C11	0.7215 (11)	1.0964 (12)	1.4269 (8)	0.049 (3)	0.587 (5)
H11	0.782586	1.154368	1.496217	0.058*	0.587 (5)
C23	−0.0398 (11)	0.0641 (10)	0.2673 (10)	0.027 (3)	0.587 (5)
C9	0.5765 (12)	0.8894 (11)	1.3146 (10)	0.027 (3)	0.587 (5)
H9A	0.539086	0.806088	1.307521	0.032*	0.587 (5)
C24	−0.0980 (8)	−0.0590 (9)	0.2595 (7)	0.0304 (18)	0.587 (5)
C13	0.6030 (9)	1.0459 (9)	1.2353 (8)	0.0339 (16)	0.587 (5)
C27	−0.1577 (7)	−0.0018 (7)	0.0731 (5)	0.0399 (19)	0.587 (5)
H27	−0.173680	0.015485	0.008419	0.048*	0.587 (5)
C30	−0.2540 (8)	−0.2783 (8)	0.1509 (6)	0.042 (2)	0.587 (5)
H30A	−0.325381	−0.325964	0.079188	0.063*	0.587 (5)
H30B	−0.294772	−0.275564	0.206639	0.063*	0.587 (5)
H30C	−0.183812	−0.317673	0.162406	0.063*	0.587 (5)
C14	0.7583 (7)	1.2636 (8)	1.3505 (6)	0.041 (2)	0.587 (5)
H14A	0.690908	1.306202	1.351182	0.062*	0.587 (5)
H14B	0.787929	1.264242	1.289419	0.062*	0.587 (5)
H14C	0.837608	1.305811	1.418431	0.062*	0.587 (5)
C10	0.6596 (7)	0.9763 (7)	1.4135 (6)	0.045 (2)	0.587 (5)
H10	0.675305	0.953062	1.475108	0.053*	0.587 (5)
C49	0.6830 (9)	1.1793 (9)	1.2619 (8)	0.042 (3)	0.413 (5)
H49	0.713423	1.254338	1.250881	0.050*	0.413 (5)
C50	−0.1677 (9)	−0.1950 (9)	0.2332 (8)	0.037 (3)	0.413 (5)
H50	−0.195888	−0.268886	0.246453	0.044*	0.413 (5)
C38	−0.0808 (11)	0.0229 (12)	0.1949 (13)	0.037 (3)	0.413 (5)
C40	−0.2279 (12)	−0.0944 (10)	−0.0094 (10)	0.057 (4)	0.413 (5)
H40A	−0.264063	−0.026398	−0.008817	0.086*	0.413 (5)
H40B	−0.301116	−0.173129	−0.055562	0.086*	0.413 (5)
H40C	−0.153417	−0.084949	−0.037618	0.086*	0.413 (5)
C41	0.5846 (11)	0.9605 (12)	1.2913 (13)	0.0339 (16)	0.413 (5)
C45	0.554 (2)	0.9681 (18)	1.1942 (19)	0.031 (4)	0.413 (5)
C46	0.7197 (16)	1.0693 (15)	1.4964 (11)	0.092 (6)	0.413 (5)
H46A	0.638610	1.057373	1.516887	0.138*	0.413 (5)
H46B	0.790257	1.147748	1.547388	0.138*	0.413 (5)
H46C	0.755171	1.001370	1.498436	0.138*	0.413 (5)
N8	0.468 (2)	0.857 (2)	1.0979 (18)	0.031 (2)	0.413 (5)
H8	0.498 (9)	0.826 (8)	1.047 (5)	0.037*	0.4127
N9	0.039 (3)	0.134 (2)	0.3857 (19)	0.031 (2)	0.413 (5)
H9	0.005 (9)	0.162 (8)	0.434 (5)	0.037*	0.413 (5)
