Enantioselectivity of chiral di­hydro­myricetin in multicomponent solid solutions regulated by subtle structural mutation

Multicomponent crystals of a chiral drug with non-chiral components have attracted increasing attention in the application of enantiomer purification and regulation of the physicochemical properties of crystalline materials. Crystalline solid solutions provide opportunities for fine-tuning material properties because of continuously adjustable component stoichiometry ratios. The synthesis, crystal structure, thermodynamics and solid-state enantioselectivity of a series of multicomponent crystals of chiral di­hydro­myricetin (DMY) with caffeine (CAF) or theophylline (THE) were investigated and the results reveal how the subtle change of molecular structure of the coformer dictates the enantiomer selectivity in multicomponent cocrystals. A series of multicomponent cocrystal solvates of chiral DMY with CAF and THE were synthesized by the slurry cocrystallization method in aceto­nitrile. Although most racemic mixtures crystallize as racemic compounds or conglomerates, both DMY–CAF and DMY–THE crystallize as chiral solid solutions, unveiled by pseudo-binary melt phase diagrams and pseudo-ternary solution phase diagrams. Crystal structures of Rac-DMY–CAF, R,R-DMY–CAF, Rac-DMY–THE and R,R-DMY–THE are reported for the first time via single-crystal X-ray diffraction, displaying two distinct types of solid solution differing in mixing scale of enantiomers spanning several orders of magnitude. Surprisingly, this remarkable impact on enantiomer discrimination was simply achieved by the reduction of a methyl group of CAF to the THE coformer, which was further rationalized from their crystal structures and intermolecular interactions. Collectively, this work has demonstrated that a subtle change in the molecular structure of a coformer can regulate enantioselectivity in crystalline materials, guiding the purification of chiral racemic compounds via the cocrystallization method and the design of solid-solution crystalline materials.

1. Introduction

In recent years, multicomponent crystals containing a chiral pharmaceutical agent and coformers have provided new opportunities for tuning the physicochemical properties of crystalline materials (Jiang et al., 2021; Huang et al., 2019) and for chiral resolution in pharmaceuticals (Guillot et al., 2020). Chiral compounds generally crystallize into three forms: racemic compounds, conglomerates and solid solutions. More than 95% of chiral compounds crystallize as racemic compounds, roughly 5% exist as conglomerates, and rarely (less than 1%) crystallize as solid solutions (Harfouche et al., 2019; Rekis, 2020). Only 25 structures of chiral solid solutions have been reported to date (Rekis et al., 2018). Despite their rare formation in chiral compounds, solid solutions appear to be prevalent in multicomponent crystals, in which the chiral discrimination or enantioselectivity may be altered by coformer selection (Scowen et al., 2020; Białońska & Ciunik, 2013). Few attempts employed this strategy to intentionally design structures that avoid enantioselectivity in the solid state (Friščić et al., 2006; Chen et al., 2010; Czapik et al., 2019; Diniz et al., 2019). However, the modulation role of the coformer on chiral discrimination or enantioselectivity in multicomponent crystals remains elusive.

Many efforts have been devoted to establishing the relationship between mixed crystals and molecular conformations (Brandel et al., 2013; Scowen et al., 2020). From a structural point of view, two types of solid solutions have been suggested in the literature (Chion et al., 1978). Type I chiral solid solution describes the case where two enantiomers are arbitrarily distributed in the crystal [type I and type II solid solutions suggested by Chion et al. (1978); see below Scheme 1(a)]. These structures appear to be disordered, with both enantiomers superimposed in asymmetric units; moreover, their occupancy corresponds to the composition of the enantiomers. In a type II chiral solid solution, the crystal structure of the racemic composition is completely ordered. Solid solutions are formed due to the substitution of minor enantiomers by excess enantiomers of essentially the same structure in the non-racemic component.

However, the molecular positions in some solid solutions (Rekis et al., 2018; Vogt et al., 2010; Heidi Lopez De Diego et al., 2011; Esteves De Castro et al., 2007) of racemic composition are somewhat enantioselective in the formation of racemic components, which are neither completely disordered like in type I, nor completely ordered like in type II. A revised classification criterion [type 1 and type 2 solid solutions; see Scheme 1(b)] was proposed by Rekis et al. (2018). The molecular structural features of type 1 solid solutions, e.g. thio­camphor (Vogt et al., 2010; Heidi Lopez De Diego et al., 2011) and pyrrolidone derivatives (Esteves De Castro et al., 2007), were further elucidated based on type I. There is a statistical mirror plane intersecting the molecule [Scheme 1(b)] which thus generates the opposite enantiomer within the same molecular site. The single enantiomeric crystal of such solid solutions has an asymmetric unit molecule number Z′ = 1, whereas the crystal structure with racemic components has an asymmetric unit molecule number Z′ = 0.5. However, in type 2 solid solutions (Esteves De Castro et al., 2007, Rekis et al.; 2018; Baert et al., 1978; Kroon et al., 1976; Rekis & d'Agostino et al., 2017; Rekis & Bērziņš et al., 2018), the number of molecules in the asymmetric unit of a single enantiomer crystal is often even, and molecular conformational adjustment allows a reasonable pseudo-inversion center between two or an even number of molecular conformations in the asymmetric unit. This enantiopure structure mimics a centrosymmetric one by adjusting the molecular conformations so a reasonable pseudo-centrosymmetry might be attained between RI and RII. When some amount of the opposite enantiomer S is introduced, it can adopt conformation I and occupy the former RII sites in the crystal structure. Thus, locally there is genuine centrosymmetry between RI and SI present.

DMY is the main flavanol compound isolated from a traditional Chinese medicine ampelopsis grossedentata, which shows hepatoprotective, antioxidative, anti-inflammatory and antihypertensive effects (Liu et al., 2019). DMY has two chiral centers and thus has four potential enantiomers (Lin et al., 2019). Note that Rac-DMY crystallizes as a racemic compound containing R,R-DMY and S,S-DMY in the asymmetric unit (Xu et al., 2007), nonetheless, homochiral R,R-DMY showed higher anti-inflammatory activity than Rac-DMY (Wang et al., 2016). In this work, we used DMY as a chiral model substance to examine the role of the molecular structure of the coformer on chiral discrimination in multicomponent crystals from the perspectives of crystal structure, thermodynamics and intermolecular interactions. Two cocrystal coformers, caffeine (CAF) and theophylline (THE), were selected with a subtle difference in molecular structure. The crystal structures of R,R-DMY–THE, Rac-DMY–THE, R,R-DMY–CAF and Rac-DMY–CAF cocrystal solvates are, to our knowledge, reported for the first time, revealing the two types of solid solutions constituting chiral cocrystals that display several orders of magnitude mixing performance of two enantiomers within the crystals. The distinct enantioselectivity difference in the two chiral cocrystal systems can be attributed to the hydrogen-bonding donor–acceptor capacity of the coformers.

2. Materials and methods

2.1. Materials

Racemic DMY (>99.9%, GC) and R,R-DMY (>99.9%, GC) were purchased from Hangzhou Lin Ran Biotech Co. Ltd. Aceto­nitrile (purity >99.9%, GC) was purchased from Concord Technology Co. Ltd. CAF and THE of purity >99.0% (GC) were purchased from Aladdin (Shanghai) Bio-Chem Technology Co. Ltd. All chemicals were used as received.

2.2. Preparation and characterization of cocrystals

A suspension of 0.1 mmol (32 mg) DMY with 0.1 mmol CAF (19.4 mg) or 0.1 mmol THE (18 mg) and 2 ml aceto­nitrile was prepared and stirred at 30°C for 24 h. The cocrystals obtained were filtered from the suspension, and the supernatant was slowly volatilized at room temperature to prepare single crystals of suitable size that were structurally resolved using single-crystal X-ray diffraction (SCXRD).

Powder X-ray diffraction (PXRD) was performed on a D/MAX 2500 diffractometer at 40 kV and 100 mA coupled with Cu Kα radiation (λ = 1.5406 Å). The samples were scanned over the 2θ range 4−40 ° at a speed of 8° min⁻¹.

Scanning electron microscopy (SEM) was used to observe the twin crystal structure of the Rac-DMY–THE samples. All samples were observed on a TESCAN MIRA LMS scanning electron microscope operated under a vacuum with an accelerating voltage of 15.00 kV.

2.3. Construction of the binary melt phase diagram

A series of known enantiomeric compositions of DMY powders were completely dissolved in aceto­nitrile with equimolar THE at 50°C. The clear solution was slowly cooled to 25°C and stirred for 8 h to prepare DMY–THE cocrystals with a uniform size distribution. The harvested crystals were characterized by PXRD to verify the cocrystal formation. The samples were dried at 50°C for 12 h and characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and hot-stage microscopy (HSM) to determine the melting properties.

DSC was performed on a Mettler Toledo DSC 1 STARe system under a nitro­gen atmosphere. Approximately 6 mg of sample was added to a standard DSC aluminium pan and heated at a rate of 10°C min⁻¹. The onset of the endotherm was chosen as the melting temperature for the construction of the binary phase diagram.

TGA experiments were conducted on a Mettler TGA/DSC 1 STARe System. Approximately 6.0 mg of the sample was heated from 30 to 200°C at 10 °C min⁻¹ under a nitro­gen flow (50 ml min⁻¹).

HSM studies were performed on an Olympus BX-51 microscope equipped with a DSC600 hot stage Linkam system.

2.4. Measurement of the ternary phase diagram

The ternary phase diagram of the DMY–THE cocrystal was constructed in aceto­nitrile at temperatures ranging from 25 to 45°C. Known proportions of racemic and R,R-DMY mixture as well as THE powders were added to a crystallizer with approximately 30 ml aceto­nitrile at a given temperature. The suspension was stirred at a speed of 300 rpm. The crystalline phase of solid samples was monitored by PXRD for 30 min to evaluate the status of the solid–liquid equilibrium at a given temperature. The equilibrium time on solubility measurements was determined by measuring the concentration and components of the extracted clear supernatant using chiral high-performance liquid chromatography (HPLC) every 24 h until the concentration no longer varied. The preliminary tests provide an equilibrium time of 120 h. The suspended solid samples were subjected to PXRD analysis for the determination of the crystalline phase. The saturated liquid phase was suitably diluted before concentration measurements using chiral HPLC. The measurement at each condition was repeated three times to ensure the reliability of experimental results. Finally, the ternary phase diagram was constructed from the determined masses of DMY, THE and the solvent.

Solubility and solution concentration were determined using chiral HPLC [column: Phenomenex Lux Amylose-1, 250 mm × 4.6 mm × 5 µm; eluent: methanol and water with 0.1% tri­fluoro­acetic acid (2:8 v/v); flow rate 0.4 ml min⁻¹; injection volume 10 µl; column temperature 25 °C; retention time 30 min]. The sampling of 0.1–0.2 ml solution was performed using a syringe and a syringe filter (0.22 µm pore size). The calibration curves of S,S-DMY, R,R-DMY and THE show a good linear fit with R² > 0.999 (Fig. S9).

2.5. Single-crystal X-ray diffraction

SCXRD data were collected on an Agilent Rigaku Super Nova diffractometer with a CCD detector system. Suitable crystals of appropriate dimensions were chosen and mounted on loops for data collection. Preliminary unit-cell parameters were obtained with three sets of twelve narrow frame scans. The CrysAlisPro data reduction package (Rigaku, 2019) was used for acquisition, indexing, integration, absorption correction and scaling of Bragg reflections. The final cell parameters were determined from all reflection data. A Gaussian face-indexed absorption correction was applied to the three datasets collected. CrysAlisPro was also used for the analysis of systematic absences and space group determination. Thereafter, the OLEX2 software (Dolomanov et al., 2009) was used to the solve crystal structure by direct methods (SHELXT; Sheldrick, 2015) and refined by full-matrix least-squares on F² for all data (SHELXL; Sheldrick, 2008; Parsons et al., 2013). The non-hydrogen atoms were refined anisotropically. All hydrogen atoms were located from electron-density difference maps and were positioned geometrically and refined using the riding model [U_iso(H) = 1.2U_eq or 1.5U_eq]. The occupation of parts attributed to the enantiomers in the crystal were refined freely. Mercury (version 3.10; Macrae et al., 2020) was used for structure analysis and visualization.

2.6. Selective dissolution experiments of the Rac-DMY–THE cocrystal

Rac-DMY–THE cocrystals grown from a racemic solution were selected and placed in a saturated solution of R,R-DMY–THE for selective dissolution experiments. When Rac-DMY–THE cocrystals crystallized as epitaxial conglomerates or inversion twins, the racemic cocrystals are expected to partially dissolve. A polarizing optical microscope (Zeiss Primotech) was used to monitor the dissolution of the Rac-DMY–THE cocrystals over time.

2.7. Hirshfeld surface and 2D fingerprint plots

The Hirshfeld surface (HS) and 2D fingerprint plots were generated using the Crystal Explorer software package (version 3.148; Spackman et al., 2021) with the experimental SCXRD data as input. The color pattern on the HS shows the areas involved in interactions. On the d_norm surfaces, the red, white and blue areas represent the atomic contacts shorter than, equal to and longer than the sum of their van der Waals radii, respectively.

3. Results and discussion

3.1. Characterization of racemic and enantiomorph cocrystals

Two chiral carbons exist in the molecular structure of DMY [Fig. 1(a)] which constitute two coplanar six-membered rings (highlighted in red) A and C, and another perpendicular plane of the six-membered ring B. The hydrogen atom at each chiral carbon position is located on the same side of the coplane of the A and C rings. The structural characteristics produce a total of four potential enantiomers in which S,S-DMY and R,R-DMY are the dominant enantiomers in solution and crystallize to be Rac-DMY dihydrate from aqueous solution (Wang et al., 2016).

Figure 1 Molecular structure of (a) DMY and the two selected coformers (b) CAF and THE. The two chiral carbons are highlighted in red stars with the two predominant enantiomers of DMY in solution (coplanar A and C six-membered rings are highlighted in light red).

The suspension crystallization of Rac-DMY or R,R-DMY with CAF powders in aceto­nitrile results in the formation of a new phase. As shown in Fig. 2(a), the PXRD pattern of Rac-DMY–CAF displays several characteristic peaks located at 6.5, 7.4, 7.8, 12.3, 13.0 and 13.7°, differing from that of DMY or CAF crystals. Further, the experimental PXRD pattern matches well with the calculated one derived from the solved crystal structure (Fig. S1 in supporting information). These results corroborate the formation of the Rac-DMY–CAF cocrystal. Besides, the characteristic peaks of the R,R-DMY–CAF phase are identical to those of Rac-DMY–CAF cocrystals, indicating the formation of either a conglomerate of enantiomorph cocrystals or a chiral solid solution.

Figure 2 (a) PXRD patterns of Rac-DMY–CAF and R,R-DMY–CAF in comparison with Rac-DMY, R,R-DMY and CAF. (b) PXRD patterns of Rac-DMY–THE and R,R-DMY–THE in comparison with Rac-DMY, R,R-DMY and THE.

In contrast to CAF, the structure of THE coformer only lacks a methyl group on the five-membered ring, as shown in Fig. 1(b). This structural nuance was previously used to probe the chiral discrimination in cocrystal formation (Friščić et al., 2006). Here, we observed that R,R-DMY–THE and Rac-DMY–THE exhibit identical PXRD patterns that are different from the DMY or THE samples [Fig. 2(b)], suggesting the formation of a new crystalline phase. PXRD patterns of these samples are identical to the calculated ones simulated from the solved crystal structure (Fig. S2), corroborating the formation of R,R-DMY–THE and Rac-DMY–THE cocrystals.

3.2. Crystal structure analysis

3.2.1. Rac-DMY–CAF and R,R-DMY–CAF cocrystals

Further crystallographic structure determinations of Rac-DMY–CAF and R,R-DMY–CAF cocrystals were performed to differentiate conglomerates or solid solutions of enantiomorph cocrystals. Single crystals of sufficient size and mass were grown from aceto­nitrile solution to perform SCXRD analysis. Owing to the presence of compositional disorder of the racemic component (i.e. solid solution), Ga Kα radiation was employed to collect crystallographic data of Rac-DMY–CAF and R,R-DMY–CAF cocrystals. The high density of disorder/defects in the crystal structure may result from the wrong sites occupied by enantiomers in the structure, generating high R₁ values (Table 1).

Table 1
Crystallographic data of DMY–CAF crystal structures

	R,R-DMY–CAF	Rac-DMY–CAF
Radiation type	Ga Kα, λ = 1.34139 Å	Ga Kα, λ = 1.34139 Å
Temperature (K)	193	193
Crystal system	Monoclinic	Monoclinic
Space group	P21	P21/n
a (Å)	14.650	14.5994
b (Å)	7.124	7.1223
c (Å)	24.455	24.470
α (°)	90	90
β (°)	101.688	101.455
γ (°)	90	90
V (Å^−3)	2399.4	2493.7
ρcalc (g cm^−3)	1.476	1.48
Z, Z′, Z′′†	8, 2, 6	4, 1, 3
R1 [I > 2σ(I)]	0.0520	0.0904
S	1.041	1.074
Flack (μ)	0.1 (4)	–
Hooft (μ)	−0.0 (2)	–
Parson'q	−0.1 (3)	–
Disorder	–	0.57–0.43
CCDC No.	2192790	2178936

†Z′ is often defined as the number of formula units in the crystallographic unit cell divided by the number of independent general positions, but in this work Z′ = 1 represents only one set of THE, DMY and aceto­nitrile molecules in the asymmetric unit. The total number of chemical entities in the asymmetric unit has been referred to as Z″ by van Eijck & Kroon (2000).

The Rac-DMY–CAF cocrystal crystallizes in the monoclinic space group P2₁/n. The asymmetric unit is composed of equimolar amounts of DMY, CAF and aceto­nitrile, as illustrated in Fig. 3. The analyses of the anisotropic shift ellipsoid and the differential electron density map confirm the inclusion of a disordering coformer in the crystal structure and the proportion of disorder confirmed is 0.43–0.57. We thus conclude that Rac-DMY–CAF does not belong to the typical racemic compound crystallizing system.

Figure 3 Asymmetric units and unit cells of (a) Rac-DMY–CAF (P21/n, Z′ = 1, Z′′ = 3) and (b) R,R-DMY–CAF (P21, Z′ = 2, Z′′ = 6).

As shown in Fig. 4(a), two types of intermolecular hydrogen bonds are observed in the crystal structure: an O—H⋯O—H hydrogen bond is formed between hydroxyl groups of DMY molecules, and an O—H⋯O=C hydrogen bond is formed between the hydroxyl group of the DMY molecule and the carbonyl group of the CAF molecule. DMY and CAF form long zigzag chains that constitute alternating layers perpendicular to the b axis [Fig. 4(b)]. In each layer, the hydroxyl group on the DMY chiral C center passes through the O—H⋯O=C hydrogen bond (2.635, 1.90, θ: 144.8) with the carbonyl group of CAF (green arrow), and the hydroxyl group of DMY resorcinol connects with another carbonyl group of CAF via an O—H⋯O=C hydrogen bond (2.652, 2.29, θ: 106.0). In the perpendicular direction (orange arrow), the hydroxyl group of DMY resorcinol links to the adjacent catechol of DMY via an O—H⋯H—O hydrogen bond (2.769, 2.15, θ: 133.0). These layers were stacked by an O—H⋯N hydrogen bond (2.716,1.90, θ: 164.1) to form a 3D network with aceto­nitrile molecules included in the channel. Detailed data on hydrogen bonding interactions are shown in Table S2. The single crystal of the Rac-DMY–CAF cocrystal obtained through the slow volatilization of the solvent contains a disordering coformer with a proportion of 0.57. However, the crystal structure is largely (but not completely) an ordered arrangement in terms of enantiomer layout.

Figure 4 Structure analysis of the Rac-DMY–CAF cocrystal. (a) Hydrogen-bonding pattern showing the formation of a channel structure with aceto­nitrile included. (b) 3D molecular packing arrangements between DMY and CAF molecules along the b direction. (c) Hydrogen-bonding arrangement and (d) 3D molecular packing with an aceto­nitrile molecule included, viewed along the b direction.

In previous studies, it was suggested that the functional groups near the chiral center do not participate in hydrogen bonding interactions in the crystal structure of the solid solution forming system, to assure the replacement of the conformation of the enantiomer (Rekis & d'Agostino et al., 2017; Rekis et al., 2017). But in this case, we observed the direct formation of hydrogen bonding interactions of the hydroxyl group or ophthalmic triol group of DMY at the chiral carbon center with adjacent molecules. Interestingly, this packing arrangement will not be altered when enantiomer replacement occurs within the crystal structure, leading to the formation of Rac-DMY–CAF cocrystal solid solution.

The R,R-DMY–CAF cocrystal crystallizes in the monoclinic space group P2₁. As shown in Fig. 3(b), the asymmetric unit of R,R-DMY–CAF contains two sets of equimolar DMY, CAF and aceto­nitrile molecules. The anisotropic displacement parameters (ADPs) do not show any disorder in the R,R-DMY–CAF crystal structure. In general, the rigidity and stable stacking of molecules limit the possibility of molecular disorder encountered in solid solutions. The packing arrangments of the R,R-DMY–CAF and Rac-DMY–CAF cocrystals are almost identical, which explains their similar PXRD patterns [Fig. 2(a)].

The determination of the space group P2₁ in the crystal structure of R,R-DMY–CAF rather than P2₁/n is based on R₁ and R_int values. Electron statistical analysis suggests the presence of centrosymmetric space groups which can be explained by the pseudosymmetry of the crystal structure, illustrated in Fig. 5. The true centrosymmetry of the racemic composition can be achieved by the pairs SI–RI or SII–RII. For enantiomerically pure samples, two groups of molecules with homochirality can adjust the conformation to form a centrosymmetric pair, so that the formation of a quasi-centrosymmetric structure is also able to host the opposite enantiomer when the scalar composition phase was considered. The requirement for a solid solution is that the two (or another even number of) enantiomeric molecules in the asymmetric unit mirror are approximately mirror images of each other. The crystal structure of the DMY–CAF cocrystal meets all structural prerequisites to be the type 2 solid solution; moreover, the crystal structure of R,R-DMY–CAF is similar to that of Rac-DMY–CAF (see Fig. 3). The structural origin of such type of solid solution formation could be presumably due to non-racemic mixtures forming quasi-centrosymmetric structures, in which the number of missing enantiomers is compensated by the adoption of enriched enantiomers in a conformation similar to that of the minority enantiomer. This phenomenon can be referred to as shape mimicry (Fayzullin et al., 2017). Thus, the enantiomerically pure and racemic structures are isomeric, and continuous changes in their enantiomeric composition may form identical isomeric stacks. For conformationally flexible molecules, the stability of the crystal structure usually depends on a subtle compromise between the intermolecular interaction energy and the stacking efficiency. Overall, the DMY–CAF cocrystal system conforms to the crystallographically pseudo-centrosymmetric mixed-phase structure of typical type 2 solid solutions as classified by Rekis & Bērziņš (2018).

Figure 5 Graphical representation of the solid solution formation of the Rac-DMY–CAF cocrystal structure. (a) Enantiopure composition (note that the depicted inversion centers are not genuine, but only indicate a pseudosymmetry between coformers RI and RII). (b) Racemic composition as observed for most experimentally determined structures (statistical inversion centers). (c) Racemic composition as proposed by Chion et al. (1978) (genuine inversion centers).

3.2.2. Rac-DMY–THE and R,R-DMY–THE cocrystals

The SCXRD data of R,R-DMY–THE were collected using Mo Kα radiation, and the conformation of R,R-DMY was determined by chiral HPLC as its chiral conformation remains stable during the formation of cocrystals (Wang et al., 2016). The R,R-DMY–THE cocrystal crystallizes in an orthorhombic crystal system with the space group P2₁2₁2₁, and the crystallographic data are shown in Table 2. The asymmetric unit of the cocrystal consists of THE, R,R-DMY and aceto­nitrile in the molar ratio 1:1:1, and there is no disorder in the crystal structure.