C51	−0.0437 (17)	0.0150 (16)	0.2908 (15)	0.027 (3)	0.413 (5)
C39	−0.0418 (17)	0.1290 (15)	0.1622 (15)	0.041 (5)	0.413 (5)
H39A	−0.124376	0.143826	0.125102	0.062*	0.413 (5)
H39B	0.008062	0.111433	0.113210	0.062*	0.413 (5)
H39C	0.017010	0.202396	0.226633	0.062*	0.413 (5)
C43	0.533 (2)	0.845 (2)	1.314 (2)	0.065 (8)	0.413 (5)
H43A	0.473113	0.777244	1.245425	0.098*	0.413 (5)
H43B	0.482528	0.860003	1.362236	0.098*	0.413 (5)
H43C	0.611598	0.822604	1.347963	0.098*	0.413 (5)
C47	0.598 (2)	1.073 (2)	1.176 (2)	0.043 (7)	0.413 (5)
H47	0.571435	1.073170	1.104189	0.052*	0.413 (5)
C42	−0.1736 (17)	−0.0925 (19)	0.106 (2)	0.037 (3)	0.413 (5)
C44	−0.0824 (18)	−0.089 (2)	0.3162 (16)	0.037 (3)	0.413 (5)
H44	−0.050426	−0.086610	0.388531	0.044*	0.413 (5)
C48	0.7213 (16)	1.1758 (12)	1.3590 (18)	0.028 (4)	0.413 (5)
H48	0.780998	1.250068	1.417241	0.034*	0.413 (5)
C52	0.6811 (15)	1.0717 (16)	1.3833 (14)	0.0339 (16)	0.413 (5)
C53	−0.2125 (14)	−0.1953 (13)	0.1327 (14)	0.027 (5)	0.413 (5)
H53	−0.274475	−0.270211	0.076412	0.032*	0.413 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0319 (14)	0.0342 (16)	0.0239 (15)	0.0124 (12)	0.0032 (13)	−0.0072 (13)
O3	0.0302 (15)	0.0363 (17)	0.0298 (16)	0.0113 (13)	0.0067 (13)	−0.0092 (14)
O4	0.0270 (16)	0.0341 (16)	0.0319 (15)	0.0103 (12)	0.0070 (12)	−0.0041 (12)
O1	0.0296 (16)	0.0336 (15)	0.0328 (15)	0.0131 (12)	0.0092 (12)	−0.0040 (12)
N4	0.0322 (18)	0.032 (2)	0.0308 (19)	0.0109 (16)	0.0096 (15)	−0.0011 (16)
N3	0.0298 (17)	0.0244 (17)	0.0324 (18)	0.0104 (14)	0.0106 (15)	0.0029 (15)
N2	0.023 (2)	0.030 (6)	0.027 (6)	0.000 (4)	0.015 (3)	−0.007 (3)
N1	0.023 (2)	0.030 (6)	0.027 (6)	0.000 (4)	0.015 (3)	−0.007 (3)
C1	0.027 (2)	0.022 (2)	0.028 (2)	0.0089 (17)	0.0082 (19)	0.0057 (19)
C2	0.026 (2)	0.019 (2)	0.024 (2)	0.0076 (17)	0.0040 (17)	−0.0006 (17)
C16	0.024 (2)	0.022 (2)	0.023 (2)	0.0066 (17)	0.0035 (18)	0.0033 (18)
C17	0.024 (2)	0.021 (2)	0.023 (2)	0.0087 (17)	0.0053 (17)	0.0007 (17)
C21	0.030 (2)	0.025 (2)	0.031 (2)	0.0106 (18)	0.0071 (18)	−0.0020 (18)
C33	0.033 (2)	0.025 (2)	0.025 (2)	0.0102 (18)	0.0071 (17)	0.0051 (17)