Table 2
Crystallographic data of the DMY–THE cocrystal

	R,R-DMY–THE	Rac-DMY–THE-1	Rac-DMY–THE-2	Scalemic-DMY–THE-3
Diffraction source type	Rigaku Mo Kα radiation	Rigaku Cu Kα radiation	Rigaku Cu Kα radiation	Rigaku Cu Kα radiation
Temperature (K)	113	150	150	193
Crystal system	Orthorhombic	Orthorhombic	Orthorhombic	Orthorhombic
Space group	P212121	P212121	P212121	P212121
a (Å)	6.7292	6.7397	6.7429	6.7719
b (Å)	15.1840	15.2234	15.2146	15.2411
c (Å)	23.3897	23.4621	23.45083	23.471
α (°)	90	90	90	90
β (°)	90	90	90	90
γ (°)	90	90	90	90
V (Å^−3)	2389.87	2407.24	2405.85	2422.5
ρcalc (g cm^−3)	1.505	1.494	1.495	1.485
Z, Z′, Z′′†	4, 1, 3	4, 1, 3	4, 1, 3	4, 1, 3
R1 [I > 2σ(I)]	0.0669	0.0378	0.0393	0.0355
S	1.056	1.062	1.138	1.071
Flack (μ)	–	0.49 (0.04)	0.54 (0.03)	0.4 (0.3)
Disorder	–	0.68–0.32	0.74–0.26	0.79–0.21
CCDC No.	2178963	2178966	2179023	2178975

†Z′ is often defined as the number of formula units in the crystallographic unit cell divided by the number of independent general positions, but in this work Z′ = 1 represents only one set of THE, DMY and aceto­nitrile molecules in the asymmetric unit. The total number of chemical entities in the asymmetric unit has been referred to as Z″ by Van Eijck & Kroon (2000).

In the crystal structure, R,R-DMY interacts with two THE molecules by forming O—H⋯N and O—H⋯O hydrogen bonds, where one THE molecule interacts with R,R-DMY via O—H⋯N (2.764, 1.95, θ: 162.7), and the other THE also forms hydrogen bonds with the second R,R-DMY via O—H⋯O (2.720, 2.00, θ: 142.6) and N—H⋯O (2.738, 1.97, θ: 145.3), forming channels in the crystal structure to accommodate the aceto­nitrile guest molecule [Fig. 6(a)]. The adjacent R,R-DMY molecules interact with each other by forming O—H⋯O hydrogen bonds (2.7203, 1.9, θ: 156.1; 2.834, 2.27, θ: 125.1) between pyrogallol rings along the a direction and between the pyrogallol ring (B ring) and resorcinol ring (A ring) along the c direction [Fig. 6(b)], which results in a 3D host network [Fig. 6(c)]. The aceto­nitrile guest molecule is included within the host network through weak C—H⋯N hydrogen bonding interactions. Detailed hydrogen bonding interaction data are shown in Table S3. Unlike the structure of the R,R-DMY–CAF co-crystal, the asymmetric unit of the R,R-DMY–THE co-crystal has only one set of THE, R,R-DMY and aceto­nitrile molecules and does not form another set of conformational molecules to mimic the conformations of THE, S,S-DMY and aceto­nitrile in the racemic structure. Therefore, it does not conform to the typical crystallographic pseudo-centrosymmetric mixed-phase structural features of type 2 solid solutions.

Figure 6 Structure analysis of the R,R-DMY–THE cocrystal. (a) Hydrogen-bonding pattern showing the formation of the channel structure with aceto­nitrile included. (b) 3D molecular packing arrangement between pyrogallol–pyrogallol along the a direction and hydrogen bonding arrangement between resorcinol–pyrogallol along the c direction; (c) 3D molecular packing with an aceto­nitrile molecule included, viewed along the a direction.

Single crystals of the Rac-DMY–THE cocrystal were obtained by slow volatilization from a 1:1 solution of the racemic composition of DMY and THE in aceto­nitrile. Single crystals of suitable size and relatively good quality were selected, and crystallographic data were collected using a Cu target to receive information on reliable chiral conformations. Single-crystal structure determination shows that both enantiomers crystallized in the orthorhombic Sohncke space group P2₁2₁2₁. The asymmetric units contain equimolar amounts of THE, DMY and aceto­nitrile (Fig. 7). Crystal packing analysis reveals the identical molecular conformation and packing arrangements between Rac-DMY–THE-1 (or Rac-DMY–THE-2) (Table 2) and R,R-DMY–THE cocrystals. This likely indicates that the Rac-DMY–THE cocrystal is a conglomerate, but the analyses of anisotropic shift ellipsoids and differential electron density maps show the presence of disordered molecules. To demonstrate the lack of enantioselectivity in the solid state, the structure of the third scalar crystal (Scalemic-DMY–THE-3) was also determined, unveiling the disordered nature of scalemic crystals. The Flack values of Rac-DMY–THE-1 and Rac-DMY–THE-2 cocrystals are equal to 0.49(0.04) and 0.54(0.03), respectively, which, given plausible uncertainties, indicate that single crystals grown in saturated solutions of racemization are racemic twins, with domains of opposite absolute structure, statistically mosaic in the same crystal. The ratio of two absolute structured crystal domains can be determined by the Flack value. The disorder percentages in Rac-DMY–THE-1 and Rac-DMY–THE-2 cocrystals are 0.68 and 0.74, respectively. In each case (as long as the phases are assumed to be thermodynamically equilibrated), the exact degree of disorder should be related to the conformational entropy, which is determined by several isoenergetic local structure models. Disorder in crystal structures of other types of molecules has been explained and is thought to be controlled by Boltzmann statistics (Rekis, 2019). The degree of disorder and the conformational ratio or molecular positional enantioselectivity should be directly related to the energetic aspects of the intermolecular interactions (Zhang et al., 2017; Vogt et al., 2010b). The Flack value for Scalemic-DMY–THE-3 is 0.4 with an R₁ value of 3.55%, but the uncertainty of 0.3 is too large. The lattice parameters and molecular volumes of the cocrystals are shown in Table 2. There is no significant enantiomeric composition-dependent variation in the cell parameters, unit-cell volume and crystal density. The cell parameters (i.e. a, b and c) of the racemic samples are slightly increased compared with the enantiomerically pure crystals, which implies a slight expansion of the cell volume because of the disorder, although the experimental temperature may increase the cell parameters. We thus concluded that either the racemic or the enantiomerically pure sample of the DMY–THE cocrystal can form a uniformly stacked crystal structure without crystallization into a true conglomerate. Furthermore, the Rac-DMY–THE cocrystal does not belong to the type 1 solid solution, which requires the number of molecules in the asymmetric unit of the racemate crystal to be half that of a single enantiomer crystal (Rekis & Bērziņš, 2018).

Figure 7 Asymmetric units and unit cells of R,R-DMY–THE (P212121, Z′ = 1, Z′′ = 3), Rac-DMY–THE (P212121, Z′ = 1, Z′′ = 3) and Scalemic-DMY–THE (P212121, Z′ = 1, Z′′ = 3).

3.3. Thermodynamics of Rac-DMY–THE cocrystals

Racemic twins that crystallize in the Sohncke space group are a different type of conglomerate in which each crystal contains two enantiomers in separate structural domains, each containing only one of the two enantiomers. There are several reports of epitaxially grown conglomerates that can display racemic composition (Kaptein et al., 2008; Davey et al., 2014; Spix et al., 2014). In solid solution, although the two enantiomers are present in equal numbers, they are randomly distributed in the structure (irregular enantiomeric arrangement) and have no longevity. Solid solutions can crystallize in non-Sohncke or Sohncke space groups. Because of different scales of enantiomeric distribution, we explored the thermodynamic characteristics of racemic twinned crystals of the Rac-DMY–THE cocrystal in this section.

3.3.1. Pseudo-binary melt phase diagram of Rac-DMY–THE cocrystals

A series of DMY–THE cocrystals composed of different chiral DMY enantiomers were prepared for DSC analysis. As shown in Fig. 8(a), there is no weight loss observed in cocrystal samples until about 180°C. This is further confirmed by temperature-variant hot-stage microscopy presented in Figs. S3–S4 of the supporting information. The observed endothermic peak around 140–150°C can be attributed to the melting of cocrystal samples. The onset temperature is considered to be the melting point of the samples, and the measured data are given in Table S1 of the supporting information. We found that each cocrystal mixture, regardless of enantiomeric composition, has only one broad endothermic peak, indicative of chiral solid solutions. Further, the melting point decreases monotonically with the increase of S,S-DMY in the cocrystal with the maximum at 150.29°C for the 96.32%ee DMY–THE cocrystal mixtures and the minimum at 141.31°C for the 0.84%ee DMY–THE sample. These measured melting point data can be used to construct a Pseudo-binary melt phase diagram [Fig. 8(b)]. The Rac-DMY–THE cocrystal is a continuous solid solution exhibiting the lowest melting point at the racemic composition.

Figure 8 (a) TGA-DSC curves for the DMY–THE cocrystals at various ee. (b) Pseudo-binary melt phase diagram of DMY–THE cocrystals.

3.3.2. Pseudo-ternary solution phase diagram of Rac-DMY–THE cocrystals

Solution ternary phase diagrams are useful for distinguishing the crystalline form of a chiral compound and can provide the most basic and reliable data for chiral resolution (Srisanga & Horst, 2010). The solubility data of a series of DMY–THE cocrystal mixtures composed of different enantiomeric compositions in aceto­nitrile were measured at 25, 35 and 40 °C. Solid–liquid phase equilibrium experiments were performed, and the concentration of the clear supernatant was measured with an interval of 24 h by chiral HPLC to determine the solubility of the DMY–THE cocrystal mixtures of different enantiomeric compositions. The solid phase was subjected to PXRD analysis to rule out any phase transformation throughout the experiments. We found that the pseudo-ternary phase diagram reaches an equilibrium state after 120 h. Fig. 9 shows the established pseudo-ternary phase diagram, and the colored lines represent the solid–liquid equilibrium lines at different temperatures. The solubility of DMY–THE cocrystals increases with the rise in temperature and the decreases of R,R-DMY enantiomer in the solid phase. The solubility curves conform to the shape of a type of continuous solid solution, which is consistent with the results of the pseudo-binary melt phase diagram that displays a downward-concave shape. When the enantiomer system crystallized as a conglomerate or lamellar conglomerates (van Enckevort, 2010; Zlokazov & Pivnitsky, 2020), the solubility of the crystal mixtures composed of equimolar enantiomers should be twice the solubility of the single enantiomer crystal, conforming to the `Meyerhoffer' double solubility rule (Izumi & Blackmond, 2009). The colored hollow squares represent the eutectic point when the solubility of the racemic co-crystal is twice the solubility of an enantiomeric co-crystal. However, a closer look at the lowest point of the curve shows that the measured solubility of the DMY–THE cocrystals composed of equimolar enantiomers is much smaller than the expected value of the double solubility curve. An epitaxial lamellar conglomerate or multilayered conglomerate displaying single enantiomeric crystals crystallized in a chiral space group but in different chiral compositions, even with no enantiomeric excess, has been reported in the literature and is similar to our case. By combining the determined binary melt phase diagram and the ternary solution phase diagram, the chiral DMY–THE cocrystal system is considered to be a type of continuous solid solution.

Figure 9 Pseudo-ternary solution phase diagram of Rac-DMY–THE cocrystals in aceto­nitrile.

3.3.3. Selective dissolution of enantiomers

We further employed selective dissolution experiments to understand the mixing scale of enantiomeric cocrystals in a solid solution of DMY–THE, which is not suggested on the whole crystal scale nor on the molecular scale. The selective dissolution experiments were previously used in epitaxially grown conglomerate-forming systems to probe the distribution of enantiomeric domains in the crystal (Kaptein et al., 2008; van Eupen et al., 2008). When the Rac-DMY–THE cocrystal was placed in a saturated enantiomerically pure solution, we observed the enantioselective dissolution of crystal fragments under an optical microscope (Fig. 10), which suggests the presence of enantiomeric crystal domains. The Rac-DMY–THE cocrystal is composed of many R,R and S,S enantiomeric domains but displays near-racemic domains. Moreover, a small flake was peeled off the crystal of the racemate by the needle and measured by chiral HPLC which shows an enantiomeric excess value of about 79.8% (Fig. S7) and thus confirms the spatial heterogeneity of enantiomer domains in the solid solution of the Rac-DMY–THE cocrystal.

Figure 10 Time-resolved optical micrographs of the Rac-DMY–THE cocrystal in a saturated R,R-DMY–THE solution showing the selective dissolution of crystal fragments.

3.3.4. Observation of racemic twins

The careful examination of the crystal morphology of the Rac-DMY–THE cocrystal reveals the presence of a twinning boundary that separates the crystal into several domains (Fig. 11). These domains are ordered and stacked parallel to the identical crystallographic orientation. The facet indexing results clarify the mutually epitaxial twin boundary that appears on the {010} and {001} sets. The width of the twins is roughly 5–20 µm, which is comparable to the coherent spot size of the utilized single-crystal X-ray beam in this study (∼10 µm). The mixing behavior of enantiomer domains within the crystal is likely on the micrometre-scale, neither as a molecular disorder in the molecular-scale mixing nor as an even large macroscopic crystal-scale mixing resemble that in the epitaxial conglomerate system.

Figure 11 Twin boundary and indexed twin faces of the Rac-DMY–THE cocrystal.

The twin structure forms on the basal growing {010} and {001} surface, along the a axis, indicating a weaker interaction between the two enantiomers in the b and c directions. Fig. 6 suggests the rapid growth of DMY along the a axis is facilitated by strong hydrogen bonding interactions between o-phenyl­ene triols groups of the DMY molecule. The possible binding mode of the two enantiomeric molecules in Rac-DMY–THE cocrystals was illustrated in Fig. 11(c), with the twin boundaries highlighted. In both enantiomerically pure and racemic crystal structures of DMY–THE cocrystals, the THE and DMY molecules are linked by O—H⋯N and O—H⋯O hydrogen bonds along the b direction; in the c direction, the resorcinol groups R,R-DMY and S,S-DMY are joined together via an O—H⋯O hydrogen bond [dark-blue dashed line in Fig. 11(d)]. These hydrogen bonding interactions may be key factors in the early stages of nucleation and growth of enantiomorph cocrystals that lead to the formation of twin boundaries. However, note that the micrometre-scale mixing of enantiomer domains formed by epitaxial crystallization on Rac-DMY–THE cocrystals impedes the use of conventional chiral resolution methods, e.g. preferential crystallization.

3.4. Effect of molecular structure on the formation of the cocrystal solid solution of enantiomers

Two types of solid solution were found in our study in which the DMY–CAF cocrystal forms a type 2 chiral solid solution with molecular-scale mixing, whereas the DMY–THE cocrystal displays an inversion twin with micrometre-scale enantiomer mixing. The distinct mixing performance displaying several orders of magnitude difference is achieved only by the slight modification of the CAF coformer structure with the deletion of one methyl group on the five-membered ring of CAF (i.e. THE). Fig. 12 shows visually the difference in typical hydrogen bonding interactions of DMY and the coformer in a single enantiomeric cocrystal by HS analysis and 2D fingerprint plots. The red circles highlight the difference in the primary hydrogen-bonding mode, with THE forming hydrogen bonds through the carbonyl oxygen on the six-membered ring, N—H on the five-membered ring and the hydroxyl group of DMY. The HS in Fig. 12(a) displays two strong interactions (red regions indicated by arrows), whereas CAF forms only one strong O—H⋯O=C hydrogen bond between the carbonyl oxygen on the six-membered ring and the hydroxyl group of DMY [red region indicated by the arrow in Fig. 12(b)]. Besides, the B ring of DMY and the methyl H of CAF also form C—H⋯π weak interactions (blue region indicated by the arrow). 2D fingerprint plots reveal contributions of 15.3, 7.5 and 24.8% for H⋯O, C⋯H and O⋯H contacts in DMY–THE cocrystals, respectively, and 15.9, 9.3 and 25.1% for H⋯O, C⋯H and O⋯H in DMY–CAF cocrystals, respectively. The formation of C—H⋯π weak interactions between the B ring of DMY and the methyl of CAF may not satisfy the requirement of a tightly packed structure, and the optimal balance of interactions is achieved by forming two conformations for energy minimization and by forming pseudo-inversion centers, which allow for the (partial) replacement of chiral enantiomers in a pseudo-inversion center, resulting in molecular-level mixing. In contrast, there is only one set of molecular conformations in the asymmetric unit for the Rac-DMY–THE or R,R-DMY–THE cocrystal solid solution system, and the composition of the racemates is achieved by mixing crystal domains of differing chirality.

Figure 12 Comparisons of intermolecular interactions of R,R-DMY–THE and R,R-DMY–CAF cocrystals with HS and 2D fingerprint plots based on the dnorm value and the percentage contributions to the HS.

4. Conclusions

In this work, we investigated the enantioselectivity of chiral cocrystals of DMY enantiomers with two non-chiral coformers, CAF and THE, in solid-state chemistry. Although the mono-component enantiomer crystals rarely form a solid solution, we reported the two types of solid solutions constituting chiral cocrystals that display several orders of magnitude mixing performance of two enantiomers within the crystals. Rac-DMY–CAF co-crystals form a type 2 solid solution with an enantiomer mixed at the molecular scale, in which the single enantiomer adjusts its conformation to form a pseudo-inversion center to mimic the true symmetry center in the racemic crystal, allowing the formation of a solid solution. In contrast, Rac-DMY–THE cocrystals develop a racemic twin that shows enantiomer domains on the micrometre scale distributed in the crystal with the presence of racemic twins. The distinct enantioselectivity difference in two chiral cocrystal systems was attributed to the hydrogen-bonding donor–acceptor capacity of coformers where CAF co-crystallized with R,R-DMY can form two sets of conformations that satisfy pseudo-centric symmetry and realize the molecular-scale mixing of enantiomers. The stability of the cocrystal structure may be a subtle compromise between molecular energy and stacking efficiency. The degree of enantiomer mixing of cocrystals could impact their resolution method. Our findings could provide guidance for the separation of chiral racemic compounds with the cocrystallization method and the design of solid solution crystalline materials.

Supporting information

Computing details

Data collection: CrysAlis PRO 1.171.39.45g (Rigaku OD, 2018) for Rac-DMY-THE-1; CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for RR-DMY-THE. Cell refinement: SAINT V8.40A (Bruker, 2019) for Rac-DMY-CAF; SAINT V8.40B (?, 2016) for RR-DYM-CAF, Scalemic-DMY-THE-3; CrysAlis PRO 1.171.39.45g (Rigaku OD, 2018) for Rac-DMY-THE-1; CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for RR-DMY-THE. Data reduction: SAINT V8.40A (Bruker, 2019) for Rac-DMY-CAF; SAINT V8.40B (?, 2016) for RR-DYM-CAF, Scalemic-DMY-THE-3; CrysAlis PRO 1.171.39.45g (Rigaku OD, 2018) for Rac-DMY-THE-1; CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for RR-DMY-THE. Program(s) used to solve structure: SHELXT 2018/2 (Sheldrick, 2018) for Rac-DMY-CAF, Rac-DMY-THE-1, Scalemic-DMY-THE-3; olex2.solve (Bourhis et al., 2015) for RR-DYM-CAF; ShelXT (Sheldrick, 2015) for RR-DMY-THE. Program(s) used to refine structure: SHELXL 2018/3 (Sheldrick, 2015) for Rac-DMY-CAF, Rac-DMY-THE-1, Rac-DMY-THE-2, Scalemic-DMY-THE-3, RR-DMY-THE; XL (Sheldrick, 2008) for RR-DYM-CAF. Molecular graphics: Olex2 1.5 (Dolomanov et al., 2009) for Rac-DMY-CAF, Rac-DMY-THE-1, Rac-DMY-THE-2, Scalemic-DMY-THE-3, RR-DMY-THE; Olex2 (Dolomanov et al., 2009) for RR-DYM-CAF. Software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009) for Rac-DMY-CAF, Rac-DMY-THE-1, Rac-DMY-THE-2, Scalemic-DMY-THE-3, RR-DMY-THE; Olex2 (Dolomanov et al., 2009) for RR-DYM-CAF.

(Rac-DMY-CAF)

Crystal data

C8H10N4O2·C15H12O8·C2H3N	F(000) = 1160
Mr = 555.50	Dx = 1.480 Mg m^−3
Monoclinic, P21/n	Ga Kα radiation, λ = 1.34139 Å
a = 14.5994 (15) Å	Cell parameters from 1236 reflections
b = 7.1223 (7) Å	θ = 6.0–52.4°
c = 24.470 (2) Å	µ = 0.63 mm^−1
β = 101.455 (5)°	T = 193 K
V = 2493.8 (4) Å^3	Block
Z = 4	0.12 × 0.1 × 0.1 mm

Data collection

Bruker APEX-II CCD diffractometer	Rint = 0.066
φ and ω scans	θmax = 60.4°, θmin = 2.8°
17964 measured reflections	h = −17→18
5407 independent reflections	k = −9→5
3425 reflections with I > 2σ(I)	l = −31→29

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.090	w = 1/[σ^2(Fo^2) + (0.0807P)^2 + 5.3321P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.257	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.32 e Å^−3
5407 reflections	Δρmin = −0.38 e Å^−3
390 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
15 restraints	Extinction coefficient: 0.0023 (4)

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	0.6803 (2)	0.1402 (5)	0.35181 (12)	0.0640 (9)
O2	0.5086 (2)	0.2489 (6)	0.48558 (14)	0.0707 (10)
N1	0.8533 (2)	0.2193 (6)	0.44361 (14)	0.0522 (9)
N2	0.8341 (3)	0.2985 (6)	0.53030 (14)	0.0590 (10)
N3	0.6649 (2)	0.2775 (6)	0.51171 (13)	0.0525 (9)
N4	0.5959 (2)	0.1918 (6)	0.41963 (14)	0.0525 (9)
C1	0.9004 (4)	0.1778 (9)	0.3979 (2)	0.0699 (15)
H1A	0.883293	0.051319	0.383707	0.105*
H1B	0.968205	0.184593	0.411293	0.105*
H1C	0.881472	0.269542	0.367947	0.105*
C2	0.8938 (3)	0.2688 (8)	0.49610 (18)	0.0604 (12)
H2	0.959496	0.281542	0.507880	0.072*
C3	0.7503 (3)	0.2648 (7)	0.49649 (17)	0.0507 (10)
C4	0.6570 (4)	0.3329 (8)	0.56867 (17)	0.0633 (13)
H4A	0.654154	0.220176	0.591238	0.095*
H4B	0.599983	0.407127	0.567133	0.095*
H4C	0.711482	0.408217	0.585467	0.095*
C5	0.5866 (3)	0.2411 (7)	0.47344 (18)	0.0553 (11)
C6	0.5099 (3)	0.1545 (9)	0.3787 (2)	0.0720 (15)
H6C	0.525290	0.088337	0.346586	0.108*
H6D	0.479015	0.273619	0.366335	0.108*
H6E	0.467941	0.076681	0.395836	0.108*
C7	0.6808 (3)	0.1799 (7)	0.40077 (17)	0.0534 (11)
C8	0.7584 (3)	0.2183 (6)	0.44376 (16)	0.0482 (10)
O3	0.3254 (2)	0.2200 (5)	0.47800 (12)	0.0628 (9)
H3	0.351441	0.312444	0.466120	0.094*
O4	0.09273 (19)	0.3191 (6)	0.58244 (13)	0.0607 (9)
H4	0.086828	0.332478	0.615667	0.091*
O5	0.1468 (2)	0.4155 (5)	0.68786 (12)	0.0604 (9)
O6	0.2873 (2)	0.4837 (6)	0.77755 (12)	0.0721 (11)
H6B	0.254250	0.420773	0.795308	0.108*	0.570 (16)
H6A	0.242780	0.410059	0.778742	0.108*	0.430 (16)
O7	0.5943 (3)	0.7871 (5)	0.85849 (13)	0.0668 (10)
H7	0.623014	0.773703	0.891585	0.100*
O8	0.6988 (2)	0.4807 (5)	0.89852 (12)	0.0641 (9)
H8	0.724219	0.376141	0.907145	0.096*
O9	0.6559 (3)	0.1394 (5)	0.85495 (15)	0.0746 (10)
H9	0.632193	0.037316	0.841958	0.112*
O10	0.41799 (19)	0.3633 (5)	0.66971 (11)	0.0542 (8)
C9	0.5264 (3)	0.2685 (9)	0.78661 (19)	0.0665 (14)
H9A	0.509127	0.148747	0.770733	0.080*
C10	0.6014 (3)	0.2850 (7)	0.83101 (17)	0.0561 (11)
C11	0.6253 (3)	0.4585 (7)	0.85446 (15)	0.0506 (11)
C12	0.5743 (3)	0.6134 (7)	0.83438 (16)	0.0533 (11)
C13	0.5001 (3)	0.5952 (9)	0.78922 (16)	0.0630 (14)
H13	0.465321	0.703197	0.774833	0.076*
C14	0.4769 (3)	0.4257 (9)	0.76556 (18)	0.0676 (15)
C15A	0.3951 (7)	0.452 (2)	0.7164 (4)	0.054 (3)	0.570 (16)
H15A	0.385741	0.589627	0.708497	0.065*	0.570 (16)
C15B	0.3901 (9)	0.352 (2)	0.7231 (4)	0.045 (3)	0.430 (16)
H15B	0.375325	0.219443	0.731756	0.054*	0.430 (16)
C16A	0.3074 (7)	0.481 (2)	0.7250 (4)	0.042 (3)	0.430 (16)
H16A	0.321419	0.610660	0.713498	0.050*	0.430 (16)
C16B	0.3083 (6)	0.372 (2)	0.7325 (3)	0.056 (3)	0.570 (16)
H16B	0.317567	0.237411	0.743653	0.067*	0.570 (16)
C17	0.2285 (3)	0.3946 (8)	0.68133 (17)	0.0574 (12)
C18	0.2529 (3)	0.3462 (7)	0.62908 (16)	0.0470 (10)
C19	0.3473 (3)	0.3357 (6)	0.62482 (15)	0.0468 (10)
C20	0.3737 (3)	0.2955 (7)	0.57492 (16)	0.0495 (10)
H20	0.437795	0.289637	0.572622	0.059*
C21	0.3040 (3)	0.2637 (7)	0.52817 (16)	0.0502 (10)
C22	0.2092 (3)	0.2685 (7)	0.53065 (17)	0.0531 (11)
H22	0.162555	0.242431	0.498554	0.064*
C23	0.1853 (3)	0.3115 (7)	0.58037 (17)	0.0493 (10)
N5	0.3296 (6)	0.0294 (16)	0.2909 (4)	0.180 (4)
C24	0.1856 (6)	0.0232 (15)	0.2120 (3)	0.131 (3)
H24A	0.198649	−0.052439	0.180959	0.197*
H24B	0.169288	0.151383	0.198995	0.197*
H24C	0.133295	−0.032311	0.225963	0.197*
C25	0.2668 (6)	0.0278 (16)	0.2559 (4)	0.132 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.072 (2)	0.081 (2)	0.0374 (15)	0.0031 (18)	0.0048 (14)	−0.0056 (15)
O2	0.0512 (18)	0.099 (3)	0.063 (2)	0.0028 (18)	0.0122 (16)	−0.0080 (19)
N1	0.049 (2)	0.069 (2)	0.0367 (17)	0.0001 (18)	0.0032 (14)	0.0035 (17)
N2	0.050 (2)	0.081 (3)	0.0412 (18)	−0.005 (2)	−0.0031 (16)	0.0087 (19)
N3	0.048 (2)	0.073 (3)	0.0341 (16)	0.0031 (18)	0.0025 (14)	−0.0005 (17)
N4	0.0469 (19)	0.069 (3)	0.0372 (17)	0.0049 (17)	−0.0018 (14)	0.0002 (17)
C1	0.061 (3)	0.098 (4)	0.052 (3)	0.001 (3)	0.016 (2)	−0.002 (3)
C2	0.052 (2)	0.076 (3)	0.047 (2)	0.000 (2)	−0.003 (2)	0.005 (2)
C3	0.049 (2)	0.061 (3)	0.038 (2)	0.003 (2)	−0.0003 (17)	0.0068 (19)
C4	0.067 (3)	0.085 (4)	0.037 (2)	0.002 (3)	0.008 (2)	−0.003 (2)
C5	0.055 (3)	0.064 (3)	0.044 (2)	0.004 (2)	0.0024 (19)	0.001 (2)
C6	0.057 (3)	0.098 (4)	0.053 (3)	0.000 (3)	−0.009 (2)	−0.005 (3)
C7	0.061 (3)	0.059 (3)	0.039 (2)	0.002 (2)	0.0046 (19)	0.0055 (19)
C8	0.047 (2)	0.057 (3)	0.039 (2)	0.0024 (19)	0.0051 (17)	0.0076 (18)
O3	0.0556 (19)	0.091 (3)	0.0382 (15)	−0.0069 (18)	0.0011 (13)	−0.0151 (16)
O4	0.0386 (15)	0.085 (2)	0.0538 (17)	−0.0048 (15)	−0.0015 (13)	−0.0058 (17)
O5	0.0461 (17)	0.084 (2)	0.0509 (17)	−0.0002 (16)	0.0083 (13)	0.0009 (16)
O6	0.0600 (19)	0.115 (3)	0.0413 (16)	−0.009 (2)	0.0107 (14)	−0.0039 (18)
O7	0.079 (2)	0.071 (2)	0.0414 (16)	0.0025 (18)	−0.0106 (15)	0.0036 (15)
O8	0.065 (2)	0.071 (2)	0.0432 (16)	0.0036 (17)	−0.0220 (14)	0.0008 (16)
O9	0.079 (2)	0.069 (2)	0.066 (2)	−0.001 (2)	−0.0099 (18)	−0.0016 (19)
O10	0.0402 (14)	0.087 (2)	0.0310 (13)	−0.0012 (15)	−0.0029 (11)	−0.0041 (14)
C9	0.057 (3)	0.090 (4)	0.050 (3)	−0.008 (3)	0.003 (2)	−0.020 (3)
C10	0.056 (3)	0.070 (3)	0.039 (2)	−0.003 (2)	0.0010 (18)	−0.004 (2)
C11	0.051 (2)	0.066 (3)	0.0301 (18)	0.001 (2)	−0.0031 (16)	0.0035 (18)
C12	0.055 (2)	0.068 (3)	0.0334 (19)	0.005 (2)	−0.0008 (18)	0.0028 (19)
C13	0.055 (3)	0.101 (4)	0.0285 (19)	0.014 (3)	−0.0021 (18)	0.002 (2)
C14	0.046 (2)	0.118 (5)	0.035 (2)	0.003 (3)	−0.0036 (18)	−0.017 (3)
C15A	0.047 (5)	0.075 (8)	0.036 (4)	−0.003 (6)	−0.001 (3)	−0.015 (5)
C15B	0.041 (6)	0.059 (8)	0.029 (5)	−0.002 (6)	−0.004 (4)	0.003 (5)
C16A	0.042 (5)	0.054 (8)	0.030 (5)	−0.004 (5)	0.010 (4)	−0.001 (5)
C16B	0.046 (5)	0.073 (8)	0.046 (5)	−0.003 (5)	0.001 (3)	0.004 (5)
C17	0.042 (2)	0.086 (4)	0.042 (2)	−0.003 (2)	0.0041 (18)	−0.002 (2)
C18	0.0372 (19)	0.062 (3)	0.0377 (19)	−0.0044 (19)	−0.0014 (16)	0.0030 (18)
C19	0.042 (2)	0.061 (3)	0.0329 (18)	−0.0012 (19)	−0.0026 (16)	0.0001 (18)
C20	0.041 (2)	0.067 (3)	0.0372 (19)	0.000 (2)	−0.0003 (16)	−0.0029 (19)
C21	0.051 (2)	0.061 (3)	0.0346 (19)	−0.002 (2)	−0.0019 (17)	−0.0030 (18)
C22	0.045 (2)	0.067 (3)	0.042 (2)	−0.006 (2)	−0.0048 (17)	−0.004 (2)
C23	0.040 (2)	0.057 (3)	0.046 (2)	−0.0034 (19)	−0.0024 (17)	0.0003 (19)
N5	0.115 (6)	0.244 (10)	0.163 (7)	0.007 (7)	−0.017 (5)	−0.075 (7)
C24	0.127 (6)	0.178 (9)	0.090 (5)	0.013 (6)	0.026 (5)	−0.011 (6)
C25	0.092 (5)	0.191 (9)	0.109 (6)	0.011 (6)	0.012 (4)	−0.045 (6)

Geometric parameters (Å, º)

O1—C7	1.229 (5)	O9—H9	0.8400
O2—C5	1.233 (5)	O9—C10	1.367 (6)
N1—C1	1.455 (6)	O10—C15A	1.404 (8)
N1—C2	1.350 (6)	O10—C15B	1.445 (10)
N1—C8	1.387 (5)	O10—C19	1.364 (4)
N2—C2	1.338 (6)	C9—H9A	0.9500
N2—C3	1.356 (5)	C9—C10	1.386 (6)
N3—C3	1.373 (6)	C9—C14	1.376 (8)
N3—C4	1.475 (5)	C10—C11	1.378 (7)
N3—C5	1.351 (5)	C11—C12	1.366 (6)
N4—C5	1.395 (5)	C12—C13	1.391 (6)
N4—C6	1.466 (5)	C13—H13	0.9500
N4—C7	1.409 (6)	C13—C14	1.353 (8)
C1—H1A	0.9800	C14—C15A	1.529 (12)
C1—H1B	0.9800	C14—C15B	1.563 (14)
C1—H1C	0.9800	C15A—H15A	1.0000
C2—H2	0.9500	C15A—C16B	1.512 (12)
C3—C8	1.360 (6)	C15B—H15B	1.0000
C4—H4A	0.9800	C15B—C16A	1.524 (13)
C4—H4B	0.9800	C16A—H16A	1.0000
C4—H4C	0.9800	C16A—C17	1.535 (10)
C6—H6C	0.9800	C16B—H16B	1.0000
C6—H6D	0.9800	C16B—C17	1.541 (9)
C6—H6E	0.9800	C17—C18	1.436 (6)
C7—C8	1.411 (6)	C18—C19	1.404 (6)
O3—H3	0.8400	C18—C23	1.410 (5)
O3—C21	1.362 (5)	C19—C20	1.381 (6)
O4—H4	0.8400	C20—H20	0.9500
O4—C23	1.363 (5)	C20—C21	1.390 (5)
O5—C17	1.243 (5)	C21—C22	1.399 (6)
O6—H6B	0.8400	C22—H22	0.9500
O6—H6A	0.8400	C22—C23	1.366 (6)
O6—C16A	1.376 (11)	N5—C25	1.125 (10)
O6—C16B	1.440 (12)	C24—H24A	0.9800
O7—H7	0.8400	C24—H24B	0.9800
O7—C12	1.377 (6)	C24—H24C	0.9800
O8—H8	0.8400	C24—C25	1.434 (11)
O8—C11	1.371 (5)
C2—N1—C1	126.9 (4)	C11—C12—C13	119.6 (5)
C2—N1—C8	104.3 (4)	C12—C13—H13	119.6
C8—N1—C1	128.8 (4)	C14—C13—C12	120.8 (5)
C2—N2—C3	102.2 (4)	C14—C13—H13	119.6
C3—N3—C4	121.3 (4)	C9—C14—C15A	131.7 (7)
C5—N3—C3	119.2 (4)	C9—C14—C15B	105.7 (7)
C5—N3—C4	119.5 (4)	C13—C14—C9	119.9 (4)
C5—N4—C6	117.3 (4)	C13—C14—C15A	108.4 (7)
C5—N4—C7	125.6 (4)	C13—C14—C15B	133.3 (7)
C7—N4—C6	117.1 (4)	O10—C15A—C14	108.0 (7)
N1—C1—H1A	109.5	O10—C15A—H15A	109.3
N1—C1—H1B	109.5	O10—C15A—C16B	112.9 (9)
N1—C1—H1C	109.5	C14—C15A—H15A	109.3
H1A—C1—H1B	109.5	C16B—C15A—C14	108.2 (9)
H1A—C1—H1C	109.5	C16B—C15A—H15A	109.3
H1B—C1—H1C	109.5	O10—C15B—C14	104.2 (8)
N1—C2—H2	122.6	O10—C15B—H15B	110.9
N2—C2—N1	114.8 (4)	O10—C15B—C16A	111.2 (9)
N2—C2—H2	122.6	C14—C15B—H15B	110.9
N2—C3—N3	125.5 (4)	C16A—C15B—C14	108.7 (10)
N2—C3—C8	112.6 (4)	C16A—C15B—H15B	110.9
C8—C3—N3	121.9 (4)	O6—C16A—C15B	110.8 (9)
N3—C4—H4A	109.5	O6—C16A—H16A	110.0
N3—C4—H4B	109.5	O6—C16A—C17	112.7 (8)
N3—C4—H4C	109.5	C15B—C16A—H16A	110.0
H4A—C4—H4B	109.5	C15B—C16A—C17	103.2 (9)
H4A—C4—H4C	109.5	C17—C16A—H16A	110.0
H4B—C4—H4C	109.5	O6—C16B—C15A	108.0 (9)
O2—C5—N3	121.2 (4)	O6—C16B—H16B	111.1
O2—C5—N4	120.4 (4)	O6—C16B—C17	108.9 (7)
N3—C5—N4	118.3 (4)	C15A—C16B—H16B	111.1
N4—C6—H6C	109.5	C15A—C16B—C17	106.7 (8)
N4—C6—H6D	109.5	C17—C16B—H16B	111.1
N4—C6—H6E	109.5	O5—C17—C16A	118.0 (5)
H6C—C6—H6D	109.5	O5—C17—C16B	119.9 (5)
H6C—C6—H6E	109.5	O5—C17—C18	123.9 (4)
H6D—C6—H6E	109.5	C18—C17—C16A	115.5 (5)
O1—C7—N4	119.8 (4)	C18—C17—C16B	114.7 (5)
O1—C7—C8	128.3 (4)	C19—C18—C17	120.0 (3)
N4—C7—C8	111.8 (4)	C19—C18—C23	117.4 (4)
N1—C8—C7	130.8 (4)	C23—C18—C17	122.6 (4)
C3—C8—N1	106.0 (4)	O10—C19—C18	121.9 (3)
C3—C8—C7	123.2 (4)	O10—C19—C20	116.3 (4)
C21—O3—H3	109.5	C20—C19—C18	121.8 (4)
C23—O4—H4	109.5	C19—C20—H20	120.8
C16A—O6—H6A	109.5	C19—C20—C21	118.3 (4)
C16B—O6—H6B	109.5	C21—C20—H20	120.8
C12—O7—H7	109.5	O3—C21—C20	121.2 (4)
C11—O8—H8	109.5	O3—C21—C22	116.8 (3)
C10—O9—H9	109.5	C20—C21—C22	121.9 (4)
C19—O10—C15A	117.2 (5)	C21—C22—H22	120.8
C19—O10—C15B	114.5 (6)	C23—C22—C21	118.3 (4)
C10—C9—H9A	120.1	C23—C22—H22	120.8
C14—C9—H9A	120.1	O4—C23—C18	119.6 (4)
C14—C9—C10	119.9 (5)	O4—C23—C22	118.2 (4)
O9—C10—C9	125.0 (5)	C22—C23—C18	122.2 (4)
O9—C10—C11	115.1 (4)	H24A—C24—H24B	109.5
C11—C10—C9	119.9 (5)	H24A—C24—H24C	109.5
O8—C11—C10	121.6 (4)	H24B—C24—H24C	109.5
C12—C11—O8	118.4 (4)	C25—C24—H24A	109.5
C12—C11—C10	119.9 (4)	C25—C24—H24B	109.5
O7—C12—C13	119.3 (4)	C25—C24—H24C	109.5
C11—C12—O7	121.1 (4)	N5—C25—C24	178.7 (13)
O1—C7—C8—N1	−1.2 (9)	C9—C14—C15A—C16B	72.9 (11)
O1—C7—C8—C3	178.6 (5)	C9—C14—C15B—O10	−95.9 (8)
N2—C3—C8—N1	0.9 (6)	C9—C14—C15B—C16A	145.5 (9)
N2—C3—C8—C7	−178.9 (4)	C10—C9—C14—C13	−1.8 (8)
N3—C3—C8—N1	179.9 (4)	C10—C9—C14—C15A	177.2 (6)
N3—C3—C8—C7	0.1 (7)	C10—C9—C14—C15B	−171.6 (6)
N4—C7—C8—N1	179.0 (5)	C10—C11—C12—O7	177.3 (4)
N4—C7—C8—C3	−1.3 (7)	C10—C11—C12—C13	−1.9 (7)
C1—N1—C2—N2	−179.7 (5)	C11—C12—C13—C14	1.1 (7)
C1—N1—C8—C3	179.4 (5)	C12—C13—C14—C9	0.7 (7)
C1—N1—C8—C7	−0.8 (8)	C12—C13—C14—C15A	−178.5 (5)
C2—N1—C8—C3	−0.8 (5)	C12—C13—C14—C15B	167.2 (7)
C2—N1—C8—C7	179.0 (5)	C13—C14—C15A—O10	129.6 (7)
C2—N2—C3—N3	−179.6 (5)	C13—C14—C15A—C16B	−108.0 (10)
C2—N2—C3—C8	−0.6 (6)	C13—C14—C15B—O10	96.3 (9)
C3—N2—C2—N1	0.1 (6)	C13—C14—C15B—C16A	−22.3 (14)
C3—N3—C5—O2	179.2 (5)	C14—C9—C10—O9	−179.4 (5)
C3—N3—C5—N4	0.0 (7)	C14—C9—C10—C11	1.0 (7)
C4—N3—C3—N2	0.5 (7)	C14—C15A—C16B—O6	65.3 (13)
C4—N3—C3—C8	−178.4 (5)	C14—C15A—C16B—C17	−177.8 (7)
C4—N3—C5—O2	−1.8 (7)	C14—C15B—C16A—O6	−59.8 (14)
C4—N3—C5—N4	179.0 (4)	C14—C15B—C16A—C17	179.3 (7)
C5—N3—C3—N2	179.5 (5)	C15A—O10—C19—C18	−17.1 (9)
C5—N3—C3—C8	0.6 (7)	C15A—O10—C19—C20	163.3 (7)
C5—N4—C7—O1	−177.9 (5)	C15A—C16B—C17—O5	−150.1 (9)
C5—N4—C7—C8	2.0 (7)	C15A—C16B—C17—C18	43.5 (12)
C6—N4—C5—O2	1.3 (7)	C15B—O10—C19—C18	16.3 (9)
C6—N4—C5—N3	−179.5 (5)	C15B—O10—C19—C20	−163.3 (7)
C6—N4—C7—O1	0.2 (7)	C15B—C16A—C17—O5	151.4 (8)
C6—N4—C7—C8	−179.9 (4)	C15B—C16A—C17—C18	−46.2 (12)
C7—N4—C5—O2	179.4 (5)	C16A—C17—C18—C19	15.2 (9)
C7—N4—C5—N3	−1.4 (7)	C16A—C17—C18—C23	−163.4 (7)
C8—N1—C2—N2	0.4 (6)	C16B—C17—C18—C19	−17.9 (8)
O3—C21—C22—C23	179.9 (4)	C16B—C17—C18—C23	163.5 (7)
O5—C17—C18—C19	176.4 (5)	C17—C18—C19—O10	2.5 (7)
O5—C17—C18—C23	−2.2 (8)	C17—C18—C19—C20	−177.9 (5)
O6—C16A—C17—O5	31.8 (12)	C17—C18—C23—O4	−1.7 (7)
O6—C16A—C17—C18	−165.8 (7)	C17—C18—C23—C22	179.0 (5)
O6—C16B—C17—O5	−33.8 (11)	C18—C19—C20—C21	−0.4 (7)
O6—C16B—C17—C18	159.8 (6)	C19—O10—C15A—C14	166.3 (6)
O7—C12—C13—C14	−178.1 (4)	C19—O10—C15A—C16B	46.8 (14)
O8—C11—C12—O7	−1.6 (7)	C19—O10—C15B—C14	−169.4 (5)
O8—C11—C12—C13	179.2 (4)	C19—O10—C15B—C16A	−52.6 (14)
O9—C10—C11—O8	0.1 (7)	C19—C18—C23—O4	179.6 (4)
O9—C10—C11—C12	−178.8 (4)	C19—C18—C23—C22	0.2 (7)
O10—C15A—C16B—O6	−175.2 (7)	C19—C20—C21—O3	−178.8 (4)
O10—C15A—C16B—C17	−58.4 (15)	C19—C20—C21—C22	−1.1 (7)
O10—C15B—C16A—O6	−173.9 (8)	C20—C21—C22—C23	2.1 (7)
O10—C15B—C16A—C17	65.2 (15)	C21—C22—C23—O4	179.0 (4)
O10—C19—C20—C21	179.2 (4)	C21—C22—C23—C18	−1.7 (7)
C9—C10—C11—O8	179.8 (4)	C23—C18—C19—O10	−178.7 (4)
C9—C10—C11—C12	0.9 (7)	C23—C18—C19—C20	0.8 (7)
C9—C14—C15A—O10	−49.5 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.84	2.29	2.652 (5)	106
O4—H4···O5	0.84	1.90	2.635 (4)	145
O6—H6B···O1^i	0.84	1.96	2.765 (5)	159
O7—H7···N2^ii	0.84	1.90	2.716 (5)	164
O8—H8···O3^iii	0.84	2.15	2.796 (4)	133
O9—H9···O7^iv	0.84	1.93	2.672 (5)	146

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

(RR-DYM-CAF)

Crystal data

C15H12O8·C8H10N4O2·C2H3N	F(000) = 1160
Mr = 555.50	Dx = 1.476 Mg m^−3
Monoclinic, P21	Ga Kα radiation, λ = 1.34139 Å
a = 14.650 (5) Å	Cell parameters from 5362 reflections
b = 7.124 (2) Å	θ = 3.6–60.3°
c = 24.455 (7) Å	µ = 0.63 mm^−1
β = 101.688 (11)°	T = 193 K
V = 2499.5 (13) Å^3	BLOCK
Z = 4

Data collection

Bruker APEX-II CCD diffractometer	6236 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.057
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1032 before and 0.0781 after correction. The Ratio of minimum to maximum transmission is 0.8921. The λ/2 correction factor is Not present.	θmax = 54.2°, θmin = 1.6°
Tmin = 0.670, Tmax = 0.751	h = −17→16
18510 measured reflections	k = −8→7
8489 independent reflections	l = −26→29

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.052	w = 1/[σ^2(Fo^2) + (0.0743P)^2 + 0.1168P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.147	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.28 e Å^−3
8489 reflections	Δρmin = −0.31 e Å^−3
744 parameters	Absolute structure: Flack x determined using 2073 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: −0.1 (3)
Primary atom site location: iterative