C22	0.025 (2)	0.026 (2)	0.034 (2)	0.0115 (18)	0.0060 (18)	0.0027 (18)
C31	0.024 (2)	0.018 (2)	0.025 (2)	0.0024 (17)	0.0059 (18)	−0.0019 (18)
C7	0.024 (2)	0.026 (2)	0.032 (2)	0.0109 (17)	0.0035 (18)	0.0005 (18)
C4	0.023 (2)	0.039 (2)	0.032 (2)	0.0099 (18)	0.0032 (18)	−0.004 (2)
C6	0.030 (2)	0.024 (2)	0.032 (2)	0.0100 (18)	0.0066 (18)	−0.0038 (18)
C32	0.033 (2)	0.027 (2)	0.033 (2)	0.0130 (18)	0.0101 (19)	0.0069 (19)
C5	0.031 (2)	0.031 (2)	0.027 (2)	0.0178 (18)	0.0108 (18)	0.0024 (18)
C34	0.032 (2)	0.026 (2)	0.030 (2)	0.0110 (18)	0.0082 (18)	0.0056 (19)
C20	0.033 (2)	0.033 (2)	0.034 (2)	0.0192 (19)	0.0099 (19)	0.0009 (19)
C35	0.033 (2)	0.027 (2)	0.033 (2)	0.0097 (18)	0.0091 (18)	0.0053 (18)
C3	0.030 (2)	0.031 (2)	0.024 (2)	0.0091 (18)	0.0013 (18)	−0.0069 (18)
C36	0.042 (2)	0.026 (2)	0.044 (2)	0.0153 (19)	0.0224 (19)	0.0065 (19)
C37	0.035 (2)	0.035 (2)	0.032 (2)	0.0145 (18)	0.0136 (18)	0.0077 (19)
C18	0.031 (2)	0.034 (2)	0.029 (2)	0.0115 (19)	0.0019 (18)	−0.0082 (18)
C19	0.024 (2)	0.039 (3)	0.039 (2)	0.0079 (19)	0.0063 (19)	−0.007 (2)
C25	0.036 (4)	0.014 (5)	0.041 (5)	0.014 (4)	0.015 (4)	0.005 (4)
C12	0.034 (4)	0.016 (5)	0.047 (6)	0.015 (4)	0.010 (3)	0.005 (3)
C28	0.044 (4)	0.049 (5)	0.024 (3)	0.018 (4)	0.001 (3)	0.018 (3)
C26	0.022 (6)	0.039 (7)	0.037 (9)	0.014 (6)	−0.002 (5)	0.003 (6)
C8	0.024 (3)	0.020 (8)	0.038 (9)	0.005 (6)	0.014 (4)	−0.008 (6)
C29	0.051 (6)	0.036 (5)	0.042 (7)	0.011 (4)	0.000 (5)	0.006 (6)
C15	0.036 (8)	0.033 (7)	0.043 (8)	0.016 (5)	0.011 (6)	0.011 (5)
C11	0.043 (7)	0.047 (8)	0.035 (8)	0.020 (6)	0.006 (5)	−0.011 (6)
C23	0.021 (3)	0.006 (7)	0.039 (6)	0.005 (5)	0.004 (3)	−0.006 (5)
C9	0.030 (7)	0.022 (10)	0.023 (6)	0.007 (7)	0.003 (5)	0.008 (6)
C24	0.036 (4)	0.014 (5)	0.041 (5)	0.014 (4)	0.015 (4)	0.005 (4)
C13	0.034 (4)	0.016 (5)	0.047 (6)	0.015 (4)	0.010 (3)	0.005 (3)
C27	0.044 (4)	0.049 (5)	0.024 (3)	0.018 (4)	0.001 (3)	0.018 (3)
C30	0.044 (5)	0.030 (5)	0.045 (5)	0.020 (4)	0.007 (4)	0.006 (4)
C14	0.047 (5)	0.042 (5)	0.035 (5)	0.024 (4)	0.011 (4)	0.010 (5)
C10	0.052 (5)	0.055 (6)	0.023 (5)	0.030 (4)	0.003 (4)	0.009 (5)
C49	0.035 (6)	0.022 (6)	0.042 (8)	−0.002 (5)	0.008 (6)	−0.009 (7)
C50	0.027 (5)	0.027 (5)	0.039 (7)	0.002 (4)	0.006 (5)	−0.002 (5)
C38	0.021 (6)	0.032 (8)	0.045 (8)	0.017 (5)	−0.001 (5)	0.000 (6)
C40	0.065 (8)	0.044 (7)	0.026 (7)	0.014 (6)	−0.018 (6)	−0.005 (6)
C41	0.034 (4)	0.016 (5)	0.047 (6)	0.015 (4)	0.010 (3)	0.005 (3)
C45	0.024 (3)	0.020 (8)	0.038 (9)	0.005 (6)	0.014 (4)	−0.008 (6)
C46	0.110 (12)	0.089 (12)	0.028 (8)	0.010 (9)	−0.018 (8)	0.011 (9)
N8	0.023 (2)	0.030 (6)	0.027 (6)	0.000 (4)	0.015 (3)	−0.007 (3)
N9	0.023 (2)	0.030 (6)	0.027 (6)	0.000 (4)	0.015 (3)	−0.007 (3)
C51	0.021 (3)	0.006 (7)	0.039 (6)	0.005 (5)	0.004 (3)	−0.006 (5)
C39	0.037 (8)	0.055 (11)	0.026 (8)	0.018 (7)	0.010 (5)	0.006 (6)
C43	0.053 (15)	0.036 (13)	0.079 (13)	0.000 (9)	−0.002 (9)	0.019 (9)
C47	0.022 (10)	0.034 (11)	0.08 (2)	0.015 (8)	0.011 (12)	0.024 (12)
C42	0.021 (6)	0.032 (8)	0.045 (8)	0.017 (5)	−0.001 (5)	0.000 (6)
C44	0.027 (5)	0.027 (5)	0.039 (7)	0.002 (4)	0.006 (5)	−0.002 (5)
C48	0.035 (9)	0.020 (12)	0.033 (11)	0.018 (9)	0.011 (8)	0.009 (9)
C52	0.034 (4)	0.016 (5)	0.047 (6)	0.015 (4)	0.010 (3)	0.005 (3)
C53	0.020 (7)	0.014 (11)	0.031 (10)	0.007 (8)	−0.004 (6)	−0.002 (8)

Geometric parameters (Å, º)

O2—C1	1.261 (4)	C26—H26	0.9500
O3—H3	0.84 (2)	C26—C27	1.366 (16)
O3—C16	1.322 (4)	C8—C9	1.425 (18)
O4—C16	1.212 (4)	C8—C13	1.393 (16)
O1—C1	1.264 (4)	C29—H29A	0.9800
N4—H4A	0.919 (19)	C29—H29B	0.9800
N4—C33	1.343 (5)	C29—H29C	0.9800
N4—C34	1.339 (5)	C29—C24	1.484 (13)
N3—C31	1.345 (4)	C15—H15A	0.9800
N3—C36	1.452 (5)	C15—H15B	0.9800
N3—C37	1.455 (5)	C15—H15C	0.9800
N2—H2	0.87 (2)	C15—C13	1.497 (16)
N2—C22	1.325 (17)	C11—H11	0.9500
N2—C23	1.39 (2)	C11—C10	1.373 (15)
N1—H1	0.88 (2)	C23—C24	1.422 (14)
N1—C7	1.333 (16)	C9—H9A	0.9500
N1—C8	1.40 (2)	C9—C10	1.360 (14)
C1—C2	1.502 (5)	C27—H27	0.9500
C2—C7	1.415 (5)	C30—H30A	0.9800
C2—C3	1.377 (5)	C30—H30B	0.9800
C16—C17	1.486 (5)	C30—H30C	0.9800
C17—C22	1.420 (5)	C14—H14A	0.9800
C17—C18	1.380 (5)	C14—H14B	0.9800
C21—H21	0.9500	C14—H14C	0.9800
C21—C22	1.412 (5)	C10—H10	0.9500
C21—C20	1.361 (5)	C49—H49	0.9500
C33—H33	0.9500	C49—C47	1.37 (3)