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
O5	0.8335 (2)	0.3533 (5)	0.08057 (12)	0.0350 (8)
O8	0.5899 (2)	0.6117 (5)	−0.10748 (16)	0.0458 (10)
H8	0.615450	0.715821	−0.098365	0.069*
O12	0.4604 (2)	0.7091 (6)	0.47237 (13)	0.0448 (9)
H12	0.501757	0.654953	0.458837	0.067*
O7	0.5509 (2)	0.2630 (6)	−0.14828 (14)	0.0459 (9)
H7	0.517841	0.360191	−0.153822	0.069*
O13	0.3321 (2)	0.5836 (5)	0.57989 (13)	0.0383 (9)
O11	0.6018 (2)	0.6454 (5)	0.56262 (14)	0.0447 (10)
O17	0.5686 (2)	0.5889 (6)	0.39880 (14)	0.0469 (10)
O15	0.0536 (2)	0.7185 (6)	0.35011 (14)	0.0476 (10)
H15A	0.028608	0.612537	0.343550	0.071*
O1	0.9242 (2)	0.5097 (6)	0.27172 (14)	0.0492 (11)
H1	0.866452	0.526545	0.267500	0.074*
O2	1.1568 (2)	0.4199 (6)	0.16821 (15)	0.0476 (10)
H2	1.162850	0.408322	0.134945	0.071*
O6	0.6600 (3)	−0.0341 (5)	−0.10708 (14)	0.0426 (9)
H6	0.634065	−0.022763	−0.140845	0.064*
O19	0.0739 (3)	0.3658 (6)	0.89823 (14)	0.0507 (10)
O16	0.1514 (3)	1.0355 (5)	0.38982 (16)	0.0517 (11)
O10	0.6570 (2)	0.5587 (6)	0.66852 (15)	0.0465 (10)
H10	0.663291	0.610615	0.638678	0.070*
O9	0.4252 (2)	0.4623 (6)	0.77273 (14)	0.0478 (10)
H9A	0.367405	0.472755	0.770363	0.072*
O3	1.1042 (2)	0.3160 (6)	0.06322 (14)	0.0439 (9)
O18	0.7397 (2)	0.4839 (7)	0.26487 (15)	0.0577 (12)
N2	0.5833 (3)	0.4609 (6)	0.23798 (17)	0.0372 (10)
N3	0.4149 (3)	0.4454 (7)	0.21927 (16)	0.0427 (11)
O14	0.1007 (3)	0.3876 (5)	0.39632 (18)	0.0513 (10)
H14	0.127586	0.286702	0.407819	0.077*
O20	0.2428 (2)	0.4801 (8)	0.76429 (16)	0.0629 (12)
N4	0.3958 (3)	0.5176 (7)	0.30573 (16)	0.0380 (11)
N1	0.6524 (3)	0.5421 (7)	0.33069 (16)	0.0375 (10)
O4	0.9660 (3)	0.2450 (9)	−0.02721 (14)	0.0672 (13)
H4	1.000384	0.336082	−0.031314	0.101*
N5	0.1573 (3)	0.4212 (7)	0.83030 (17)	0.0397 (11)
N8	−0.0993 (3)	0.4512 (7)	0.80742 (16)	0.0395 (11)
N6	0.0870 (3)	0.5126 (7)	0.73886 (17)	0.0389 (11)
N7	−0.0821 (3)	0.5354 (7)	0.72127 (15)	0.0415 (11)
C26	0.1735 (3)	0.8667 (7)	0.4145 (2)	0.0322 (11)
C11	0.7226 (3)	0.4961 (7)	−0.04098 (19)	0.0347 (12)
H11	0.738520	0.618535	−0.026778	0.042*
C27	0.1260 (4)	0.7062 (8)	0.3952 (2)	0.0350 (12)
C25	0.2455 (3)	0.8582 (8)	0.46099 (19)	0.0333 (11)
H25	0.276739	0.969948	0.475466	0.040*
C43	0.0729 (4)	0.4084 (8)	0.8495 (2)	0.0371 (12)
C00Y	0.4026 (3)	0.5617 (7)	0.62547 (19)	0.0326 (12)
C20	0.4969 (3)	0.5739 (7)	0.6211 (2)	0.0327 (11)
C12	0.6471 (3)	0.4709 (8)	−0.0833 (2)	0.0334 (11)
C41	0.0022 (3)	0.4997 (7)	0.75449 (19)	0.0334 (12)
C1	0.9455 (3)	0.4665 (8)	0.2222 (2)	0.0382 (12)
C6	0.9431 (3)	0.2550 (8)	0.02529 (17)	0.0362 (11)
H6A	0.926525	0.125214	0.035489	0.043*
C8	0.9026 (3)	0.3883 (7)	0.12584 (19)	0.0319 (11)
C4	0.9979 (3)	0.3791 (7)	0.12146 (19)	0.0313 (11)
C2	1.0399 (3)	0.4667 (8)	0.2193 (2)	0.0389 (13)
H2A	1.085949	0.495952	0.251498	0.047*
C42	−0.0053 (3)	0.4493 (8)	0.80690 (19)	0.0339 (12)
C9	0.8766 (3)	0.4287 (8)	0.17511 (19)	0.0348 (12)
H9	0.812582	0.430998	0.177271	0.042*
C5	1.0231 (3)	0.3215 (8)	0.0704 (2)	0.0368 (12)
C10	0.7761 (3)	0.3432 (8)	−0.01870 (19)	0.0347 (12)
C21	0.5214 (3)	0.6134 (8)	0.5682 (2)	0.0369 (12)
C19	0.5644 (3)	0.5504 (8)	0.6704 (2)	0.0364 (12)
C34	0.4905 (3)	0.5184 (8)	0.30626 (19)	0.0343 (12)
C3	1.0655 (3)	0.4246 (7)	0.1699 (2)	0.0344 (12)
C16	0.3767 (3)	0.5249 (8)	0.67511 (19)	0.0342 (12)
H16A	0.312760	0.518221	0.677281	0.041*
C24	0.2720 (3)	0.6878 (7)	0.48636 (19)	0.0324 (11)
C32	0.5912 (4)	0.4082 (10)	0.18121 (19)	0.0492 (15)
H32A	0.599338	0.521396	0.159944	0.074*
H32B	0.534501	0.342392	0.162863	0.074*
H32C	0.645166	0.325447	0.182860	0.074*
C23	0.3557 (3)	0.6884 (7)	0.53367 (17)	0.0341 (11)
H23	0.370132	0.821011	0.545869	0.041*
C28	0.1529 (3)	0.5351 (8)	0.4201 (2)	0.0348 (12)
C40	0.1659 (3)	0.4705 (9)	0.7772 (2)	0.0414 (13)
C17	0.4463 (3)	0.4977 (8)	0.72221 (19)	0.0369 (12)
C18	0.5401 (3)	0.5091 (8)	0.7200 (2)	0.0409 (13)
H18	0.586623	0.488341	0.752625	0.049*
C22	0.4415 (3)	0.6024 (8)	0.51770 (17)	0.0358 (11)
H22	0.429000	0.468652	0.506181	0.043*
C37	0.3550 (3)	0.4734 (9)	0.2533 (2)	0.0457 (14)
H37	0.289315	0.462773	0.241277	0.055*
C44	−0.1414 (3)	0.5037 (9)	0.7554 (2)	0.0445 (14)
H44	−0.207040	0.517055	0.743986	0.053*
C14	0.6794 (4)	0.1419 (7)	−0.0837 (2)	0.0337 (12)
C35	0.5676 (3)	0.5530 (8)	0.3494 (2)	0.0361 (12)
C13	0.6243 (3)	0.2934 (8)	−0.1054 (2)	0.0328 (12)
C31	0.6626 (3)	0.4958 (8)	0.2772 (2)	0.0399 (12)
C38	0.2432 (3)	0.3802 (10)	0.8716 (2)	0.0587 (17)
H38A	0.238333	0.434024	0.907762	0.088*
H38B	0.296718	0.435416	0.859089	0.088*
H38C	0.251520	0.244039	0.875311	0.088*
C7	0.8604 (3)	0.3784 (7)	0.02666 (17)	0.0346 (11)
H7A	0.879983	0.511970	0.023839	0.041*
C33	0.4983 (3)	0.4736 (8)	0.25259 (19)	0.0368 (12)
C15	0.7546 (3)	0.1659 (7)	−0.0404 (2)	0.0351 (12)
H15	0.791507	0.061106	−0.025493	0.042*
C29	0.2267 (3)	0.5245 (8)	0.46586 (19)	0.0369 (12)
H29	0.245606	0.406937	0.482754	0.044*
C36	0.3488 (4)	0.5555 (10)	0.3516 (2)	0.0547 (17)
H36A	0.356086	0.447539	0.376919	0.082*
H36B	0.282346	0.577476	0.336694	0.082*
H36C	0.376196	0.667035	0.371966	0.082*
C39	0.0942 (4)	0.5670 (10)	0.68230 (19)	0.0522 (16)
H39A	0.096517	0.454071	0.659726	0.078*
H39B	0.151070	0.640741	0.683699	0.078*
H39C	0.039809	0.642545	0.665537	0.078*
C45	−0.1466 (4)	0.4084 (10)	0.8529 (2)	0.0547 (17)
H45A	−0.144388	0.272784	0.859774	0.082*
H45B	−0.211741	0.449225	0.842697	0.082*
H45C	−0.115600	0.474310	0.886734	0.082*
C30	0.7384 (3)	0.5785 (10)	0.3721 (2)	0.0538 (16)
H30A	0.723719	0.652750	0.402911	0.081*
H30B	0.782399	0.648050	0.354396	0.081*
H30C	0.766484	0.458941	0.386529	0.081*
C47	0.5719 (5)	0.2657 (13)	1.0393 (3)	0.072 (2)
H47A	0.625469	0.241817	1.021867	0.108*
H47B	0.567211	0.165403	1.065970	0.108*
H47C	0.580276	0.386485	1.058847	0.108*
C49	0.9810 (5)	0.7109 (13)	0.4941 (4)	0.073 (2)
N10	0.9199 (6)	0.7109 (15)	0.4587 (4)	0.128 (3)
C46	0.4889 (6)	0.2708 (12)	0.9973 (4)	0.072 (2)
N9	0.4224 (6)	0.2715 (14)	0.9633 (3)	0.117 (3)
C48	1.0612 (5)	0.7147 (13)	0.5399 (3)	0.075 (2)
H48A	1.112452	0.781971	0.528269	0.112*
H48B	1.080800	0.585896	0.550408	0.112*
H48C	1.044620	0.778801	0.571978	0.112*
H16	0.122 (4)	1.028 (10)	0.353 (2)	0.08 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O5	0.0231 (15)	0.055 (2)	0.0250 (16)	−0.0025 (15)	−0.0003 (13)	−0.0042 (15)
O8	0.044 (2)	0.037 (2)	0.050 (2)	0.0076 (17)	−0.0071 (18)	0.0040 (18)
O12	0.038 (2)	0.062 (3)	0.0349 (18)	0.0059 (19)	0.0098 (15)	0.000 (2)
O7	0.042 (2)	0.047 (2)	0.039 (2)	0.0054 (19)	−0.0151 (16)	−0.0020 (18)
O13	0.0260 (16)	0.058 (2)	0.0277 (17)	0.0000 (16)	−0.0033 (13)	0.0053 (16)
O11	0.0268 (18)	0.060 (3)	0.047 (2)	−0.0020 (17)	0.0080 (16)	−0.0052 (19)
O17	0.048 (2)	0.061 (3)	0.030 (2)	0.000 (2)	0.0039 (16)	−0.0014 (19)
O15	0.052 (2)	0.044 (2)	0.0352 (19)	−0.005 (2)	−0.0184 (16)	0.0008 (19)
O1	0.036 (2)	0.075 (3)	0.034 (2)	0.000 (2)	−0.0003 (16)	−0.013 (2)
O2	0.0224 (17)	0.069 (3)	0.049 (2)	−0.0065 (18)	0.0019 (16)	−0.004 (2)
O6	0.050 (2)	0.039 (2)	0.0318 (18)	0.0023 (18)	−0.0072 (16)	0.0017 (17)
O19	0.056 (2)	0.064 (3)	0.031 (2)	−0.005 (2)	0.0039 (17)	0.0076 (19)
O16	0.069 (3)	0.037 (2)	0.038 (2)	−0.002 (2)	−0.0165 (19)	0.0016 (18)
O10	0.0206 (17)	0.071 (3)	0.044 (2)	−0.0009 (19)	−0.0044 (15)	0.006 (2)
O9	0.035 (2)	0.074 (3)	0.032 (2)	0.008 (2)	0.0001 (16)	0.014 (2)
O3	0.0254 (18)	0.058 (3)	0.047 (2)	0.0002 (17)	0.0062 (16)	0.0023 (19)
O18	0.033 (2)	0.090 (3)	0.050 (2)	−0.002 (2)	0.0092 (17)	−0.016 (2)
N2	0.034 (2)	0.048 (3)	0.030 (2)	0.003 (2)	0.0065 (19)	0.000 (2)
N3	0.034 (2)	0.056 (3)	0.034 (2)	−0.003 (2)	−0.0003 (19)	0.007 (2)
O14	0.050 (2)	0.040 (2)	0.055 (2)	−0.001 (2)	−0.0116 (19)	0.000 (2)
O20	0.035 (2)	0.094 (4)	0.061 (2)	−0.003 (2)	0.0115 (19)	0.007 (3)
N4	0.025 (2)	0.053 (3)	0.035 (2)	0.004 (2)	0.0031 (18)	0.003 (2)
N1	0.028 (2)	0.050 (3)	0.033 (2)	−0.001 (2)	0.0007 (17)	−0.002 (2)
O4	0.043 (2)	0.120 (4)	0.040 (2)	−0.007 (3)	0.0117 (18)	−0.003 (3)
N5	0.034 (2)	0.045 (3)	0.036 (2)	−0.004 (2)	−0.0013 (19)	0.005 (2)
N8	0.032 (2)	0.050 (3)	0.034 (2)	−0.001 (2)	0.0032 (19)	−0.002 (2)
N6	0.032 (2)	0.055 (3)	0.029 (2)	−0.003 (2)	0.0048 (18)	0.000 (2)
N7	0.036 (2)	0.054 (3)	0.030 (2)	0.001 (2)	−0.0048 (18)	−0.006 (2)
C26	0.032 (2)	0.034 (3)	0.027 (2)	0.001 (2)	−0.002 (2)	0.000 (2)
C11	0.033 (2)	0.037 (3)	0.033 (2)	−0.001 (2)	0.0036 (19)	−0.001 (2)
C27	0.035 (3)	0.040 (3)	0.026 (3)	0.005 (3)	−0.003 (2)	0.001 (2)
C25	0.037 (3)	0.037 (3)	0.024 (2)	−0.001 (2)	0.0020 (19)	0.000 (2)
C43	0.040 (3)	0.036 (3)	0.033 (3)	−0.003 (2)	0.002 (2)	−0.005 (2)
C00Y	0.023 (2)	0.038 (3)	0.032 (3)	0.003 (2)	−0.005 (2)	0.000 (2)
C20	0.025 (2)	0.038 (3)	0.033 (3)	0.001 (2)	0.0003 (19)	0.001 (2)
C12	0.029 (2)	0.039 (3)	0.030 (2)	0.003 (2)	0.000 (2)	0.004 (2)
C41	0.033 (3)	0.034 (3)	0.032 (3)	−0.001 (2)	0.004 (2)	−0.005 (2)
C1	0.034 (3)	0.046 (3)	0.032 (3)	−0.005 (3)	0.001 (2)	−0.003 (3)
C6	0.031 (2)	0.052 (3)	0.026 (2)	−0.002 (2)	0.0069 (18)	−0.002 (2)
C8	0.027 (2)	0.034 (3)	0.031 (3)	−0.004 (2)	−0.002 (2)	−0.001 (2)
C4	0.024 (2)	0.033 (3)	0.033 (3)	0.001 (2)	−0.0013 (19)	0.003 (2)
C2	0.030 (3)	0.044 (3)	0.038 (3)	−0.002 (2)	−0.003 (2)	−0.003 (3)
C42	0.034 (3)	0.035 (3)	0.031 (3)	0.001 (2)	0.002 (2)	−0.003 (2)
C9	0.025 (2)	0.043 (3)	0.034 (3)	−0.002 (2)	0.000 (2)	−0.003 (2)
C5	0.024 (2)	0.046 (3)	0.037 (3)	−0.001 (2)	−0.001 (2)	0.005 (2)
C10	0.028 (2)	0.046 (3)	0.029 (2)	−0.001 (2)	0.0041 (19)	−0.002 (2)
C21	0.027 (2)	0.045 (3)	0.037 (3)	0.004 (2)	0.003 (2)	−0.006 (2)
C19	0.025 (2)	0.042 (3)	0.039 (3)	0.003 (2)	−0.003 (2)	−0.005 (3)
C34	0.027 (2)	0.043 (3)	0.033 (3)	0.004 (2)	0.005 (2)	0.005 (2)
C3	0.023 (2)	0.036 (3)	0.041 (3)	−0.001 (2)	−0.002 (2)	0.001 (2)
C16	0.025 (2)	0.045 (3)	0.030 (3)	0.000 (2)	−0.002 (2)	0.004 (2)
C24	0.027 (2)	0.040 (3)	0.027 (2)	−0.005 (2)	−0.0027 (18)	−0.001 (2)
C32	0.049 (3)	0.067 (4)	0.032 (3)	−0.001 (3)	0.009 (2)	−0.007 (3)
C23	0.030 (2)	0.043 (3)	0.028 (2)	0.001 (2)	0.0023 (18)	−0.001 (2)
C28	0.030 (2)	0.038 (3)	0.033 (3)	−0.002 (2)	0.000 (2)	−0.002 (2)
C40	0.034 (3)	0.050 (3)	0.039 (3)	−0.003 (3)	0.004 (2)	−0.001 (3)
C17	0.036 (3)	0.041 (3)	0.030 (3)	0.002 (2)	−0.003 (2)	0.004 (2)
C18	0.029 (3)	0.052 (4)	0.036 (3)	0.007 (3)	−0.007 (2)	0.006 (3)
C22	0.029 (2)	0.045 (3)	0.033 (2)	0.006 (2)	0.0037 (18)	−0.002 (2)
C37	0.033 (3)	0.064 (4)	0.037 (3)	−0.003 (3)	−0.001 (2)	0.004 (3)
C44	0.032 (3)	0.057 (4)	0.042 (3)	0.002 (3)	0.000 (2)	−0.004 (3)
C14	0.043 (3)	0.033 (3)	0.024 (2)	−0.002 (2)	0.002 (2)	0.000 (2)
C35	0.035 (3)	0.037 (3)	0.036 (3)	0.006 (2)	0.007 (2)	0.004 (2)
C13	0.029 (3)	0.045 (3)	0.023 (2)	0.000 (2)	0.002 (2)	0.003 (2)
C31	0.035 (3)	0.046 (3)	0.037 (3)	0.002 (3)	0.002 (2)	0.001 (3)
C38	0.037 (3)	0.077 (5)	0.054 (4)	0.007 (3)	−0.010 (3)	0.009 (3)
C7	0.031 (2)	0.039 (3)	0.031 (2)	0.003 (2)	0.0016 (18)	0.004 (2)
C33	0.034 (3)	0.045 (3)	0.030 (3)	0.004 (2)	0.003 (2)	0.007 (3)
C15	0.027 (2)	0.044 (3)	0.032 (3)	0.006 (2)	−0.001 (2)	0.002 (2)
C29	0.032 (2)	0.041 (3)	0.035 (3)	0.006 (2)	0.000 (2)	0.006 (2)
C36	0.040 (3)	0.082 (5)	0.044 (3)	0.005 (3)	0.014 (3)	−0.002 (3)
C39	0.054 (3)	0.070 (4)	0.033 (3)	−0.004 (3)	0.011 (3)	0.004 (3)
C45	0.052 (4)	0.071 (5)	0.044 (3)	−0.010 (3)	0.016 (3)	−0.004 (3)
C30	0.032 (3)	0.075 (5)	0.048 (3)	0.002 (3)	−0.005 (2)	−0.008 (3)
C47	0.066 (4)	0.094 (6)	0.059 (5)	−0.006 (4)	0.022 (4)	−0.002 (4)
C49	0.063 (5)	0.081 (5)	0.073 (5)	−0.005 (4)	0.007 (4)	−0.013 (5)
N10	0.083 (5)	0.147 (8)	0.136 (7)	−0.005 (6)	−0.023 (5)	−0.048 (7)
C46	0.066 (4)	0.077 (5)	0.074 (4)	−0.007 (4)	0.018 (4)	0.019 (4)
N9	0.079 (5)	0.146 (8)	0.107 (6)	−0.017 (5)	−0.026 (4)	0.041 (6)
C48	0.067 (4)	0.103 (6)	0.054 (4)	0.017 (5)	0.009 (3)	−0.006 (5)

Geometric parameters (Å, º)

O5—C8	1.363 (5)	N7—C41	1.358 (6)
O5—C7	1.462 (5)	N7—C44	1.340 (6)
O8—C12	1.363 (6)	C26—C27	1.372 (7)
O12—C22	1.417 (5)	C26—C25	1.387 (6)
O7—C13	1.360 (6)	C11—C12	1.365 (6)
O13—C00Y	1.367 (5)	C11—C10	1.388 (7)
O13—C23	1.454 (5)	C27—C28	1.384 (7)
O11—C21	1.234 (5)	C25—C24	1.383 (7)
O17—C35	1.232 (5)	C43—C42	1.414 (6)
O15—C27	1.368 (5)	C00Y—C20	1.409 (6)
O1—C1	1.345 (6)	C00Y—C16	1.369 (6)
O2—C3	1.346 (5)	C20—C21	1.439 (6)
O6—C14	1.384 (6)	C20—C19	1.406 (6)
O19—C43	1.226 (6)	C12—C13	1.389 (7)
O16—C26	1.355 (6)	C41—C42	1.357 (6)
O10—C19	1.367 (5)	C1—C2	1.399 (6)
O9—C17	1.357 (6)	C1—C9	1.395 (6)
O3—C5	1.237 (5)	C6—C5	1.513 (6)
O18—C31	1.231 (5)	C6—C7	1.502 (6)
N2—C32	1.466 (6)	C8—C4	1.423 (6)
N2—C31	1.371 (6)	C8—C9	1.366 (6)
N2—C33	1.366 (6)	C4—C5	1.432 (6)
N3—C37	1.342 (6)	C4—C3	1.420 (6)
N3—C33	1.338 (6)	C2—C3	1.369 (7)
O14—C28	1.359 (6)	C10—C7	1.504 (6)
O20—C40	1.232 (5)	C10—C15	1.381 (7)
N4—C34	1.385 (6)	C21—C22	1.522 (6)
N4—C37	1.337 (6)	C19—C18	1.364 (7)
N4—C36	1.455 (6)	C34—C35	1.402 (6)
N1—C35	1.411 (6)	C34—C33	1.378 (6)
N1—C31	1.386 (6)	C16—C17	1.389 (6)
N1—C30	1.471 (6)	C24—C23	1.506 (6)
O4—C6	1.393 (5)	C24—C29	1.382 (7)
N5—C43	1.413 (6)	C23—C22	1.518 (6)
N5—C40	1.375 (6)	C28—C29	1.392 (6)
N5—C38	1.474 (6)	C17—C18	1.388 (6)
N8—C42	1.380 (6)	C14—C13	1.387 (7)
N8—C44	1.350 (6)	C14—C15	1.375 (7)
N8—C45	1.457 (6)	C47—C46	1.425 (11)
N6—C41	1.375 (6)	C49—N10	1.112 (10)
N6—C40	1.367 (6)	C49—C48	1.451 (9)
N6—C39	1.461 (6)	C46—N9	1.144 (10)
C8—O5—C7	114.7 (3)	O3—C5—C6	120.7 (4)
C00Y—O13—C23	115.6 (3)	O3—C5—C4	123.9 (5)
C31—N2—C32	119.4 (4)	C4—C5—C6	115.3 (4)
C33—N2—C32	121.1 (4)	C11—C10—C7	118.2 (5)
C33—N2—C31	119.5 (4)	C15—C10—C11	120.0 (4)
C33—N3—C37	103.4 (4)	C15—C10—C7	121.7 (5)
C34—N4—C36	128.4 (4)	O11—C21—C20	123.6 (5)
C37—N4—C34	105.3 (4)	O11—C21—C22	121.0 (4)
C37—N4—C36	126.3 (4)	C20—C21—C22	115.4 (4)
C35—N1—C30	117.1 (4)	O10—C19—C20	119.7 (4)
C31—N1—C35	126.1 (4)	C18—C19—O10	118.7 (4)
C31—N1—C30	116.8 (4)	C18—C19—C20	121.5 (4)
C43—N5—C38	116.3 (4)	N4—C34—C35	131.3 (5)
C40—N5—C43	125.8 (4)	C33—C34—N4	105.4 (4)
C40—N5—C38	117.9 (4)	C33—C34—C35	123.3 (4)
C42—N8—C45	129.4 (4)	O2—C3—C4	119.8 (4)
C44—N8—C42	105.1 (4)	O2—C3—C2	119.0 (4)
C44—N8—C45	125.5 (4)	C2—C3—C4	121.1 (4)
C41—N6—C39	121.6 (4)	C00Y—C16—C17	118.2 (4)
C40—N6—C41	118.8 (4)	C25—C24—C23	116.9 (4)
C40—N6—C39	119.7 (4)	C29—C24—C25	120.4 (4)
C44—N7—C41	102.8 (4)	C29—C24—C23	122.5 (5)
O16—C26—C27	121.8 (4)	O13—C23—C24	108.1 (4)
O16—C26—C25	118.5 (5)	O13—C23—C22	109.4 (4)
C27—C26—C25	119.7 (5)	C24—C23—C22	112.9 (4)
C12—C11—C10	120.1 (5)	O14—C28—C27	114.0 (4)
O15—C27—C26	118.7 (5)	O14—C28—C29	125.5 (5)
O15—C27—C28	121.1 (5)	C27—C28—C29	120.5 (5)
C26—C27—C28	120.2 (4)	O20—C40—N5	121.4 (5)
C24—C25—C26	120.3 (5)	O20—C40—N6	120.1 (5)
O19—C43—N5	120.0 (5)	N6—C40—N5	118.5 (4)
O19—C43—C42	128.0 (5)	O9—C17—C16	121.1 (4)
N5—C43—C42	112.0 (4)	O9—C17—C18	117.1 (4)
O13—C00Y—C20	121.5 (4)	C18—C17—C16	121.8 (5)
O13—C00Y—C16	116.4 (4)	C19—C18—C17	119.1 (4)
C16—C00Y—C20	122.1 (4)	O12—C22—C21	111.5 (4)
C00Y—C20—C21	120.4 (4)	O12—C22—C23	106.8 (4)
C19—C20—C00Y	117.2 (4)	C23—C22—C21	108.1 (4)
C19—C20—C21	122.3 (4)	N4—C37—N3	114.0 (4)
O8—C12—C11	124.4 (5)	N7—C44—N8	113.8 (4)
O8—C12—C13	115.1 (4)	O6—C14—C13	119.5 (4)
C11—C12—C13	120.6 (5)	C15—C14—O6	119.8 (5)
N7—C41—N6	125.8 (4)	C15—C14—C13	120.7 (5)
C42—C41—N6	122.1 (5)	O17—C35—N1	119.5 (4)
C42—C41—N7	112.1 (4)	O17—C35—C34	128.5 (5)
O1—C1—C2	117.2 (4)	C34—C35—N1	112.0 (4)
O1—C1—C9	121.8 (4)	O7—C13—C12	122.4 (4)
C9—C1—C2	121.0 (5)	O7—C13—C14	118.7 (5)
O4—C6—C5	113.1 (4)	C14—C13—C12	119.0 (4)
O4—C6—C7	113.3 (4)	O18—C31—N2	120.4 (5)
C7—C6—C5	108.0 (4)	O18—C31—N1	121.8 (4)
O5—C8—C4	120.6 (4)	N2—C31—N1	117.8 (4)
O5—C8—C9	117.4 (4)	O5—C7—C6	108.3 (4)
C9—C8—C4	122.0 (4)	O5—C7—C10	108.3 (3)
C8—C4—C5	120.5 (4)	C6—C7—C10	115.5 (4)
C3—C4—C8	117.1 (4)	N2—C33—C34	121.3 (5)
C3—C4—C5	122.3 (4)	N3—C33—N2	126.7 (5)
C3—C2—C1	119.7 (5)	N3—C33—C34	112.0 (4)
N8—C42—C43	131.0 (5)	C14—C15—C10	119.6 (5)
C41—C42—N8	106.2 (4)	C24—C29—C28	119.0 (5)
C41—C42—C43	122.9 (5)	N10—C49—C48	178.8 (12)
C8—C9—C1	119.0 (4)	N9—C46—C47	178.7 (12)