C33—C32	1.362 (5)	C49—C48	1.31 (3)
C22—N9	1.45 (2)	C50—H50	0.9500
C31—C32	1.414 (5)	C50—C44	1.35 (2)
C31—C35	1.413 (5)	C50—C53	1.34 (2)
C7—C6	1.412 (5)	C38—C51	1.31 (2)
C7—N8	1.46 (2)	C38—C39	1.471 (19)
C4—H4	0.9500	C38—C42	1.47 (3)
C4—C5	1.372 (5)	C40—H40A	0.9800
C4—C3	1.377 (5)	C40—H40B	0.9800
C6—H6	0.9500	C40—H40C	0.9800
C6—C5	1.362 (5)	C40—C42	1.52 (3)
C32—H32	0.9500	C41—C45	1.32 (3)
C5—H5	0.9500	C41—C43	1.51 (2)
C34—H34	0.9500	C41—C52	1.47 (2)
C34—C35	1.364 (5)	C45—N8	1.47 (3)
C20—H20	0.9500	C45—C47	1.36 (3)
C20—C19	1.374 (5)	C46—H46A	0.9800
C35—H35	0.9500	C46—H46B	0.9800
C3—H3A	0.9500	C46—H46C	0.9800
C36—H36A	0.9800	C46—C52	1.51 (2)
C36—H36B	0.9800	N8—H8	0.88 (2)
C36—H36C	0.9800	N9—H9	0.87 (2)
C37—H37A	0.9800	N9—C51	1.50 (3)
C37—H37B	0.9800	C51—C44	1.39 (3)
C37—H37C	0.9800	C39—H39A	0.9800
C18—H18	0.9500	C39—H39B	0.9800
C18—C19	1.372 (5)	C39—H39C	0.9800
C19—H19	0.9500	C43—H43A	0.9800
C25—C26	1.35 (2)	C43—H43B	0.9800
C25—C24	1.409 (19)	C43—H43C	0.9800
C25—C30	1.522 (16)	C47—H47	0.9500
C12—C11	1.37 (3)	C42—C53	1.39 (3)
C12—C13	1.42 (2)	C44—H44	0.9500
C12—C14	1.507 (18)	C48—H48	0.9500
C28—H28	0.9500	C48—C52	1.38 (4)
C28—C23	1.401 (19)	C53—H53	0.9500
C28—C27	1.402 (18)
C16—O3—H3	117 (3)	C24—C29—H29C	109.5
C33—N4—H4A	115 (2)	H15A—C15—H15B	109.5
C34—N4—H4A	124 (2)	H15A—C15—H15C	109.5
C34—N4—C33	120.7 (3)	H15B—C15—H15C	109.5
C31—N3—C36	120.3 (3)	C13—C15—H15A	109.5
C31—N3—C37	120.7 (3)	C13—C15—H15B	109.5
C36—N3—C37	119.0 (3)	C13—C15—H15C	109.5
C22—N2—H2	121 (5)	C12—C11—H11	120.3
C22—N2—C23	127.4 (15)	C12—C11—C10	119.3 (11)
C23—N2—H2	110 (5)	C10—C11—H11	120.3
C7—N1—H1	119 (5)	N2—C23—C28	118.0 (10)
C7—N1—C8	127.4 (13)	N2—C23—C24	123.4 (11)
C8—N1—H1	113 (5)	C28—C23—C24	118.6 (13)
O2—C1—O1	124.4 (3)	C8—C9—H9A	119.9
O2—C1—C2	117.3 (3)	C10—C9—C8	120.2 (12)
O1—C1—C2	118.3 (3)	C10—C9—H9A	119.9
C7—C2—C1	123.5 (3)	C25—C24—C29	123.0 (13)
C3—C2—C1	118.3 (3)	C25—C24—C23	118.7 (11)
C3—C2—C7	118.3 (3)	C23—C24—C29	118.4 (10)
O3—C16—C17	113.0 (3)	C12—C13—C15	120.3 (15)
O4—C16—O3	123.0 (3)	C8—C13—C12	119.6 (13)
O4—C16—C17	123.9 (3)	C8—C13—C15	120.0 (12)
C22—C17—C16	121.1 (3)	C28—C27—H27	120.1
C18—C17—C16	120.0 (3)	C26—C27—C28	119.8 (9)
C18—C17—C22	118.8 (3)	C26—C27—H27	120.1
C22—C21—H21	119.1	C25—C30—H30A	109.5
C20—C21—H21	119.1	C25—C30—H30B	109.5
C20—C21—C22	121.8 (3)	C25—C30—H30C	109.5
N4—C33—H33	119.5	H30A—C30—H30B	109.5
N4—C33—C32	121.0 (4)	H30A—C30—H30C	109.5
C32—C33—H33	119.5	H30B—C30—H30C	109.5
N2—C22—C17	123.3 (8)	C12—C14—H14A	109.5
N2—C22—C21	118.5 (8)	C12—C14—H14B	109.5
C17—C22—N9	119.5 (11)	C12—C14—H14C	109.5
C21—C22—C17	117.2 (3)	H14A—C14—H14B	109.5
C21—C22—N9	122.1 (11)	H14A—C14—H14C	109.5
N3—C31—C32	121.2 (3)	H14B—C14—H14C	109.5
N3—C31—C35	122.0 (3)	C11—C10—H10	119.0
C35—C31—C32	116.9 (3)	C9—C10—C11	122.0 (9)
N1—C7—C2	124.0 (8)	C9—C10—H10	119.0
N1—C7—C6	117.4 (7)	C47—C49—H49	120.4
C2—C7—N8	118.9 (10)	C48—C49—H49	120.4
C6—C7—C2	117.7 (3)	C48—C49—C47	119.1 (15)
C6—C7—N8	122.0 (11)	C44—C50—H50	120.0
C5—C4—H4	120.8	C53—C50—H50	120.0
C5—C4—C3	118.4 (3)	C53—C50—C44	120.0 (15)
C3—C4—H4	120.8	C51—C38—C39	130.0 (15)
C7—C6—H6	119.2	C51—C38—C42	115.3 (16)
C5—C6—C7	121.6 (3)	C42—C38—C39	114.8 (19)
C5—C6—H6	119.2	H40A—C40—H40B	109.5
C33—C32—C31	120.2 (3)	H40A—C40—H40C	109.5
C33—C32—H32	119.9	H40B—C40—H40C	109.5
C31—C32—H32	119.9	C42—C40—H40A	109.5
C4—C5—H5	119.6	C42—C40—H40B	109.5
C6—C5—C4	120.8 (3)	C42—C40—H40C	109.5
C6—C5—H5	119.6	C45—C41—C43	125.0 (18)
N4—C34—H34	119.2	C45—C41—C52	117.0 (15)
N4—C34—C35	121.6 (3)	C52—C41—C43	117.9 (19)
C35—C34—H34	119.2	C41—C45—N8	119.5 (13)
C21—C20—H20	119.6	C41—C45—C47	124 (2)
C21—C20—C19	120.7 (3)	C47—C45—N8	116.3 (19)
C19—C20—H20	119.7	H46A—C46—H46B	109.5
C31—C35—H35	120.2	H46A—C46—H46C	109.5
C34—C35—C31	119.6 (4)	H46B—C46—H46C	109.5
C34—C35—H35	120.2	C52—C46—H46A	109.5
C2—C3—C4	123.2 (3)	C52—C46—H46B	109.5
C2—C3—H3A	118.4	C52—C46—H46C	109.5
C4—C3—H3A	118.4	C7—N8—C45	120.9 (18)
N3—C36—H36A	109.5	C7—N8—H8	117 (7)
N3—C36—H36B	109.5	C45—N8—H8	122 (7)
N3—C36—H36C	109.5	C22—N9—H9	119 (7)
H36A—C36—H36B	109.5	C22—N9—C51	120.0 (19)
H36A—C36—H36C	109.5	C51—N9—H9	120 (7)
H36B—C36—H36C	109.5	C38—C51—N9	116.8 (15)
N3—C37—H37A	109.5	C38—C51—C44	127.2 (18)