(Rac-DMY-THE-1)

Crystal data

C15H12O8·C7H8N4O2·C2H3N	Dx = 1.494 Mg m^−3
Mr = 541.47	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 60039 reflections
a = 6.73972 (5) Å	θ = 2.9–74.5°
b = 15.22336 (8) Å	µ = 1.01 mm^−1
c = 23.46214 (13) Å	T = 150 K
V = 2407.24 (2) Å^3	Block, colourless
Z = 4	0.25 × 0.1 × 0.05 mm
F(000) = 1128

Data collection

ROD, Synergy Custom system, HyPix diffractometer	4828 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	4783 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.035
ω scans	θmax = 74.8°, θmin = 3.5°
Absorption correction: multi-scan CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→7
Tmin = 0.398, Tmax = 1.000	k = −19→19
77924 measured reflections	l = −29→28

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 1.2074P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.21 e Å^−3
4828 reflections	Δρmin = −0.21 e Å^−3
387 parameters	Absolute structure: Flack x determined using 1978 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
0 restraints	Absolute structure parameter: 0.49 (4)

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	0.6951 (3)	0.54170 (10)	0.44934 (7)	0.0257 (4)
O2	0.6778 (3)	0.73497 (12)	0.57029 (8)	0.0332 (4)
O3	0.7167 (3)	0.61387 (12)	0.64956 (7)	0.0328 (4)
H3	0.709993	0.663699	0.636429	0.049*
O4	0.7585 (3)	0.32011 (11)	0.58983 (7)	0.0328 (4)
H4	0.769671	0.290154	0.560962	0.049*
O5	0.6908 (3)	−0.06711 (11)	0.51871 (7)	0.0305 (4)
O6	0.5746 (3)	0.68881 (14)	0.20198 (7)	0.0347 (4)
H6	0.671511	0.711978	0.187139	0.052*
O7	0.6612 (4)	0.78047 (12)	0.45871 (8)	0.0368 (5)
H7B	0.657828	0.810320	0.487789	0.055*	0.680 (12)
H7A	0.689504	0.815929	0.483731	0.055*	0.320 (12)
O8	0.2729 (3)	0.62854 (14)	0.26854 (8)	0.0399 (5)
H8	0.286391	0.608463	0.236342	0.060*
O9	0.7931 (4)	0.22784 (11)	0.49477 (8)	0.0386 (5)
O10	0.9402 (4)	0.72254 (16)	0.24616 (10)	0.0483 (6)
H10	1.056309	0.703934	0.257009	0.058*
N2	0.7065 (4)	−0.07805 (14)	0.38741 (9)	0.0282 (4)
H2A	0.693100	−0.132657	0.395981	0.034*
N1	0.7401 (4)	0.04337 (14)	0.33524 (9)	0.0305 (5)
N4	0.7364 (3)	0.08083 (14)	0.50593 (9)	0.0269 (4)
N3	0.7620 (3)	0.14656 (13)	0.41487 (9)	0.0278 (5)
C3	0.7093 (4)	0.51943 (16)	0.50549 (9)	0.0235 (5)
C4	0.7045 (4)	0.58355 (15)	0.54922 (9)	0.0234 (5)
C19	0.7409 (4)	0.06421 (16)	0.39164 (10)	0.0263 (5)
C20	0.7207 (4)	−0.00878 (16)	0.42498 (10)	0.0254 (5)
C21	0.7130 (4)	−0.00535 (16)	0.48545 (10)	0.0255 (5)
C5	0.7197 (4)	0.55478 (16)	0.60631 (10)	0.0249 (5)
C23	0.7654 (4)	0.15514 (16)	0.47275 (11)	0.0282 (5)
C6	0.7362 (4)	0.46686 (17)	0.61961 (10)	0.0272 (5)
H6A	0.743675	0.448511	0.657358	0.033*
C8	0.7414 (4)	0.40602 (16)	0.57511 (10)	0.0256 (5)
C9	0.7282 (4)	0.43121 (16)	0.51790 (10)	0.0253 (5)
H9	0.731997	0.389532	0.488942	0.030*
C15	0.4575 (5)	0.64463 (18)	0.29202 (11)	0.0321 (6)
C7	0.6790 (5)	0.67406 (17)	0.53508 (10)	0.0327 (6)
C18	0.7178 (4)	−0.04381 (17)	0.33502 (11)	0.0317 (6)
H18	0.710711	−0.077209	0.301894	0.038*
C13	0.7959 (5)	0.69146 (18)	0.28231 (12)	0.0364 (6)
C14	0.6102 (4)	0.67636 (17)	0.25849 (10)	0.0285 (5)
C22	0.7887 (5)	0.22492 (17)	0.37908 (11)	0.0376 (6)
H22A	0.927654	0.234719	0.372789	0.056*
H22B	0.732318	0.275024	0.397929	0.056*
H22C	0.723433	0.216189	0.343151	0.056*
C11	0.4889 (6)	0.63023 (18)	0.34993 (12)	0.0433 (8)
H11	0.385753	0.610290	0.372875	0.052*
C24	0.7399 (6)	0.0928 (2)	0.56814 (12)	0.0413 (7)
H24A	0.636 (6)	0.144 (3)	0.5778 (18)	0.062*
H24B	0.856 (7)	0.110 (3)	0.5815 (19)	0.062*
H24C	0.678 (6)	0.036 (3)	0.5849 (17)	0.062*
C10	0.6755 (6)	0.64585 (18)	0.37329 (11)	0.0478 (9)
C12	0.8285 (6)	0.67617 (18)	0.33989 (13)	0.0447 (8)
H12	0.952799	0.686368	0.355750	0.054*
C17	0.6202 (15)	0.4175 (3)	0.2956 (2)	0.091 (2)
C16	0.8307 (12)	0.4389 (3)	0.2931 (2)	0.100 (2)
H16A	0.855188	0.476781	0.261114	0.150*
H16B	0.906301	0.385854	0.288830	0.150*
H16C	0.869243	0.468134	0.327573	0.150*
N5	0.4562 (11)	0.3997 (3)	0.2959 (2)	0.104 (2)
C1	0.7383 (10)	0.6315 (2)	0.43470 (15)	0.0227 (12)	0.680 (12)
H1	0.880250	0.643529	0.439289	0.027*	0.680 (12)
C2	0.6171 (11)	0.6916 (3)	0.47244 (15)	0.0263 (12)	0.680 (12)
H2	0.475179	0.679982	0.467351	0.032*	0.680 (12)
C1A	0.6170 (19)	0.6307 (5)	0.4404 (4)	0.024 (2)	0.320 (12)
H1A	0.474309	0.635442	0.447716	0.029*	0.320 (12)
C1B	0.739 (2)	0.6964 (5)	0.4733 (3)	0.025 (3)	0.320 (12)
H1B	0.881698	0.691120	0.466406	0.030*	0.320 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0385 (9)	0.0214 (8)	0.0171 (7)	−0.0002 (7)	−0.0009 (7)	0.0001 (6)
O2	0.0517 (12)	0.0234 (9)	0.0244 (8)	0.0018 (8)	0.0036 (8)	−0.0036 (7)
O3	0.0510 (12)	0.0289 (9)	0.0185 (8)	0.0033 (9)	−0.0016 (8)	−0.0032 (7)
O4	0.0530 (12)	0.0223 (8)	0.0230 (8)	−0.0008 (9)	−0.0039 (9)	0.0040 (7)
O5	0.0406 (11)	0.0260 (9)	0.0248 (8)	−0.0002 (8)	0.0017 (8)	0.0019 (7)
O6	0.0451 (11)	0.0409 (11)	0.0180 (8)	0.0021 (9)	−0.0006 (8)	0.0021 (8)
O7	0.0653 (14)	0.0209 (9)	0.0244 (9)	−0.0014 (9)	−0.0032 (9)	0.0004 (7)
O8	0.0442 (12)	0.0437 (11)	0.0317 (10)	−0.0027 (10)	0.0054 (9)	−0.0072 (8)
O9	0.0585 (13)	0.0228 (9)	0.0345 (10)	0.0007 (9)	−0.0030 (10)	−0.0043 (8)
O10	0.0429 (12)	0.0522 (13)	0.0499 (13)	−0.0040 (10)	−0.0055 (10)	0.0088 (11)
N2	0.0365 (12)	0.0235 (10)	0.0247 (10)	−0.0002 (9)	−0.0021 (9)	−0.0001 (8)
N1	0.0378 (12)	0.0297 (10)	0.0240 (10)	−0.0021 (10)	−0.0041 (9)	0.0028 (8)
N4	0.0328 (11)	0.0246 (10)	0.0233 (10)	0.0025 (9)	0.0015 (9)	−0.0007 (8)
N3	0.0351 (12)	0.0221 (10)	0.0261 (10)	−0.0011 (9)	−0.0040 (9)	0.0028 (8)
C3	0.0261 (12)	0.0266 (11)	0.0178 (10)	−0.0012 (10)	0.0003 (9)	0.0006 (9)
C4	0.0271 (11)	0.0246 (11)	0.0186 (10)	−0.0002 (9)	0.0005 (10)	0.0008 (9)
C19	0.0274 (12)	0.0266 (11)	0.0249 (11)	0.0002 (10)	−0.0022 (10)	0.0015 (9)
C20	0.0277 (12)	0.0226 (11)	0.0260 (11)	0.0013 (10)	−0.0014 (10)	0.0003 (9)
C21	0.0254 (12)	0.0255 (11)	0.0257 (11)	0.0020 (10)	0.0001 (10)	−0.0002 (9)
C5	0.0264 (12)	0.0290 (12)	0.0193 (10)	0.0004 (10)	−0.0011 (9)	−0.0012 (9)
C23	0.0311 (13)	0.0245 (11)	0.0289 (12)	0.0027 (10)	−0.0018 (10)	−0.0011 (10)
C6	0.0321 (13)	0.0312 (12)	0.0183 (10)	0.0001 (10)	−0.0021 (9)	0.0026 (9)
C8	0.0290 (13)	0.0232 (11)	0.0247 (11)	−0.0009 (10)	−0.0021 (10)	0.0038 (9)
C9	0.0309 (13)	0.0245 (11)	0.0206 (10)	−0.0005 (10)	−0.0014 (9)	−0.0020 (9)
C15	0.0464 (16)	0.0270 (12)	0.0228 (12)	0.0015 (12)	0.0017 (11)	−0.0025 (10)
C7	0.0502 (16)	0.0271 (12)	0.0208 (11)	0.0002 (12)	0.0040 (11)	−0.0012 (10)
C18	0.0416 (15)	0.0296 (12)	0.0238 (11)	0.0003 (12)	−0.0024 (12)	−0.0002 (10)
C13	0.0510 (17)	0.0271 (12)	0.0313 (13)	0.0018 (13)	−0.0088 (13)	0.0012 (10)
C14	0.0442 (15)	0.0244 (12)	0.0170 (11)	0.0028 (11)	0.0001 (10)	0.0000 (9)
C22	0.0564 (18)	0.0249 (12)	0.0316 (13)	−0.0047 (13)	−0.0090 (13)	0.0066 (10)
C11	0.085 (2)	0.0232 (13)	0.0220 (13)	−0.0047 (14)	0.0109 (14)	−0.0005 (10)
C24	0.065 (2)	0.0329 (14)	0.0261 (13)	0.0009 (15)	0.0041 (14)	−0.0049 (11)
C10	0.101 (3)	0.0207 (12)	0.0216 (13)	0.0004 (16)	−0.0201 (16)	−0.0023 (10)
C12	0.074 (2)	0.0266 (13)	0.0336 (15)	−0.0034 (14)	−0.0236 (15)	0.0020 (11)
C17	0.191 (8)	0.039 (2)	0.044 (2)	0.018 (4)	−0.042 (4)	−0.0072 (18)
C16	0.185 (7)	0.052 (3)	0.063 (3)	0.019 (4)	−0.032 (4)	−0.005 (2)
N5	0.193 (6)	0.060 (3)	0.059 (3)	0.011 (4)	−0.038 (4)	−0.004 (2)
C1	0.029 (3)	0.0205 (17)	0.0183 (17)	−0.0010 (16)	−0.0022 (16)	0.0011 (12)
C2	0.034 (3)	0.024 (2)	0.0205 (18)	0.0008 (17)	0.0002 (17)	0.0023 (15)
C1A	0.023 (6)	0.020 (4)	0.029 (4)	0.004 (3)	−0.004 (4)	−0.002 (3)
C1B	0.037 (7)	0.017 (4)	0.022 (4)	0.004 (4)	−0.003 (4)	0.002 (3)

Geometric parameters (Å, º)

O1—C3	1.364 (3)	C20—C21	1.421 (3)
O1—C1	1.439 (4)	C5—C6	1.379 (3)
O1—C1A	1.468 (8)	C6—H6A	0.9300
O2—C7	1.242 (3)	C6—C8	1.396 (3)
O3—H3	0.8200	C8—C9	1.399 (3)
O3—C5	1.356 (3)	C9—H9	0.9300
O4—H4	0.8200	C15—C14	1.382 (4)
O4—C8	1.358 (3)	C15—C11	1.392 (4)
O5—C21	1.231 (3)	C7—C2	1.551 (5)
O6—H6	0.8200	C7—C1B	1.541 (9)
O6—C14	1.360 (3)	C18—H18	0.9300
O7—H7B	0.8200	C13—C14	1.390 (4)
O7—H7A	0.8200	C13—C12	1.388 (4)
O7—C2	1.423 (4)	C22—H22A	0.9600
O7—C1B	1.424 (8)	C22—H22B	0.9600
O8—H8	0.8200	C22—H22C	0.9600
O8—C15	1.382 (4)	C11—H11	0.9300
O9—C23	1.236 (3)	C11—C10	1.393 (5)
O10—H10	0.8704	C24—H24A	1.07 (4)
O10—C13	1.374 (4)	C24—H24B	0.88 (5)
N2—H2A	0.8600	C24—H24C	1.04 (4)
N2—C20	1.378 (3)	C10—C12	1.374 (5)
N2—C18	1.337 (3)	C10—C1	1.518 (4)
N1—C19	1.361 (3)	C10—C1A	1.639 (10)
N1—C18	1.336 (3)	C12—H12	0.9300
N4—C21	1.406 (3)	C17—C16	1.457 (11)
N4—C23	1.387 (3)	C17—N5	1.138 (10)
N4—C24	1.471 (3)	C16—H16A	0.9600
N3—C19	1.374 (3)	C16—H16B	0.9600
N3—C23	1.364 (3)	C16—H16C	0.9600
N3—C22	1.470 (3)	C1—H1	0.9800
C3—C4	1.416 (3)	C1—C2	1.513 (7)
C3—C9	1.380 (3)	C2—H2	0.9800
C4—C5	1.413 (3)	C1A—H1A	0.9800
C4—C7	1.428 (3)	C1A—C1B	1.508 (16)
C19—C20	1.366 (3)	C1B—H1B	0.9800
C3—O1—C1	116.9 (2)	O10—C13—C14	116.5 (2)
C3—O1—C1A	113.1 (4)	O10—C13—C12	123.1 (3)
C5—O3—H3	109.5	C12—C13—C14	120.4 (3)
C8—O4—H4	109.5	O6—C14—C15	118.2 (3)
C14—O6—H6	109.5	O6—C14—C13	121.8 (3)
C2—O7—H7B	109.5	C15—C14—C13	120.0 (2)
C1B—O7—H7A	109.5	N3—C22—H22A	109.5
C15—O8—H8	109.5	N3—C22—H22B	109.5
C13—O10—H10	110.1	N3—C22—H22C	109.5
C20—N2—H2A	126.7	H22A—C22—H22B	109.5
C18—N2—H2A	126.7	H22A—C22—H22C	109.5
C18—N2—C20	106.6 (2)	H22B—C22—H22C	109.5
C18—N1—C19	103.6 (2)	C15—C11—H11	120.2
C21—N4—C24	117.2 (2)	C15—C11—C10	119.6 (3)
C23—N4—C21	125.8 (2)	C10—C11—H11	120.2
C23—N4—C24	117.0 (2)	N4—C24—H24A	107 (2)
C19—N3—C22	121.8 (2)	N4—C24—H24B	114 (3)
C23—N3—C19	118.9 (2)	N4—C24—H24C	105 (2)
C23—N3—C22	119.3 (2)	H24A—C24—H24B	107 (4)
O1—C3—C4	121.8 (2)	H24A—C24—H24C	105 (3)
O1—C3—C9	116.9 (2)	H24B—C24—H24C	118 (4)
C9—C3—C4	121.3 (2)	C11—C10—C1	126.9 (4)
C3—C4—C7	120.0 (2)	C11—C10—C1A	97.8 (5)
C5—C4—C3	118.1 (2)	C12—C10—C11	120.7 (2)
C5—C4—C7	121.9 (2)	C12—C10—C1	112.4 (4)
N1—C19—N3	126.8 (2)	C12—C10—C1A	140.8 (5)
N1—C19—C20	111.5 (2)	C13—C12—H12	120.2
C20—C19—N3	121.7 (2)	C10—C12—C13	119.5 (3)
N2—C20—C21	131.6 (2)	C10—C12—H12	120.2
C19—C20—N2	105.3 (2)	N5—C17—C16	177.9 (7)
C19—C20—C21	123.1 (2)	C17—C16—H16A	109.5
O5—C21—N4	120.6 (2)	C17—C16—H16B	109.5
O5—C21—C20	127.5 (2)	C17—C16—H16C	109.5
N4—C21—C20	111.8 (2)	H16A—C16—H16B	109.5
O3—C5—C4	120.2 (2)	H16A—C16—H16C	109.5
O3—C5—C6	118.4 (2)	H16B—C16—H16C	109.5
C6—C5—C4	121.4 (2)	O1—C1—C10	107.9 (3)
O9—C23—N4	121.1 (2)	O1—C1—H1	110.4
O9—C23—N3	120.3 (2)	O1—C1—C2	109.0 (4)
N3—C23—N4	118.6 (2)	C10—C1—H1	110.4
C5—C6—H6A	120.8	C2—C1—C10	108.5 (4)
C5—C6—C8	118.5 (2)	C2—C1—H1	110.4
C8—C6—H6A	120.8	O7—C2—C7	108.8 (3)
O4—C8—C6	116.8 (2)	O7—C2—C1	109.3 (4)
O4—C8—C9	120.9 (2)	O7—C2—H2	110.3
C6—C8—C9	122.3 (2)	C7—C2—H2	110.3
C3—C9—C8	118.4 (2)	C1—C2—C7	107.8 (4)
C3—C9—H9	120.8	C1—C2—H2	110.3
C8—C9—H9	120.8	O1—C1A—C10	100.5 (6)
O8—C15—C11	119.8 (3)	O1—C1A—H1A	113.3
C14—C15—O8	120.3 (2)	O1—C1A—C1B	110.1 (8)
C14—C15—C11	119.8 (3)	C10—C1A—H1A	113.3
O2—C7—C4	124.5 (2)	C1B—C1A—C10	105.6 (8)
O2—C7—C2	120.0 (3)	C1B—C1A—H1A	113.3
O2—C7—C1B	117.5 (4)	O7—C1B—C7	109.2 (6)
C4—C7—C2	114.7 (2)	O7—C1B—C1A	105.8 (9)
C4—C7—C1B	113.6 (3)	O7—C1B—H1B	113.3
N2—C18—H18	123.5	C7—C1B—H1B	113.3
N1—C18—N2	113.0 (2)	C1A—C1B—C7	101.2 (9)
N1—C18—H18	123.5	C1A—C1B—H1B	113.3
O1—C3—C4—C5	179.9 (2)	C5—C6—C8—O4	179.7 (2)
O1—C3—C4—C7	1.7 (4)	C5—C6—C8—C9	−0.7 (4)
O1—C3—C9—C8	−179.5 (2)	C23—N4—C21—O5	179.0 (3)
O1—C1—C2—O7	179.2 (3)	C23—N4—C21—C20	−0.5 (4)
O1—C1—C2—C7	61.2 (6)	C23—N3—C19—N1	−178.0 (3)
O1—C1A—C1B—O7	175.9 (6)	C23—N3—C19—C20	0.9 (4)
O1—C1A—C1B—C7	−70.3 (11)	C6—C8—C9—C3	0.0 (4)
O2—C7—C2—O7	28.6 (6)	C9—C3—C4—C5	0.0 (4)
O2—C7—C2—C1	147.0 (4)	C9—C3—C4—C7	−178.2 (3)
O2—C7—C1B—O7	−37.5 (11)	C15—C11—C10—C12	0.7 (4)
O2—C7—C1B—C1A	−148.7 (6)	C15—C11—C10—C1	−178.1 (3)
O3—C5—C6—C8	−179.3 (2)	C15—C11—C10—C1A	173.3 (4)
O4—C8—C9—C3	179.5 (2)	C7—C4—C5—O3	−2.2 (4)
O8—C15—C14—O6	−1.7 (4)	C7—C4—C5—C6	177.3 (3)
O8—C15—C14—C13	−179.3 (2)	C18—N2—C20—C19	−0.3 (3)
O8—C15—C11—C10	179.5 (2)	C18—N2—C20—C21	178.2 (3)
O10—C13—C14—O6	2.1 (4)	C18—N1—C19—N3	179.4 (3)
O10—C13—C14—C15	179.7 (2)	C18—N1—C19—C20	0.4 (3)
O10—C13—C12—C10	179.3 (3)	C14—C15—C11—C10	−1.6 (4)
N2—C20—C21—O5	0.0 (5)	C14—C13—C12—C10	0.1 (4)
N2—C20—C21—N4	179.4 (3)	C22—N3—C19—N1	−0.4 (4)
N1—C19—C20—N2	−0.1 (3)	C22—N3—C19—C20	178.5 (3)
N1—C19—C20—C21	−178.7 (2)	C22—N3—C23—O9	−0.9 (4)
N3—C19—C20—N2	−179.1 (2)	C22—N3—C23—N4	178.9 (2)
N3—C19—C20—C21	2.2 (4)	C11—C15—C14—O6	179.4 (2)
C3—O1—C1—C10	−169.2 (3)	C11—C15—C14—C13	1.8 (4)
C3—O1—C1—C2	−51.5 (6)	C11—C10—C12—C13	0.1 (4)
C3—O1—C1A—C10	165.3 (4)	C11—C10—C1—O1	55.1 (5)
C3—O1—C1A—C1B	54.3 (11)	C11—C10—C1—C2	−62.9 (5)
C3—C4—C5—O3	179.7 (2)	C11—C10—C1A—O1	101.7 (6)
C3—C4—C5—C6	−0.8 (4)	C11—C10—C1A—C1B	−143.8 (8)
C3—C4—C7—O2	−178.2 (3)	C24—N4—C21—O5	2.0 (4)
C3—C4—C7—C2	11.5 (5)	C24—N4—C21—C20	−177.4 (3)
C3—C4—C7—C1B	−22.4 (7)	C24—N4—C23—O9	0.2 (4)
C4—C3—C9—C8	0.4 (4)	C24—N4—C23—N3	−179.6 (3)
C4—C5—C6—C8	1.2 (4)	C10—C1—C2—O7	−63.5 (6)
C4—C7—C2—O7	−160.6 (3)	C10—C1—C2—C7	178.4 (3)
C4—C7—C2—C1	−42.2 (6)	C10—C1A—C1B—O7	68.3 (11)
C4—C7—C1B—O7	164.9 (6)	C10—C1A—C1B—C7	−177.9 (5)
C4—C7—C1B—C1A	53.6 (10)	C12—C13—C14—O6	−178.5 (3)
C19—N1—C18—N2	−0.6 (3)	C12—C13—C14—C15	−1.0 (4)
C19—N3—C23—O9	176.7 (3)	C12—C10—C1—O1	−123.8 (4)
C19—N3—C23—N4	−3.5 (4)	C12—C10—C1—C2	118.2 (5)
C19—C20—C21—O5	178.3 (3)	C12—C10—C1A—O1	−88.3 (7)
C19—C20—C21—N4	−2.3 (4)	C12—C10—C1A—C1B	26.1 (11)
C20—N2—C18—N1	0.6 (3)	C1—O1—C3—C4	19.3 (4)
C21—N4—C23—O9	−176.8 (3)	C1—O1—C3—C9	−160.9 (3)
C21—N4—C23—N3	3.4 (4)	C1—C10—C12—C13	179.1 (3)
C5—C4—C7—O2	3.7 (5)	C1A—O1—C3—C4	−17.1 (6)
C5—C4—C7—C2	−166.6 (4)	C1A—O1—C3—C9	162.7 (6)
C5—C4—C7—C1B	159.5 (6)	C1A—C10—C12—C13	−168.3 (5)

(Rac-DMY-THE-2)

Crystal data

C7H8N4O2·C15H12O8·C2H3N	Dx = 1.495 Mg m^−3
Mr = 541.47	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 64161 reflections
a = 6.74295 (4) Å	θ = 2.9–74.5°
b = 15.21461 (7) Å	µ = 1.01 mm^−1
c = 23.45083 (11) Å	T = 150 K
V = 2405.85 (2) Å^3	Block, colourless
Z = 4	0.25 × 0.1 × 0.05 mm
F(000) = 1128

Data collection

ROD,Synergy Custom system,HyPix diffractometer	Rint = 0.034
Absorption correction: multi-scan CrysAlisPro 1.171.39.45g(Rigaku Oxford Diffraction)	θmax = 74.7°, θmin = 3.5°
Tmin = 0.437, Tmax = 1.000	h = −7→8
71955 measured reflections	k = −18→19
4823 independent reflections	l = −28→28
4820 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 1.7078P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 0.21 e Å^−3
4823 reflections	Δρmin = −0.23 e Å^−3
379 parameters	Absolute structure: Flack x determined using 2017 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
0 restraints	Absolute structure parameter: 0.54 (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	Occ. (<1)
N001	0.2392 (4)	0.64644 (15)	0.08510 (10)	0.0254 (5)
O002	−0.1923 (3)	0.45854 (11)	−0.05075 (7)	0.0231 (4)
O003	−0.2570 (4)	0.68005 (12)	0.08994 (8)	0.0302 (5)
H003	−0.262368	0.711003	0.060317	0.045*
N004	0.2960 (4)	0.42180 (15)	0.11264 (10)	0.0266 (5)
H004	0.310333	0.365896	0.103940	0.032*
O005	−0.2145 (4)	0.38607 (13)	0.14946 (8)	0.0306 (5)
H005	−0.209104	0.334965	0.135995	0.046*
O006	−0.1736 (4)	0.26497 (13)	0.07011 (8)	0.0304 (5)
C007	0.2607 (4)	0.56415 (18)	0.10840 (11)	0.0238 (6)
O008	0.3114 (3)	0.43247 (13)	−0.01863 (8)	0.0281 (5)
O009	−0.1570 (4)	0.21978 (13)	−0.04155 (9)	0.0346 (5)
H00A	−0.155136	0.189126	−0.011766	0.052*	0.741 (13)
H009	−0.187218	0.182442	−0.016638	0.052*	0.259 (13)
C010	0.2889 (4)	0.49442 (18)	0.01456 (11)	0.0236 (5)
C011	0.2812 (4)	0.49094 (17)	0.07487 (12)	0.0235 (5)
O012	0.2249 (3)	0.37156 (15)	−0.23135 (9)	0.0353 (5)
H012	0.211248	0.392723	−0.264197	0.053*
C013	−0.2016 (4)	0.41654 (17)	0.04911 (11)	0.0218 (5)
C014	−0.2068 (4)	0.48074 (17)	0.00555 (11)	0.0212 (5)
N015	0.2616 (4)	0.54314 (15)	0.16481 (10)	0.0277 (5)
O016	0.2079 (4)	0.72766 (13)	0.00513 (9)	0.0363 (5)
N017	0.2651 (4)	0.58056 (15)	−0.00589 (9)	0.0247 (5)
C018	−0.2398 (4)	0.59404 (17)	0.07520 (11)	0.0231 (5)
C019	−0.2261 (4)	0.56901 (17)	0.01789 (11)	0.0231 (5)
H019	−0.230045	0.611628	−0.011701	0.028*
C020	−0.2342 (4)	0.53310 (18)	0.11969 (11)	0.0248 (6)
H020	−0.241737	0.551733	0.158291	0.030*
O021	−0.0756 (3)	0.31148 (15)	−0.29828 (8)	0.0306 (5)
H021	−0.175312	0.288433	−0.313703	0.046*
C022	−0.2173 (4)	0.44517 (18)	0.10620 (11)	0.0232 (5)
C023	0.2842 (5)	0.45605 (19)	0.16500 (12)	0.0292 (6)
H023	0.291276	0.421901	0.198856	0.035*
C024	−0.1741 (5)	0.32591 (19)	0.03493 (12)	0.0302 (7)
C025	0.2359 (4)	0.65481 (18)	0.02721 (12)	0.0257 (6)
C026	0.0088 (6)	0.3699 (2)	−0.15024 (13)	0.0362 (8)
H026	0.113885	0.390258	−0.126678	0.043*
C027	−0.2979 (5)	0.30877 (19)	−0.21811 (12)	0.0317 (7)
C028	0.0406 (5)	0.35553 (19)	−0.20795 (12)	0.0277 (6)
O029	−0.4419 (4)	0.27804 (18)	−0.25452 (11)	0.0429 (6)
H029	−0.553025	0.297323	−0.244252	0.064*
C030	−0.1787 (6)	0.3543 (2)	−0.12703 (13)	0.0396 (9)
C031	0.2610 (6)	0.5926 (2)	−0.06809 (12)	0.0382 (8)
H03A	0.353894	0.639312	−0.078820	0.057*
H03B	0.126701	0.608952	−0.080064	0.057*
H03C	0.299615	0.537662	−0.086826	0.057*
C2	−0.2357 (10)	0.3688 (2)	−0.06526 (15)	0.0214 (12)	0.741 (13)
H2	−0.380353	0.356866	−0.059893	0.026*	0.741 (13)
C033	−0.1123 (5)	0.32426 (18)	−0.24171 (11)	0.0245 (6)
C034	0.2129 (6)	0.72476 (19)	0.12084 (13)	0.0343 (7)
H03D	0.071080	0.736014	0.126238	0.051*
H03E	0.274463	0.775504	0.102141	0.051*
H03F	0.275771	0.715060	0.157989	0.051*
C035	−0.3318 (6)	0.3241 (2)	−0.16063 (14)	0.0378 (8)
H035	−0.459088	0.313869	−0.144609	0.045*
C0	−0.1152 (10)	0.3088 (3)	−0.02750 (16)	0.0249 (13)	0.741 (13)
H0	0.029326	0.320953	−0.032855	0.030*	0.741 (13)
C1	−0.1207 (16)	0.5827 (4)	−0.2042 (2)	0.088 (3)
N2	0.0423 (12)	0.6005 (4)	−0.2040 (2)	0.100 (2)
C3	−0.3311 (13)	0.5613 (4)	−0.2070 (2)	0.094 (2)
H3A	−0.355466	0.522696	−0.239740	0.142*
H3B	−0.408248	0.615448	−0.211359	0.142*
H3C	−0.371037	0.531261	−0.171872	0.142*
C4	−0.240 (3)	0.3033 (7)	−0.0264 (4)	0.022 (3)	0.259 (13)
H4	−0.385860	0.308340	−0.033180	0.027*	0.259 (13)
C5	−0.115 (3)	0.3690 (7)	−0.0598 (5)	0.022 (3)	0.259 (13)
H5	0.030698	0.363435	−0.052712	0.027*	0.259 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N001	0.0311 (13)	0.0209 (11)	0.0241 (11)	0.0001 (10)	−0.0032 (10)	−0.0022 (9)
O002	0.0335 (10)	0.0185 (9)	0.0172 (8)	0.0005 (8)	0.0005 (8)	−0.0006 (7)
O003	0.0472 (13)	0.0206 (9)	0.0228 (9)	−0.0012 (10)	0.0040 (10)	−0.0040 (7)
N004	0.0344 (13)	0.0209 (11)	0.0245 (11)	0.0004 (10)	−0.0024 (11)	0.0002 (9)
O005	0.0475 (13)	0.0258 (10)	0.0187 (9)	0.0031 (10)	0.0015 (9)	0.0032 (7)
O006	0.0458 (13)	0.0212 (10)	0.0241 (10)	0.0019 (9)	−0.0035 (9)	0.0037 (8)
C007	0.0239 (14)	0.0235 (12)	0.0241 (12)	0.0006 (11)	−0.0014 (11)	−0.0009 (10)
O008	0.0361 (12)	0.0239 (10)	0.0244 (9)	−0.0007 (9)	0.0009 (9)	−0.0022 (8)
O009	0.0616 (16)	0.0186 (9)	0.0235 (10)	0.0003 (10)	0.0025 (10)	−0.0004 (8)
C010	0.0216 (13)	0.0227 (13)	0.0264 (13)	−0.0014 (12)	−0.0009 (11)	0.0003 (10)
C011	0.0246 (13)	0.0199 (12)	0.0260 (13)	−0.0007 (11)	−0.0011 (11)	−0.0004 (10)
O012	0.0366 (12)	0.0396 (12)	0.0297 (10)	−0.0026 (10)	−0.0035 (10)	0.0066 (9)
C013	0.0246 (13)	0.0220 (12)	0.0189 (12)	0.0007 (11)	−0.0006 (11)	−0.0007 (10)
C014	0.0215 (13)	0.0234 (13)	0.0187 (12)	−0.0007 (11)	−0.0006 (11)	−0.0009 (10)
N015	0.0325 (13)	0.0261 (12)	0.0244 (11)	0.0014 (11)	−0.0041 (11)	−0.0024 (9)
O016	0.0552 (15)	0.0214 (10)	0.0324 (11)	−0.0018 (10)	−0.0026 (11)	0.0040 (9)
N017	0.0286 (13)	0.0226 (11)	0.0229 (11)	−0.0046 (10)	0.0009 (10)	0.0006 (9)
C018	0.0247 (14)	0.0212 (12)	0.0234 (12)	−0.0004 (11)	0.0024 (11)	−0.0038 (10)
C019	0.0271 (14)	0.0216 (12)	0.0208 (12)	−0.0005 (11)	0.0002 (11)	0.0011 (10)
C020	0.0280 (14)	0.0275 (13)	0.0191 (12)	−0.0001 (12)	0.0030 (11)	−0.0029 (10)
O021	0.0375 (12)	0.0368 (12)	0.0174 (9)	0.0016 (10)	0.0007 (8)	−0.0021 (8)
C022	0.0237 (14)	0.0261 (13)	0.0196 (12)	−0.0013 (11)	0.0006 (11)	0.0012 (10)
C023	0.0374 (17)	0.0269 (14)	0.0232 (13)	0.0000 (13)	−0.0016 (13)	0.0007 (11)
C024	0.0457 (18)	0.0248 (14)	0.0202 (13)	0.0000 (13)	−0.0039 (13)	0.0012 (11)
C025	0.0267 (15)	0.0229 (13)	0.0274 (13)	−0.0013 (11)	−0.0011 (12)	0.0022 (11)
C026	0.065 (2)	0.0223 (15)	0.0214 (14)	−0.0029 (15)	−0.0091 (15)	0.0003 (11)
C027	0.0428 (18)	0.0236 (13)	0.0286 (14)	0.0023 (14)	0.0072 (14)	−0.0009 (11)
C028	0.0394 (17)	0.0230 (13)	0.0209 (13)	0.0023 (13)	−0.0018 (13)	0.0036 (11)
O029	0.0359 (13)	0.0472 (14)	0.0457 (14)	−0.0031 (11)	0.0037 (11)	−0.0095 (12)
C030	0.077 (3)	0.0194 (13)	0.0221 (14)	0.0014 (16)	0.0170 (17)	0.0023 (11)
C031	0.058 (2)	0.0308 (15)	0.0255 (14)	−0.0017 (16)	0.0038 (15)	0.0040 (12)
C2	0.027 (3)	0.0185 (18)	0.0188 (18)	−0.0011 (17)	0.0028 (17)	−0.0011 (13)
C033	0.0367 (16)	0.0207 (13)	0.0161 (12)	0.0022 (12)	−0.0004 (11)	0.0007 (10)
C034	0.050 (2)	0.0229 (13)	0.0303 (15)	0.0037 (14)	−0.0081 (15)	−0.0058 (12)
C035	0.057 (2)	0.0244 (15)	0.0325 (16)	−0.0042 (14)	0.0176 (16)	−0.0014 (12)
C0	0.034 (4)	0.020 (2)	0.0209 (19)	0.0025 (18)	−0.0002 (17)	−0.0017 (16)
C1	0.186 (8)	0.034 (3)	0.044 (3)	0.016 (4)	0.043 (4)	0.007 (2)
N2	0.184 (7)	0.057 (3)	0.058 (3)	0.010 (4)	0.037 (4)	0.005 (2)
C3	0.175 (8)	0.048 (3)	0.060 (3)	0.014 (4)	0.031 (4)	0.004 (2)
C4	0.027 (9)	0.016 (5)	0.024 (5)	0.004 (5)	0.006 (5)	0.000 (4)
C5	0.019 (8)	0.017 (5)	0.031 (6)	0.001 (4)	0.010 (5)	0.002 (4)

Geometric parameters (Å, º)

N001—C007	1.374 (3)	C020—H020	0.9500
N001—C025	1.364 (4)	C020—C022	1.379 (4)
N001—C034	1.467 (3)	O021—H021	0.8400
O002—C014	1.366 (3)	O021—C033	1.364 (3)
O002—C2	1.437 (4)	C023—H023	0.9500
O002—C5	1.474 (11)	C024—C0	1.539 (5)
O003—H003	0.8400	C024—C4	1.545 (12)
O003—C018	1.358 (3)	C026—H026	0.9500
N004—H004	0.8800	C026—C028	1.388 (4)
N004—C011	1.379 (4)	C026—C030	1.397 (5)
N004—C023	1.336 (4)	C027—O029	1.375 (4)
O005—H005	0.8400	C027—C033	1.389 (4)
O005—C022	1.356 (3)	C027—C035	1.387 (4)
O006—C024	1.241 (3)	C028—C033	1.384 (4)
C007—C011	1.371 (4)	O029—H029	0.8400
C007—N015	1.361 (3)	C030—C2	1.515 (4)
O008—C010	1.232 (3)	C030—C035	1.378 (5)
O009—H00A	0.8400	C030—C5	1.650 (14)
O009—H009	0.8400	C031—H03A	0.9800
O009—C0	1.422 (5)	C031—H03B	0.9800
O009—C4	1.433 (11)	C031—H03C	0.9800
C010—C011	1.416 (4)	C2—H2	1.0000
C010—N017	1.405 (3)	C2—C0	1.509 (7)
O012—H012	0.8400	C034—H03D	0.9800
O012—C028	1.380 (4)	C034—H03E	0.9800
C013—C014	1.414 (4)	C034—H03F	0.9800
C013—C022	1.412 (3)	C035—H035	0.9500
C013—C024	1.430 (4)	C0—H0	1.0000
C014—C019	1.380 (4)	C1—N2	1.132 (11)
N015—C023	1.334 (4)	C1—C3	1.457 (12)
O016—C025	1.238 (3)	C3—H3A	0.9800
N017—C025	1.385 (4)	C3—H3B	0.9800
N017—C031	1.470 (4)	C3—H3C	0.9800
C018—C019	1.400 (4)	C4—H4	1.0000
C018—C020	1.396 (4)	C4—C5	1.52 (2)
C019—H019	0.9500	C5—H5	1.0000
C007—N001—C034	121.7 (2)	O029—C027—C035	123.0 (3)
C025—N001—C007	118.9 (2)	C035—C027—C033	120.5 (3)
C025—N001—C034	119.4 (2)	O012—C028—C026	119.9 (3)
C014—O002—C2	116.7 (2)	O012—C028—C033	120.3 (3)
C014—O002—C5	113.1 (5)	C033—C028—C026	119.8 (3)
C018—O003—H003	109.5	C027—O029—H029	109.5
C011—N004—H004	126.6	C026—C030—C2	125.3 (4)
C023—N004—H004	126.6	C026—C030—C5	96.5 (6)
C023—N004—C011	106.8 (2)	C035—C030—C026	120.8 (3)
C022—O005—H005	109.5	C035—C030—C2	113.9 (4)
C011—C007—N001	121.6 (2)	C035—C030—C5	141.9 (6)
N015—C007—N001	126.9 (2)	N017—C031—H03A	109.5
N015—C007—C011	111.5 (2)	N017—C031—H03B	109.5
C0—O009—H00A	109.5	N017—C031—H03C	109.5
C4—O009—H009	109.5	H03A—C031—H03B	109.5
O008—C010—C011	127.4 (3)	H03A—C031—H03C	109.5
O008—C010—N017	120.8 (2)	H03B—C031—H03C	109.5
N017—C010—C011	111.8 (2)	O002—C2—C030	108.2 (3)
N004—C011—C010	131.9 (3)	O002—C2—H2	110.0
C007—C011—N004	105.0 (2)	O002—C2—C0	109.0 (4)
C007—C011—C010	123.1 (3)	C030—C2—H2	110.0
C028—O012—H012	109.5	C0—C2—C030	109.7 (4)
C014—C013—C024	120.1 (2)	C0—C2—H2	110.0
C022—C013—C014	118.0 (2)	O021—C033—C027	121.8 (3)
C022—C013—C024	121.8 (2)	O021—C033—C028	118.1 (3)
O002—C014—C013	121.7 (2)	C028—C033—C027	120.1 (3)
O002—C014—C019	116.7 (2)	N001—C034—H03D	109.5
C019—C014—C013	121.6 (2)	N001—C034—H03E	109.5
C023—N015—C007	103.7 (2)	N001—C034—H03F	109.5
C010—N017—C031	117.2 (2)	H03D—C034—H03E	109.5
C025—N017—C010	125.9 (2)	H03D—C034—H03F	109.5
C025—N017—C031	116.8 (2)	H03E—C034—H03F	109.5
O003—C018—C019	120.8 (2)	C027—C035—H035	120.4
O003—C018—C020	116.9 (2)	C030—C035—C027	119.3 (3)
C020—C018—C019	122.3 (2)	C030—C035—H035	120.4
C014—C019—C018	118.2 (2)	O009—C0—C024	109.3 (3)
C014—C019—H019	120.9	O009—C0—C2	109.5 (4)
C018—C019—H019	120.9	O009—C0—H0	109.9
C018—C020—H020	120.8	C024—C0—H0	109.9
C022—C020—C018	118.4 (2)	C2—C0—C024	108.5 (4)
C022—C020—H020	120.8	C2—C0—H0	109.9
C033—O021—H021	109.5	N2—C1—C3	177.4 (7)
O005—C022—C013	120.3 (2)	C1—C3—H3A	109.5
O005—C022—C020	118.2 (2)	C1—C3—H3B	109.5
C020—C022—C013	121.5 (2)	C1—C3—H3C	109.5
N004—C023—H023	123.5	H3A—C3—H3B	109.5
N015—C023—N004	113.0 (2)	H3A—C3—H3C	109.5
N015—C023—H023	123.5	H3B—C3—H3C	109.5
O006—C024—C013	124.5 (3)	O009—C4—C024	108.4 (9)
O006—C024—C0	120.4 (3)	O009—C4—H4	114.4
O006—C024—C4	117.0 (5)	O009—C4—C5	103.9 (11)
C013—C024—C0	114.7 (3)	C024—C4—H4	114.4
C013—C024—C4	113.2 (4)	C5—C4—C024	100.0 (12)
N001—C025—N017	118.7 (2)	C5—C4—H4	114.4
O016—C025—N001	120.2 (3)	O002—C5—C030	99.8 (8)
O016—C025—N017	121.2 (3)	O002—C5—C4	109.7 (11)
C028—C026—H026	120.2	O002—C5—H5	113.7
C028—C026—C030	119.5 (3)	C030—C5—H5	113.7
C030—C026—H026	120.2	C4—C5—C030	104.9 (11)
O029—C027—C033	116.5 (3)	C4—C5—H5	113.7
N001—C007—C011—N004	−179.2 (3)	C022—C013—C014—O002	180.0 (3)
N001—C007—C011—C010	2.3 (5)	C022—C013—C014—C019	0.2 (4)
N001—C007—N015—C023	179.3 (3)	C022—C013—C024—O006	4.5 (5)
O002—C014—C019—C018	−179.5 (2)	C022—C013—C024—C0	−167.4 (4)
O002—C2—C0—O009	−180.0 (3)	C022—C013—C024—C4	157.8 (8)
O002—C2—C0—C024	60.9 (6)	C023—N004—C011—C007	−0.1 (3)
O003—C018—C019—C014	179.3 (3)	C023—N004—C011—C010	178.3 (3)
O003—C018—C020—C022	179.8 (3)	C024—C013—C014—O002	2.1 (4)
O006—C024—C0—O009	27.3 (6)	C024—C013—C014—C019	−177.7 (3)
O006—C024—C0—C2	146.6 (4)	C024—C013—C022—O005	−2.6 (5)
O006—C024—C4—O009	−40.5 (13)	C024—C013—C022—C020	176.8 (3)
O006—C024—C4—C5	−148.9 (7)	C024—C4—C5—O002	−71.3 (14)
C007—N001—C025—O016	176.8 (3)	C024—C4—C5—C030	−177.8 (7)
C007—N001—C025—N017	−3.4 (4)	C025—N001—C007—C011	0.8 (4)
C007—N015—C023—N004	−0.4 (4)	C025—N001—C007—N015	−178.0 (3)
O008—C010—C011—N004	0.1 (6)	C026—C028—C033—O021	179.6 (3)
O008—C010—C011—C007	178.2 (3)	C026—C028—C033—C027	1.1 (4)
O008—C010—N017—C025	179.0 (3)	C026—C030—C2—O002	55.9 (5)
O008—C010—N017—C031	2.2 (4)	C026—C030—C2—C0	−62.9 (5)
O009—C4—C5—O002	176.7 (8)	C026—C030—C035—C027	0.3 (5)
O009—C4—C5—C030	70.3 (13)	C026—C030—C5—O002	101.8 (7)
C010—N017—C025—N001	3.3 (4)	C026—C030—C5—C4	−144.6 (10)
C010—N017—C025—O016	−176.9 (3)	C028—C026—C030—C2	−178.7 (3)
C011—N004—C023—N015	0.4 (4)	C028—C026—C030—C035	0.6 (5)
C011—C007—N015—C023	0.4 (4)	C028—C026—C030—C5	172.7 (4)
C011—C010—N017—C025	−0.4 (4)	O029—C027—C033—O021	1.4 (4)
C011—C010—N017—C031	−177.3 (3)	O029—C027—C033—C028	179.8 (3)
O012—C028—C033—O021	−1.1 (4)	O029—C027—C035—C030	179.5 (3)
O012—C028—C033—C027	−179.6 (3)	C030—C026—C028—O012	179.4 (3)
C013—C014—C019—C018	0.3 (4)	C030—C026—C028—C033	−1.3 (5)
C013—C024—C0—O009	−160.5 (3)	C030—C2—C0—O009	−61.6 (6)
C013—C024—C0—C2	−41.2 (6)	C030—C2—C0—C024	179.2 (3)
C013—C024—C4—O009	164.1 (7)	C031—N017—C025—N001	−179.8 (3)
C013—C024—C4—C5	55.7 (12)	C031—N017—C025—O016	0.0 (4)
C014—O002—C2—C030	−170.8 (3)	C2—O002—C014—C013	19.5 (5)
C014—O002—C2—C0	−51.5 (6)	C2—O002—C014—C019	−160.6 (4)
C014—O002—C5—C030	164.2 (4)	C2—C030—C035—C027	179.7 (3)
C014—O002—C5—C4	54.3 (14)	C033—C027—C035—C030	−0.4 (5)
C014—C013—C022—O005	179.5 (3)	C034—N001—C007—C011	178.7 (3)
C014—C013—C022—C020	−1.0 (4)	C034—N001—C007—N015	−0.1 (5)
C014—C013—C024—O006	−177.7 (3)	C034—N001—C025—O016	−1.1 (5)
C014—C013—C024—C0	10.4 (5)	C034—N001—C025—N017	178.6 (3)
C014—C013—C024—C4	−24.4 (8)	C035—C027—C033—O021	−178.7 (3)
N015—C007—C011—N004	−0.2 (3)	C035—C027—C033—C028	−0.3 (5)
N015—C007—C011—C010	−178.7 (3)	C035—C030—C2—O002	−123.4 (4)
N017—C010—C011—N004	179.5 (3)	C035—C030—C2—C0	117.7 (5)
N017—C010—C011—C007	−2.3 (4)	C035—C030—C5—O002	−89.2 (8)
C018—C020—C022—O005	−179.1 (3)	C035—C030—C5—C4	24.4 (15)
C018—C020—C022—C013	1.4 (5)	C5—O002—C014—C013	−16.6 (8)
C019—C018—C020—C022	−0.9 (5)	C5—O002—C014—C019	163.2 (7)
C020—C018—C019—C014	0.1 (4)	C5—C030—C035—C027	−167.0 (7)