N3—C37—H37B	109.5	C44—C51—N9	115.7 (15)
N3—C37—H37C	109.5	C38—C39—H39A	109.5
H37A—C37—H37B	109.5	C38—C39—H39B	109.5
H37A—C37—H37C	109.5	C38—C39—H39C	109.5
H37B—C37—H37C	109.5	H39A—C39—H39B	109.5
C17—C18—H18	118.7	H39A—C39—H39C	109.5
C19—C18—C17	122.6 (3)	H39B—C39—H39C	109.5
C19—C18—H18	118.7	C41—C43—H43A	109.5
C20—C19—H19	120.6	C41—C43—H43B	109.5
C18—C19—C20	118.9 (3)	C41—C43—H43C	109.5
C18—C19—H19	120.6	H43A—C43—H43B	109.5
C26—C25—C24	121.1 (15)	H43A—C43—H43C	109.5
C26—C25—C30	120.6 (12)	H43B—C43—H43C	109.5
C24—C25—C30	118.3 (13)	C49—C47—H47	120.4
C11—C12—C13	120.5 (17)	C45—C47—C49	119 (2)
C11—C12—C14	121.0 (13)	C45—C47—H47	120.4
C13—C12—C14	118.4 (19)	C38—C42—C40	120.3 (19)
C23—C28—H28	119.9	C53—C42—C38	117 (2)
C23—C28—C27	120.2 (12)	C53—C42—C40	122.9 (15)
C27—C28—H28	119.9	C50—C44—C51	116.9 (18)
C25—C26—H26	119.3	C50—C44—H44	121.5
C25—C26—C27	121.4 (11)	C51—C44—H44	121.5
C27—C26—H26	119.3	C49—C48—H48	117.7
N1—C8—C9	118.0 (9)	C49—C48—C52	124.7 (15)
C13—C8—N1	123.8 (10)	C52—C48—H48	117.7
C13—C8—C9	118.2 (13)	C41—C52—C46	119.6 (18)
H29A—C29—H29B	109.5	C48—C52—C41	116 (2)
H29A—C29—H29C	109.5	C48—C52—C46	124.6 (16)
H29B—C29—H29C	109.5	C50—C53—C42	123.9 (14)
C24—C29—H29A	109.5	C50—C53—H53	118.1
C24—C29—H29B	109.5	C42—C53—H53	118.1
O2—C1—C2—C7	−170.1 (3)	C18—C17—C22—C21	−0.6 (5)
O2—C1—C2—C3	10.4 (5)	C18—C17—C22—N9	167.6 (9)
O3—C16—C17—C22	177.3 (3)	C25—C26—C27—C28	−5.2 (16)
O3—C16—C17—C18	−0.8 (5)	C12—C11—C10—C9	3.0 (15)
O4—C16—C17—C22	−3.5 (6)	C28—C23—C24—C25	−1.7 (14)
O4—C16—C17—C18	178.4 (4)	C28—C23—C24—C29	177.3 (10)
O1—C1—C2—C7	11.3 (5)	C26—C25—C24—C29	−177.2 (11)
O1—C1—C2—C3	−168.2 (3)	C26—C25—C24—C23	1.7 (16)
N4—C33—C32—C31	−1.4 (5)	C8—N1—C7—C2	−176.4 (7)
N4—C34—C35—C31	1.0 (5)	C8—N1—C7—C6	−7.2 (12)
N3—C31—C32—C33	−177.6 (3)	C8—C9—C10—C11	−3.4 (15)
N3—C31—C35—C34	177.9 (3)	C11—C12—C13—C8	−2.9 (19)
N2—C23—C24—C25	178.2 (12)	C11—C12—C13—C15	174.6 (12)
N2—C23—C24—C29	−2.7 (15)	C23—N2—C22—C17	177.6 (8)
N1—C7—C6—C5	−170.2 (6)	C23—N2—C22—C21	8.8 (13)
N1—C8—C9—C10	−179.4 (11)	C23—C28—C27—C26	5.2 (17)
N1—C8—C13—C12	−177.6 (13)	C9—C8—C13—C12	2.5 (16)