(Scalemic-DMY-THE-3)

Crystal data

C7H8N4O2·C15H12O8·C2H3N	Dx = 1.485 Mg m^−3
Mr = 541.47	Ga Kα radiation, λ = 1.34139 Å
Orthorhombic, P212121	Cell parameters from 9183 reflections
a = 6.7719 (6) Å	θ = 5.5–53.9°
b = 15.2411 (14) Å	µ = 0.64 mm^−1
c = 23.471 (2) Å	T = 193 K
V = 2422.4 (4) Å^3	Block, colourless
Z = 4	0.2 × 0.18 × 0.15 mm
F(000) = 1128

Data collection

Bruker D8 Venture diffractometer	4142 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.053
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1377 before and 0.0841 after correction. The Ratio of minimum to maximum transmission is 0.8777. The λ/2 correction factor is Not present.	θmax = 54.0°, θmin = 3.0°
Tmin = 0.659, Tmax = 0.751	h = −8→8
27526 measured reflections	k = −18→18
4418 independent reflections	l = −27→28

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 0.4902P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.093	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.20 e Å^−3
4418 reflections	Δρmin = −0.18 e Å^−3
380 parameters	Absolute structure: Refined as an inversion twin.
44 restraints	Absolute structure parameter: 0.4 (3)
Primary atom site location: dual

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.

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.3129 (3)	1.06769 (11)	0.48160 (7)	0.0360 (4)
O4	0.4209 (3)	0.31197 (14)	0.79840 (7)	0.0407 (5)
H4	0.326032	0.284789	0.813220	0.061*
O6	0.3309 (3)	0.26509 (11)	0.43062 (7)	0.0372 (4)
O8	0.3104 (3)	0.45836 (10)	0.55101 (6)	0.0302 (4)
O10	0.2470 (3)	0.67884 (11)	0.41041 (7)	0.0396 (5)
H10	0.239626	0.709788	0.439945	0.059*
O5	0.2147 (4)	0.77308 (11)	0.50491 (8)	0.0476 (5)
O3	0.2887 (3)	0.38569 (11)	0.35131 (7)	0.0410 (5)
H3	0.296065	0.334795	0.364877	0.062*
O7	0.7204 (3)	0.37084 (14)	0.73158 (8)	0.0440 (5)
H7	0.706824	0.392356	0.764297	0.066*
O2	0.3466 (3)	0.21986 (11)	0.54179 (7)	0.0412 (5)
H2B	0.319208	0.183056	0.516358	0.062*	0.212 (13)
H2A	0.348831	0.189390	0.511980	0.062*	0.788 (13)
O9	0.0562 (3)	0.27932 (16)	0.75470 (9)	0.0535 (6)
H9	−0.055227	0.295402	0.742979	0.080*
N1	0.2648 (4)	0.95668 (14)	0.66452 (9)	0.0361 (5)
N4	0.2433 (3)	0.85385 (13)	0.58474 (9)	0.0332 (5)
N5	0.2699 (3)	0.91999 (13)	0.49423 (8)	0.0321 (5)
N3	0.2982 (4)	1.07803 (13)	0.61268 (9)	0.0341 (5)
H3A	0.311622	1.133932	0.604127	0.041*
C1	0.2652 (4)	0.93587 (16)	0.60795 (10)	0.0306 (5)
C4	0.2921 (4)	1.00571 (16)	0.51471 (10)	0.0294 (5)
C6	0.2966 (4)	0.48052 (15)	0.49493 (9)	0.0264 (5)
C8	0.2853 (4)	1.00901 (15)	0.57495 (10)	0.0297 (5)
C10	0.5373 (4)	0.35539 (18)	0.70812 (11)	0.0344 (6)
C12	0.3019 (4)	0.41623 (15)	0.45158 (9)	0.0276 (5)
C14	0.2783 (4)	0.56835 (16)	0.48238 (10)	0.0297 (5)
H14	0.274837	0.611007	0.511877	0.036*
C16	0.2695 (4)	0.53245 (16)	0.38116 (10)	0.0327 (6)
H16	0.261343	0.551037	0.342599	0.039*
C18	0.2859 (4)	0.44494 (16)	0.39437 (10)	0.0295 (5)
C20	0.2415 (4)	0.84534 (16)	0.52699 (11)	0.0341 (6)
C22	0.3846 (4)	0.32427 (17)	0.74173 (10)	0.0316 (6)
C24	0.2862 (4)	1.04332 (17)	0.66470 (11)	0.0375 (6)
H24	0.292368	1.077253	0.698604	0.045*
C26	0.2649 (4)	0.59329 (16)	0.42525 (10)	0.0301 (5)
C13	0.1998 (5)	0.30954 (18)	0.71819 (11)	0.0392 (6)
C7	0.3306 (4)	0.32626 (16)	0.46567 (10)	0.0336 (6)
C15	0.5060 (5)	0.36941 (18)	0.65041 (11)	0.0412 (7)
H15	0.610780	0.389200	0.626764	0.049*
C2	0.1663 (5)	0.32467 (18)	0.66094 (12)	0.0429 (7)
H2	0.039256	0.314812	0.644978	0.051*
C17	0.3184 (5)	0.35408 (17)	0.62741 (11)	0.0441 (7)
C9	0.2166 (5)	0.77567 (18)	0.62029 (11)	0.0448 (7)
H9A	0.278050	0.785359	0.657566	0.067*
H9B	0.278617	0.725102	0.601727	0.067*
H9C	0.075237	0.764287	0.625354	0.067*
C19	0.2675 (6)	0.9085 (2)	0.43204 (11)	0.0505 (8)
H19A	0.132117	0.896920	0.419363	0.076*
H19B	0.352338	0.858985	0.421598	0.076*
H19C	0.316436	0.962053	0.413706	0.076*
C5B	0.268 (4)	0.3042 (8)	0.5262 (5)	0.027 (4)	0.212 (13)
H5B	0.122055	0.309486	0.532613	0.032*	0.212 (13)
C21B	0.387 (3)	0.3686 (7)	0.5602 (5)	0.027 (4)	0.212 (13)
H21B	0.532878	0.363137	0.554066	0.032*	0.212 (13)
N2	0.5403 (12)	0.6001 (4)	0.7037 (2)	0.128 (2)
C3	0.3770 (13)	0.5835 (4)	0.7043 (3)	0.109 (2)
C25	0.1700 (13)	0.5625 (4)	0.7075 (2)	0.127 (2)
H25A	0.132202	0.527508	0.674202	0.190*
H25B	0.092605	0.616790	0.708221	0.190*
H25C	0.144321	0.528787	0.742292	0.190*
C5A	0.3868 (10)	0.3083 (2)	0.52801 (13)	0.0305 (12)	0.788 (13)
H5A	0.530481	0.320654	0.533757	0.037*	0.788 (13)
C21A	0.2653 (9)	0.3685 (2)	0.56560 (13)	0.0285 (11)	0.788 (13)
H21A	0.121402	0.356855	0.559635	0.034*	0.788 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0471 (11)	0.0307 (9)	0.0302 (8)	−0.0008 (8)	0.0016 (8)	0.0031 (7)
O4	0.0504 (12)	0.0493 (12)	0.0223 (9)	0.0019 (10)	−0.0014 (8)	0.0025 (8)
O6	0.0528 (11)	0.0277 (9)	0.0311 (9)	0.0015 (8)	0.0044 (8)	−0.0055 (7)
O8	0.0442 (10)	0.0254 (8)	0.0210 (7)	−0.0002 (8)	−0.0014 (7)	0.0014 (6)
O10	0.0626 (13)	0.0256 (8)	0.0305 (8)	−0.0013 (9)	−0.0054 (9)	0.0049 (7)
O5	0.0733 (15)	0.0272 (10)	0.0424 (10)	−0.0003 (10)	−0.0033 (11)	−0.0059 (8)
O3	0.0651 (13)	0.0341 (10)	0.0238 (8)	0.0057 (10)	−0.0014 (9)	−0.0052 (7)
O7	0.0441 (11)	0.0534 (12)	0.0345 (9)	−0.0029 (10)	0.0045 (9)	−0.0078 (8)
O2	0.0695 (14)	0.0228 (9)	0.0312 (9)	−0.0004 (9)	−0.0019 (9)	0.0012 (7)
O9	0.0464 (12)	0.0632 (15)	0.0510 (13)	−0.0043 (11)	−0.0024 (10)	0.0115 (11)
N1	0.0435 (13)	0.0358 (11)	0.0291 (10)	−0.0023 (10)	−0.0038 (10)	0.0030 (9)
N4	0.0413 (13)	0.0265 (10)	0.0317 (10)	−0.0005 (10)	−0.0046 (9)	0.0034 (8)
N5	0.0392 (12)	0.0289 (10)	0.0282 (10)	0.0023 (10)	0.0016 (9)	−0.0012 (8)
N3	0.0456 (13)	0.0253 (10)	0.0315 (10)	−0.0005 (10)	−0.0013 (10)	−0.0014 (8)
C1	0.0316 (13)	0.0299 (12)	0.0302 (11)	−0.0009 (11)	−0.0026 (10)	0.0004 (10)
C4	0.0281 (12)	0.0292 (12)	0.0309 (12)	0.0014 (11)	0.0005 (10)	−0.0005 (10)
C6	0.0273 (12)	0.0301 (12)	0.0217 (11)	−0.0010 (10)	0.0001 (9)	0.0009 (9)
C8	0.0321 (12)	0.0262 (12)	0.0307 (12)	0.0015 (11)	−0.0024 (10)	0.0000 (9)
C10	0.0444 (15)	0.0328 (13)	0.0260 (12)	0.0018 (12)	0.0003 (11)	−0.0047 (10)
C12	0.0303 (12)	0.0291 (12)	0.0235 (11)	0.0006 (10)	0.0004 (10)	−0.0005 (9)
C14	0.0370 (13)	0.0263 (11)	0.0259 (11)	−0.0001 (11)	−0.0020 (10)	−0.0018 (9)
C16	0.0405 (14)	0.0346 (13)	0.0232 (11)	0.0005 (11)	−0.0022 (10)	0.0023 (10)
C18	0.0317 (13)	0.0332 (12)	0.0234 (11)	0.0011 (11)	−0.0007 (10)	−0.0015 (9)
C20	0.0379 (15)	0.0278 (12)	0.0364 (13)	0.0028 (11)	−0.0025 (11)	0.0000 (10)
C22	0.0460 (15)	0.0269 (13)	0.0219 (11)	0.0049 (11)	−0.0007 (10)	0.0005 (10)
C24	0.0482 (16)	0.0342 (13)	0.0300 (12)	−0.0011 (13)	−0.0025 (13)	−0.0011 (10)
C26	0.0335 (13)	0.0270 (11)	0.0299 (11)	−0.0027 (10)	−0.0037 (10)	0.0048 (10)
C13	0.0483 (16)	0.0346 (14)	0.0346 (13)	0.0011 (13)	−0.0062 (13)	0.0017 (11)
C7	0.0435 (15)	0.0301 (13)	0.0272 (12)	−0.0009 (11)	0.0059 (11)	−0.0013 (10)
C15	0.066 (2)	0.0303 (14)	0.0269 (13)	−0.0028 (13)	0.0092 (13)	0.0005 (10)
C2	0.0567 (18)	0.0354 (14)	0.0366 (14)	−0.0027 (13)	−0.0135 (13)	0.0033 (12)
C17	0.079 (2)	0.0261 (13)	0.0271 (13)	0.0008 (15)	−0.0158 (15)	−0.0027 (10)
C9	0.065 (2)	0.0295 (13)	0.0401 (14)	−0.0047 (14)	−0.0110 (14)	0.0074 (11)
C19	0.080 (2)	0.0411 (15)	0.0307 (13)	0.0032 (16)	0.0060 (15)	−0.0047 (12)
C5B	0.034 (10)	0.021 (6)	0.025 (6)	0.000 (6)	0.002 (6)	0.003 (4)
C21B	0.035 (11)	0.018 (6)	0.027 (6)	0.001 (6)	−0.009 (6)	−0.005 (5)
N2	0.222 (6)	0.082 (3)	0.079 (3)	0.018 (4)	−0.042 (4)	0.000 (2)
C3	0.207 (7)	0.054 (3)	0.067 (3)	0.024 (4)	−0.047 (5)	−0.009 (2)
C25	0.227 (7)	0.071 (3)	0.082 (3)	0.025 (4)	−0.043 (5)	−0.005 (3)
C5A	0.039 (3)	0.0259 (18)	0.0267 (17)	−0.0007 (18)	0.0002 (16)	0.0015 (14)
C21A	0.035 (3)	0.0264 (17)	0.0247 (16)	−0.0018 (17)	−0.0020 (15)	0.0011 (12)

Geometric parameters (Å, º)

O1—C4	1.231 (3)	C10—C15	1.387 (4)
O4—H4	0.8400	C12—C18	1.417 (3)
O4—C22	1.365 (3)	C12—C7	1.424 (3)
O6—C7	1.243 (3)	C14—H14	0.9500
O8—C6	1.362 (3)	C14—C26	1.397 (3)
O8—C21B	1.480 (13)	C16—H16	0.9500
O8—C21A	1.445 (4)	C16—C18	1.374 (3)
O10—H10	0.8400	C16—C26	1.390 (3)
O10—C26	1.355 (3)	C22—C13	1.387 (4)
O5—C20	1.231 (3)	C24—H24	0.9500
O3—H3	0.8400	C13—C2	1.382 (4)
O3—C18	1.355 (3)	C7—C5B	1.521 (12)
O7—H7	0.8400	C7—C5A	1.537 (4)
O7—C10	1.377 (3)	C15—H15	0.9500
O2—H2B	0.8400	C15—C17	1.400 (5)
O2—H2A	0.8400	C2—H2	0.9500
O2—C5B	1.440 (13)	C2—C17	1.372 (5)
O2—C5A	1.413 (4)	C17—C21B	1.660 (15)
O9—H9	0.8400	C17—C21A	1.511 (4)
O9—C13	1.375 (4)	C9—H9A	0.9800
N1—C1	1.365 (3)	C9—H9B	0.9800
N1—C24	1.328 (3)	C9—H9C	0.9800
N4—C1	1.372 (3)	C19—H19A	0.9800
N4—C20	1.362 (3)	C19—H19B	0.9800
N4—C9	1.466 (3)	C19—H19C	0.9800
N5—C4	1.400 (3)	C5B—H5B	1.0000
N5—C20	1.387 (3)	C5B—C21B	1.50 (3)
N5—C19	1.470 (3)	C21B—H21B	1.0000
N3—H3A	0.8800	N2—C3	1.134 (8)
N3—C8	1.378 (3)	C3—C25	1.440 (8)
N3—C24	1.333 (3)	C25—H25A	0.9800
C1—C8	1.364 (3)	C25—H25B	0.9800
C4—C8	1.416 (3)	C25—H25C	0.9800
C6—C12	1.413 (3)	C5A—H5A	1.0000
C6—C14	1.376 (3)	C5A—C21A	1.515 (8)
C10—C22	1.384 (4)	C21A—H21A	1.0000
C22—O4—H4	109.5	C2—C13—C22	120.6 (3)
C6—O8—C21B	113.2 (5)	O6—C7—C12	124.7 (2)
C6—O8—C21A	116.7 (2)	O6—C7—C5B	116.9 (5)
C26—O10—H10	109.5	O6—C7—C5A	119.7 (2)
C18—O3—H3	109.5	C12—C7—C5B	113.0 (5)
C10—O7—H7	109.5	C12—C7—C5A	115.2 (2)
C5B—O2—H2B	109.5	C10—C15—H15	120.4
C5A—O2—H2A	109.5	C10—C15—C17	119.3 (3)
C13—O9—H9	109.5	C17—C15—H15	120.4
C24—N1—C1	103.5 (2)	C13—C2—H2	120.4
C1—N4—C9	121.9 (2)	C17—C2—C13	119.3 (3)
C20—N4—C1	118.9 (2)	C17—C2—H2	120.4
C20—N4—C9	119.2 (2)	C15—C17—C21B	95.1 (8)
C4—N5—C19	116.9 (2)	C15—C17—C21A	124.2 (4)
C20—N5—C4	126.2 (2)	C2—C17—C15	121.0 (2)
C20—N5—C19	116.8 (2)	C2—C17—C21B	143.1 (7)
C8—N3—H3A	126.8	C2—C17—C21A	114.8 (3)
C24—N3—H3A	126.8	N4—C9—H9A	109.5
C24—N3—C8	106.4 (2)	N4—C9—H9B	109.5
N1—C1—N4	126.7 (2)	N4—C9—H9C	109.5
C8—C1—N1	111.2 (2)	H9A—C9—H9B	109.5
C8—C1—N4	122.0 (2)	H9A—C9—H9C	109.5
O1—C4—N5	120.8 (2)	H9B—C9—H9C	109.5
O1—C4—C8	127.4 (2)	N5—C19—H19A	109.5
N5—C4—C8	111.9 (2)	N5—C19—H19B	109.5
O8—C6—C12	121.5 (2)	N5—C19—H19C	109.5
O8—C6—C14	117.0 (2)	H19A—C19—H19B	109.5
C14—C6—C12	121.5 (2)	H19A—C19—H19C	109.5
N3—C8—C4	131.8 (2)	H19B—C19—H19C	109.5
C1—C8—N3	105.4 (2)	O2—C5B—C7	109.3 (10)
C1—C8—C4	122.8 (2)	O2—C5B—H5B	113.6
O7—C10—C22	120.2 (2)	O2—C5B—C21B	104.3 (15)
O7—C10—C15	120.1 (3)	C7—C5B—H5B	113.6
C22—C10—C15	119.7 (3)	C21B—C5B—C7	101.6 (15)
C6—C12—C18	117.8 (2)	C21B—C5B—H5B	113.6
C6—C12—C7	120.3 (2)	O8—C21B—C17	99.3 (9)
C18—C12—C7	121.9 (2)	O8—C21B—C5B	109.7 (14)
C6—C14—H14	120.8	O8—C21B—H21B	113.7
C6—C14—C26	118.4 (2)	C17—C21B—H21B	113.7
C26—C14—H14	120.8	C5B—C21B—C17	105.5 (14)
C18—C16—H16	120.6	C5B—C21B—H21B	113.7
C18—C16—C26	118.8 (2)	N2—C3—C25	177.6 (7)
C26—C16—H16	120.6	C3—C25—H25A	109.5
O3—C18—C12	120.0 (2)	C3—C25—H25B	109.5
O3—C18—C16	118.7 (2)	C3—C25—H25C	109.5
C16—C18—C12	121.3 (2)	H25A—C25—H25B	109.5
O5—C20—N4	120.4 (2)	H25A—C25—H25C	109.5
O5—C20—N5	121.4 (2)	H25B—C25—H25C	109.5
N4—C20—N5	118.2 (2)	O2—C5A—C7	109.9 (3)
O4—C22—C10	117.9 (2)	O2—C5A—H5A	109.6
O4—C22—C13	121.9 (2)	O2—C5A—C21A	109.8 (4)
C10—C22—C13	120.2 (2)	C7—C5A—H5A	109.6
N1—C24—N3	113.5 (2)	C21A—C5A—C7	108.2 (4)
N1—C24—H24	123.3	C21A—C5A—H5A	109.6
N3—C24—H24	123.3	O8—C21A—C17	108.3 (3)
O10—C26—C14	121.0 (2)	O8—C21A—C5A	108.7 (4)
O10—C26—C16	116.9 (2)	O8—C21A—H21A	109.9
C16—C26—C14	122.1 (2)	C17—C21A—C5A	110.0 (4)
O9—C13—C22	116.4 (2)	C17—C21A—H21A	109.9
O9—C13—C2	123.1 (3)	C5A—C21A—H21A	109.9
O1—C4—C8—N3	0.3 (5)	C12—C7—C5A—C21A	40.4 (6)
O1—C4—C8—C1	−178.8 (3)	C14—C6—C12—C18	−0.5 (4)
O4—C22—C13—O9	−1.9 (4)	C14—C6—C12—C7	176.9 (3)
O4—C22—C13—C2	178.4 (3)	C18—C12—C7—O6	−5.1 (4)
O6—C7—C5B—O2	39.3 (17)	C18—C12—C7—C5B	−158.2 (10)
O6—C7—C5B—C21B	149.1 (10)	C18—C12—C7—C5A	168.1 (3)
O6—C7—C5A—O2	−26.2 (6)	C18—C16—C26—O10	−179.5 (2)
O6—C7—C5A—C21A	−146.1 (4)	C18—C16—C26—C14	0.6 (4)
O8—C6—C12—C18	179.8 (2)	C20—N4—C1—N1	178.0 (3)
O8—C6—C12—C7	−2.7 (4)	C20—N4—C1—C8	0.0 (4)
O8—C6—C14—C26	179.7 (2)	C20—N5—C4—O1	−178.6 (2)
O7—C10—C22—O4	1.7 (4)	C20—N5—C4—C8	0.9 (4)
O7—C10—C22—C13	179.4 (2)	C22—C10—C15—C17	1.8 (4)
O7—C10—C15—C17	−179.5 (2)	C22—C13—C2—C17	0.3 (4)
O2—C5B—C21B—O8	−176.0 (9)	C24—N1—C1—N4	−178.6 (3)
O2—C5B—C21B—C17	−69.8 (17)	C24—N1—C1—C8	−0.4 (3)
O2—C5A—C21A—O8	179.5 (3)	C24—N3—C8—C1	0.2 (3)
O2—C5A—C21A—C17	61.0 (6)	C24—N3—C8—C4	−179.0 (3)
O9—C13—C2—C17	−179.4 (3)	C26—C16—C18—O3	179.5 (2)
N1—C1—C8—N3	0.1 (3)	C26—C16—C18—C12	−1.2 (4)
N1—C1—C8—C4	179.4 (2)	C13—C2—C17—C15	−0.4 (4)
N4—C1—C8—N3	178.4 (2)	C13—C2—C17—C21B	166.4 (8)
N4—C1—C8—C4	−2.3 (4)	C13—C2—C17—C21A	−180.0 (3)
N5—C4—C8—N3	−179.1 (3)	C7—C12—C18—O3	3.1 (4)
N5—C4—C8—C1	1.8 (4)	C7—C12—C18—C16	−176.3 (3)
C1—N1—C24—N3	0.5 (3)	C7—C5B—C21B—O8	70.4 (19)
C1—N4—C20—O5	−177.3 (3)	C7—C5B—C21B—C17	176.6 (8)
C1—N4—C20—N5	2.5 (4)	C7—C5A—C21A—O8	−60.6 (6)
C4—N5—C20—O5	176.7 (3)	C7—C5A—C21A—C17	−179.0 (3)
C4—N5—C20—N4	−3.1 (4)	C15—C10—C22—O4	−179.5 (2)
C6—O8—C21B—C17	−163.2 (5)	C15—C10—C22—C13	−1.8 (4)
C6—O8—C21B—C5B	−53.0 (18)	C15—C17—C21B—O8	−102.1 (9)
C6—O8—C21A—C17	171.6 (3)	C15—C17—C21B—C5B	144.3 (13)
C6—O8—C21A—C5A	52.1 (5)	C15—C17—C21A—O8	−56.3 (5)
C6—C12—C18—O3	−179.5 (2)	C15—C17—C21A—C5A	62.4 (5)
C6—C12—C18—C16	1.2 (4)	C2—C17—C21B—O8	89.2 (9)
C6—C12—C7—O6	177.6 (2)	C2—C17—C21B—C5B	−24.4 (18)
C6—C12—C7—C5B	24.4 (10)	C2—C17—C21A—O8	123.3 (4)
C6—C12—C7—C5A	−9.3 (5)	C2—C17—C21A—C5A	−118.0 (5)
C6—C14—C26—O10	−179.9 (2)	C9—N4—C1—N1	−0.3 (4)
C6—C14—C26—C16	0.0 (4)	C9—N4—C1—C8	−178.4 (3)
C8—N3—C24—N1	−0.5 (3)	C9—N4—C20—O5	1.1 (4)
C10—C22—C13—O9	−179.5 (2)	C9—N4—C20—N5	−179.1 (2)
C10—C22—C13—C2	0.8 (4)	C19—N5—C4—O1	−1.6 (4)
C10—C15—C17—C2	−0.6 (4)	C19—N5—C4—C8	177.9 (3)
C10—C15—C17—C21B	−172.8 (5)	C19—N5—C20—O5	−0.3 (4)
C10—C15—C17—C21A	178.9 (3)	C19—N5—C20—N4	179.9 (3)
C12—C6—C14—C26	0.0 (4)	C21B—O8—C6—C12	16.6 (10)
C12—C7—C5B—O2	−165.3 (9)	C21B—O8—C6—C14	−163.1 (9)
C12—C7—C5B—C21B	−55.5 (16)	C21A—O8—C6—C12	−19.9 (4)
C12—C7—C5A—O2	160.3 (3)	C21A—O8—C6—C14	160.4 (3)