N1—C8—C13—C15	4.9 (18)	C9—C8—C13—C15	−175.0 (12)
C1—C2—C7—N1	−10.4 (8)	C24—C25—C26—C27	1.8 (18)
C1—C2—C7—C6	−179.6 (3)	C13—C12—C11—C10	0.2 (19)
C1—C2—C7—N8	13.6 (10)	C13—C8—C9—C10	0.5 (16)
C1—C2—C3—C4	179.1 (3)	C27—C28—C23—N2	178.4 (12)
C2—C7—C6—C5	−0.3 (6)	C27—C28—C23—C24	−1.7 (17)
C2—C7—N8—C45	173.7 (11)	C30—C25—C26—C27	−178.2 (9)
C16—C17—C22—N2	12.4 (8)	C30—C25—C24—C29	2.7 (15)
C16—C17—C22—C21	−178.7 (3)	C30—C25—C24—C23	−178.3 (8)
C16—C17—C22—N9	−10.6 (10)	C14—C12—C11—C10	178.9 (9)
C16—C17—C18—C19	178.8 (4)	C14—C12—C13—C8	178.3 (9)
C17—C22—N9—C51	−171.3 (11)	C14—C12—C13—C15	−4.2 (18)
C17—C18—C19—C20	−1.5 (6)	C49—C48—C52—C41	−2 (2)
C21—C22—N9—C51	−3.7 (19)	C49—C48—C52—C46	−176.7 (14)
C21—C20—C19—C18	2.3 (6)	C38—C51—C44—C50	0 (2)
C33—N4—C34—C35	−0.4 (5)	C38—C42—C53—C50	−2 (2)
C22—N2—C23—C28	−91.4 (14)	C40—C42—C53—C50	−178.9 (13)
C22—N2—C23—C24	88.7 (12)	C41—C45—N8—C7	69 (2)
C22—C17—C18—C19	0.6 (6)	C41—C45—C47—C49	1 (3)
C22—C21—C20—C19	−2.4 (6)	C45—C41—C52—C46	179.5 (13)
C22—N9—C51—C38	−75 (2)	C45—C41—C52—C48	5 (2)
C22—N9—C51—C44	110.2 (16)	N8—C7—C6—C5	166.1 (9)
C7—N1—C8—C9	92.2 (14)	N8—C45—C47—C49	−177.7 (18)
C7—N1—C8—C13	−87.7 (13)	N9—C51—C44—C50	173.9 (16)
C7—C2—C3—C4	−0.5 (6)	C51—C38—C42—C40	178.0 (12)
C7—C6—C5—C4	1.2 (6)	C51—C38—C42—C53	1 (2)
C6—C7—N8—C45	7.4 (18)	C39—C38—C51—N9	8 (2)
C32—C31—C35—C34	−1.7 (5)	C39—C38—C51—C44	−178.6 (15)
C5—C4—C3—C2	1.4 (6)	C39—C38—C42—C40	−3 (2)
C34—N4—C33—C32	0.7 (5)	C39—C38—C42—C53	179.6 (13)
C20—C21—C22—N2	170.9 (6)	C43—C41—C45—N8	−3 (3)
C20—C21—C22—C17	1.5 (6)	C43—C41—C45—C47	179 (2)
C20—C21—C22—N9	−166.4 (9)	C43—C41—C52—C46	−3 (2)
C35—C31—C32—C33	1.9 (5)	C43—C41—C52—C48	−178.0 (16)
C3—C2—C7—N1	169.1 (6)	C47—C49—C48—C52	−1 (2)
C3—C2—C7—C6	−0.1 (5)	C47—C45—N8—C7	−112.6 (17)
C3—C2—C7—N8	−166.9 (9)	C42—C38—C51—N9	−173.8 (16)
C3—C4—C5—C6	−1.7 (6)	C42—C38—C51—C44	0 (2)
C36—N3—C31—C32	1.2 (5)	C44—C50—C53—C42	2 (2)
C36—N3—C31—C35	−178.3 (3)	C48—C49—C47—C45	2 (3)
C37—N3—C31—C32	−177.1 (3)	C52—C41—C45—N8	174.4 (15)
C37—N3—C31—C35	3.4 (5)	C52—C41—C45—C47	−4 (2)
C18—C17—C22—N2	−169.5 (6)	C53—C50—C44—C51	−1 (2)