(RR-DMY-THE)

Crystal data

C15H12O8·C7H8N4O2·C2H3N	Dx = 1.505 Mg m^−3
Mr = 541.47	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 7249 reflections
a = 6.7292 (4) Å	θ = 2.3–33.4°
b = 15.1840 (7) Å	µ = 0.12 mm^−1
c = 23.3897 (11) Å	T = 113 K
V = 2389.9 (2) Å^3	Plate, colourless
Z = 4	0.17 × 0.15 × 0.14 mm
F(000) = 1128

Data collection

Dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images diffractometer	4891 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	4090 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ω scans	θmax = 26.4°, θmin = 1.6°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.569, Tmax = 1.000	k = −18→18
18891 measured reflections	l = −29→29

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.067	w = 1/[σ^2(Fo^2) + (0.090P)^2 + 1.3405P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.170	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.43 e Å^−3
4891 reflections	Δρmin = −0.32 e Å^−3
361 parameters	Absolute structure: Flack x determined using 1365 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
18 restraints	Absolute structure parameter: −1.0 (10)
Primary atom site location: dual

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	0.2488 (6)	0.31978 (19)	0.59073 (13)	0.0289 (8)
H1	0.246902	0.288210	0.561243	0.043*
O2	0.2914 (6)	0.6145 (2)	0.64935 (13)	0.0306 (8)
H2	0.306866	0.665274	0.635828	0.046*
O3	0.3150 (5)	0.54033 (19)	0.44927 (13)	0.0244 (8)
O4	0.3385 (6)	0.7348 (2)	0.56954 (14)	0.0277 (8)
O5	0.3553 (6)	0.7799 (2)	0.45796 (14)	0.0302 (8)
H5	0.326609	0.808636	0.487514	0.045*
O6	0.7181 (5)	0.6281 (2)	0.26915 (14)	0.0291 (8)
H6	0.705393	0.610567	0.235274	0.044*
O7	0.4224 (6)	0.6886 (2)	0.20129 (14)	0.0305 (9)
H7	0.319539	0.705552	0.184184	0.046*
O8	0.0512 (6)	0.7215 (3)	0.24343 (15)	0.0346 (9)
H8	−0.061968	0.706866	0.255242	0.052*
C1	0.2668 (8)	0.4058 (3)	0.5754 (2)	0.0245 (10)
C2	0.2807 (8)	0.4302 (3)	0.5184 (2)	0.0232 (10)
H2A	0.277149	0.387015	0.489009	0.028*
C3	0.2999 (7)	0.5190 (3)	0.50507 (18)	0.0195 (9)
C4	0.2694 (8)	0.6314 (3)	0.43474 (19)	0.0238 (10)
H4	0.125089	0.642526	0.441869	0.029*
C5	0.3907 (8)	0.6908 (3)	0.4728 (2)	0.0249 (11)
H5A	0.534649	0.677702	0.466394	0.030*
C6	0.3424 (8)	0.6732 (3)	0.53468 (19)	0.0227 (10)
C7	0.3064 (7)	0.5827 (3)	0.54918 (19)	0.0218 (9)
C8	0.2888 (8)	0.5552 (3)	0.6063 (2)	0.0236 (10)
C9	0.2711 (8)	0.4667 (3)	0.61982 (19)	0.0243 (10)
H9	0.262120	0.448056	0.658499	0.029*
C10	0.3123 (8)	0.6448 (3)	0.37252 (19)	0.0232 (10)
C11	0.4995 (7)	0.6303 (3)	0.3495 (2)	0.0244 (11)
H11	0.604907	0.610848	0.373412	0.029*
C12	0.5327 (8)	0.6440 (3)	0.2923 (2)	0.0247 (10)
C13	0.3809 (8)	0.6765 (3)	0.2575 (2)	0.0256 (11)
C14	0.1928 (8)	0.6910 (3)	0.2805 (2)	0.0258 (11)
C15	0.1593 (8)	0.6753 (3)	0.3378 (2)	0.0253 (10)
H15	0.031259	0.685464	0.353665	0.030*
O9	0.6854 (6)	0.4312 (2)	−0.01909 (13)	0.0270 (8)
O10	0.7877 (6)	0.7271 (2)	0.00414 (14)	0.0332 (9)
N1	0.7336 (7)	0.5435 (2)	0.16460 (17)	0.0270 (9)
N2	0.6971 (7)	0.4217 (2)	0.11283 (17)	0.0270 (9)
H2B	0.682286	0.365609	0.104251	0.032*
N3	0.7300 (6)	0.5799 (2)	−0.00693 (16)	0.0238 (9)
N4	0.7551 (6)	0.6464 (2)	0.08442 (16)	0.0238 (9)
C16	0.7099 (8)	0.4557 (3)	0.1650 (2)	0.0290 (11)
H16	0.703012	0.421514	0.198955	0.035*
C17	0.7113 (7)	0.4906 (3)	0.0746 (2)	0.0231 (10)
C18	0.7055 (7)	0.4935 (3)	0.01480 (19)	0.0230 (10)
C19	0.7589 (8)	0.6545 (3)	0.0272 (2)	0.0246 (10)
C20	0.7338 (7)	0.5639 (3)	0.1085 (2)	0.0224 (10)
C21	0.7359 (10)	0.5916 (3)	−0.0685 (2)	0.0353 (13)
H21A	0.870625	0.608187	−0.080167	0.053*
H21B	0.642635	0.638160	−0.079571	0.053*
H21C	0.698301	0.536383	−0.087282	0.053*
C22	0.7816 (9)	0.7251 (3)	0.1205 (2)	0.0307 (12)
H22A	0.923333	0.739412	0.123139	0.046*
H22B	0.729044	0.713474	0.158824	0.046*
H22C	0.710065	0.774901	0.103494	0.046*
N5	0.5395 (16)	0.4009 (5)	0.2969 (3)	0.082 (2)
C23	0.1668 (19)	0.4371 (5)	0.2928 (4)	0.087 (3)
H23A	0.134788	0.461789	0.255191	0.130*
H23B	0.134316	0.480125	0.322568	0.130*
H23C	0.089111	0.383281	0.298908	0.130*
C24	0.3749 (18)	0.4165 (5)	0.2953 (4)	0.066 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.046 (2)	0.0086 (14)	0.0326 (16)	0.0000 (16)	0.0025 (17)	0.0015 (12)
O2	0.050 (2)	0.0160 (16)	0.0262 (16)	−0.0053 (17)	0.0007 (17)	−0.0041 (12)
O3	0.037 (2)	0.0087 (14)	0.0277 (16)	0.0012 (14)	−0.0001 (15)	−0.0003 (12)
O4	0.037 (2)	0.0120 (15)	0.0341 (18)	−0.0017 (15)	−0.0013 (15)	−0.0033 (13)
O5	0.052 (2)	0.0074 (15)	0.0316 (17)	0.0016 (15)	0.0019 (17)	0.0007 (13)
O6	0.028 (2)	0.0290 (18)	0.0306 (17)	0.0001 (17)	−0.0003 (15)	−0.0041 (14)
O7	0.038 (2)	0.0254 (18)	0.0286 (17)	−0.0018 (17)	−0.0006 (15)	0.0007 (14)
O8	0.032 (2)	0.033 (2)	0.039 (2)	0.0014 (18)	−0.0028 (17)	0.0064 (16)
C1	0.026 (3)	0.0097 (19)	0.037 (2)	0.001 (2)	0.001 (2)	0.0009 (18)
C2	0.024 (3)	0.011 (2)	0.034 (2)	0.002 (2)	0.000 (2)	−0.0023 (17)
C3	0.019 (2)	0.0125 (19)	0.027 (2)	0.0036 (18)	0.0002 (19)	−0.0031 (16)
C4	0.032 (3)	0.0097 (19)	0.030 (2)	0.004 (2)	0.001 (2)	0.0027 (16)
C5	0.032 (3)	0.009 (2)	0.034 (2)	0.000 (2)	0.002 (2)	0.0020 (18)
C6	0.026 (3)	0.012 (2)	0.030 (2)	0.0007 (19)	−0.005 (2)	−0.0009 (17)
C7	0.021 (2)	0.011 (2)	0.033 (2)	0.0027 (19)	0.001 (2)	−0.0018 (17)
C8	0.023 (3)	0.016 (2)	0.031 (2)	0.003 (2)	0.002 (2)	−0.0038 (18)
C9	0.029 (3)	0.017 (2)	0.027 (2)	0.003 (2)	0.002 (2)	0.0019 (17)
C10	0.029 (3)	0.0093 (19)	0.031 (2)	−0.002 (2)	−0.001 (2)	−0.0044 (17)
C11	0.027 (3)	0.012 (2)	0.035 (3)	−0.0018 (19)	−0.004 (2)	−0.0018 (18)
C12	0.024 (3)	0.013 (2)	0.036 (3)	−0.002 (2)	0.001 (2)	−0.0049 (18)
C13	0.035 (3)	0.010 (2)	0.031 (2)	−0.004 (2)	−0.003 (2)	−0.0019 (18)
C14	0.029 (3)	0.015 (2)	0.034 (2)	−0.002 (2)	−0.005 (2)	−0.0014 (18)
C15	0.025 (3)	0.012 (2)	0.039 (3)	−0.0003 (19)	0.000 (2)	−0.0033 (18)
O9	0.037 (2)	0.0114 (15)	0.0328 (17)	−0.0006 (15)	−0.0010 (15)	−0.0030 (12)
O10	0.050 (3)	0.0107 (15)	0.0393 (18)	0.0002 (17)	0.0040 (18)	0.0048 (14)
N1	0.031 (2)	0.0147 (18)	0.035 (2)	0.0013 (18)	0.0009 (19)	−0.0044 (15)
N2	0.035 (3)	0.0121 (18)	0.034 (2)	0.0013 (18)	−0.0006 (19)	0.0006 (15)
N3	0.027 (2)	0.0097 (17)	0.034 (2)	0.0035 (17)	−0.0022 (18)	−0.0011 (15)
N4	0.030 (2)	0.0094 (17)	0.032 (2)	−0.0003 (17)	0.0045 (17)	−0.0052 (14)
C16	0.037 (3)	0.019 (2)	0.031 (2)	0.001 (2)	0.002 (2)	0.0014 (18)
C17	0.024 (3)	0.0088 (19)	0.036 (2)	0.001 (2)	0.001 (2)	−0.0014 (17)
C18	0.021 (3)	0.014 (2)	0.033 (2)	0.001 (2)	0.001 (2)	−0.0002 (17)
C19	0.024 (3)	0.011 (2)	0.039 (2)	0.0031 (19)	0.000 (2)	−0.0014 (18)
C20	0.019 (3)	0.013 (2)	0.035 (2)	0.0015 (19)	0.004 (2)	−0.0027 (18)
C21	0.051 (4)	0.018 (2)	0.037 (3)	0.002 (3)	−0.005 (3)	0.001 (2)
C22	0.045 (3)	0.011 (2)	0.036 (3)	−0.004 (2)	0.004 (2)	−0.0068 (18)
N5	0.137 (7)	0.041 (4)	0.067 (4)	−0.014 (5)	0.018 (5)	0.002 (3)
C23	0.154 (9)	0.040 (4)	0.066 (4)	−0.024 (5)	0.021 (5)	−0.009 (3)
C24	0.104 (5)	0.039 (4)	0.056 (4)	−0.012 (4)	0.017 (4)	0.000 (3)

Geometric parameters (Å, º)

O1—H1	0.8400	C11—C12	1.374 (7)
O1—C1	1.360 (5)	C12—C13	1.396 (7)
O2—H2	0.8400	C13—C14	1.393 (8)
O2—C8	1.351 (5)	C14—C15	1.382 (7)
O3—C3	1.348 (5)	C15—H15	0.9500
O3—C4	1.456 (5)	O9—C18	1.241 (5)
O4—C6	1.240 (5)	O10—C19	1.242 (5)
O5—H5	0.8400	N1—C16	1.344 (6)
O5—C5	1.416 (5)	N1—C20	1.348 (6)
O6—H6	0.8400	N2—H2B	0.8800
O6—C12	1.381 (6)	N2—C16	1.327 (6)
O7—H7	0.8400	N2—C17	1.380 (6)
O7—C13	1.356 (6)	N3—C18	1.416 (6)
O8—H8	0.8400	N3—C19	1.400 (6)
O8—C14	1.368 (6)	N3—C21	1.451 (6)
C1—C2	1.387 (7)	N4—C19	1.343 (6)
C1—C9	1.391 (6)	N4—C20	1.382 (6)
C2—H2A	0.9500	N4—C22	1.474 (5)
C2—C3	1.390 (6)	C16—H16	0.9500
C3—C7	1.415 (6)	C17—C18	1.399 (6)
C4—H4	1.0000	C17—C20	1.375 (6)
C4—C5	1.507 (7)	C21—H21A	0.9800
C4—C10	1.497 (6)	C21—H21B	0.9800
C5—H5A	1.0000	C21—H21C	0.9800
C5—C6	1.508 (6)	C22—H22A	0.9800
C6—C7	1.436 (6)	C22—H22B	0.9800
C7—C8	1.406 (6)	C22—H22C	0.9800
C8—C9	1.385 (6)	N5—C24	1.133 (12)
C9—H9	0.9500	C23—H23A	0.9800
C10—C11	1.387 (7)	C23—H23B	0.9800
C10—C15	1.390 (7)	C23—H23C	0.9800
C11—H11	0.9500	C23—C24	1.436 (15)
C1—O1—H1	109.5	C14—C13—C12	119.7 (4)
C8—O2—H2	109.5	O8—C14—C13	116.2 (4)
C3—O3—C4	116.0 (3)	O8—C14—C15	124.0 (5)
C5—O5—H5	109.5	C15—C14—C13	119.7 (5)
C12—O6—H6	109.5	C10—C15—H15	119.9
C13—O7—H7	109.5	C14—C15—C10	120.2 (5)
C14—O8—H8	109.5	C14—C15—H15	119.9
O1—C1—C2	121.0 (4)	C16—N1—C20	103.5 (4)
O1—C1—C9	116.3 (4)	C16—N2—H2B	126.4
C2—C1—C9	122.7 (4)	C16—N2—C17	107.2 (4)
C1—C2—H2A	120.7	C17—N2—H2B	126.4
C1—C2—C3	118.7 (4)	C18—N3—C21	118.2 (4)
C3—C2—H2A	120.7	C19—N3—C18	124.1 (4)
O3—C3—C2	117.2 (4)	C19—N3—C21	117.6 (4)
O3—C3—C7	122.6 (4)	C19—N4—C20	119.4 (4)
C2—C3—C7	120.2 (4)	C19—N4—C22	119.6 (4)
O3—C4—H4	109.0	C20—N4—C22	121.0 (4)
O3—C4—C5	108.5 (4)	N1—C16—H16	123.6
O3—C4—C10	108.4 (3)	N2—C16—N1	112.8 (4)
C5—C4—H4	109.0	N2—C16—H16	123.6
C10—C4—H4	109.0	N2—C17—C18	132.1 (4)
C10—C4—C5	112.8 (4)	C20—C17—N2	104.3 (4)
O5—C5—C4	109.6 (4)	C20—C17—C18	123.6 (4)
O5—C5—H5A	108.5	O9—C18—N3	119.3 (4)
O5—C5—C6	111.6 (4)	O9—C18—C17	128.1 (4)
C4—C5—H5A	108.5	C17—C18—N3	112.6 (4)
C4—C5—C6	110.1 (4)	O10—C19—N3	119.4 (4)
C6—C5—H5A	108.5	O10—C19—N4	121.1 (4)
O4—C6—C5	120.2 (4)	N4—C19—N3	119.4 (4)
O4—C6—C7	124.2 (4)	N1—C20—N4	127.2 (4)
C7—C6—C5	115.6 (4)	N1—C20—C17	112.1 (4)
C3—C7—C6	119.2 (4)	C17—C20—N4	120.7 (4)
C8—C7—C3	119.1 (4)	N3—C21—H21A	109.5
C8—C7—C6	121.6 (4)	N3—C21—H21B	109.5
O2—C8—C7	120.6 (4)	N3—C21—H21C	109.5
O2—C8—C9	118.6 (4)	H21A—C21—H21B	109.5
C9—C8—C7	120.8 (4)	H21A—C21—H21C	109.5
C1—C9—H9	120.8	H21B—C21—H21C	109.5
C8—C9—C1	118.4 (4)	N4—C22—H22A	109.5
C8—C9—H9	120.8	N4—C22—H22B	109.5
C11—C10—C4	122.0 (4)	N4—C22—H22C	109.5
C11—C10—C15	120.0 (4)	H22A—C22—H22B	109.5
C15—C10—C4	118.0 (5)	H22A—C22—H22C	109.5
C10—C11—H11	119.9	H22B—C22—H22C	109.5
C12—C11—C10	120.1 (5)	H23A—C23—H23B	109.5
C12—C11—H11	119.9	H23A—C23—H23C	109.5
O6—C12—C13	119.7 (4)	H23B—C23—H23C	109.5
C11—C12—O6	120.1 (4)	C24—C23—H23A	109.5
C11—C12—C13	120.2 (5)	C24—C23—H23B	109.5
O7—C13—C12	117.5 (5)	C24—C23—H23C	109.5
O7—C13—C14	122.7 (5)	N5—C24—C23	179.4 (11)
O1—C1—C2—C3	−179.7 (5)	C10—C4—C5—O5	57.6 (5)
O1—C1—C9—C8	−179.8 (5)	C10—C4—C5—C6	−179.3 (4)
O2—C8—C9—C1	179.5 (5)	C10—C11—C12—O6	−178.8 (4)
O3—C3—C7—C6	−3.8 (7)	C10—C11—C12—C13	3.0 (7)
O3—C3—C7—C8	179.8 (5)	C11—C10—C15—C14	0.3 (7)
O3—C4—C5—O5	177.6 (4)	C11—C12—C13—O7	−179.9 (4)
O3—C4—C5—C6	−59.2 (5)	C11—C12—C13—C14	−3.1 (7)
O3—C4—C10—C11	−58.7 (6)	C12—C13—C14—O8	−179.0 (4)
O3—C4—C10—C15	123.3 (4)	C12—C13—C14—C15	1.8 (7)
O4—C6—C7—C3	175.2 (5)	C13—C14—C15—C10	−0.4 (7)
O4—C6—C7—C8	−8.4 (8)	C15—C10—C11—C12	−1.6 (7)
O5—C5—C6—O4	−21.8 (7)	N2—C17—C18—O9	−0.2 (10)
O5—C5—C6—C7	159.3 (4)	N2—C17—C18—N3	−178.9 (5)
O6—C12—C13—O7	1.9 (6)	N2—C17—C20—N1	−0.1 (6)
O6—C12—C13—C14	178.7 (4)	N2—C17—C20—N4	179.3 (4)
O7—C13—C14—O8	−2.4 (7)	C16—N1—C20—N4	−179.6 (5)
O7—C13—C14—C15	178.4 (4)	C16—N1—C20—C17	−0.2 (6)
O8—C14—C15—C10	−179.6 (4)	C16—N2—C17—C18	−179.3 (6)
C1—C2—C3—O3	179.3 (4)	C16—N2—C17—C20	0.4 (6)
C1—C2—C3—C7	0.5 (8)	C17—N2—C16—N1	−0.5 (7)
C2—C1—C9—C8	0.4 (8)	C18—N3—C19—O10	176.9 (5)
C2—C3—C7—C6	175.0 (5)	C18—N3—C19—N4	−3.1 (7)
C2—C3—C7—C8	−1.4 (7)	C18—C17—C20—N1	179.6 (5)
C3—O3—C4—C5	52.0 (5)	C18—C17—C20—N4	−1.0 (8)
C3—O3—C4—C10	174.8 (4)	C19—N3—C18—O9	−178.3 (5)
C3—C7—C8—O2	−179.0 (5)	C19—N3—C18—C17	0.5 (7)
C3—C7—C8—C9	1.9 (8)	C19—N4—C20—N1	177.6 (5)
C4—O3—C3—C2	160.5 (4)	C19—N4—C20—C17	−1.7 (7)
C4—O3—C3—C7	−20.7 (7)	C20—N1—C16—N2	0.4 (6)
C4—C5—C6—O4	−143.8 (5)	C20—N4—C19—O10	−176.4 (5)
C4—C5—C6—C7	37.3 (6)	C20—N4—C19—N3	3.6 (7)
C4—C10—C11—C12	−179.5 (4)	C20—C17—C18—O9	−179.8 (5)
C4—C10—C15—C14	178.3 (4)	C20—C17—C18—N3	1.5 (7)
C5—C4—C10—C11	61.5 (5)	C21—N3—C18—O9	−1.6 (7)
C5—C4—C10—C15	−116.5 (5)	C21—N3—C18—C17	177.2 (5)
C5—C6—C7—C3	−5.9 (7)	C21—N3—C19—O10	0.1 (7)
C5—C6—C7—C8	170.5 (5)	C21—N3—C19—N4	−179.8 (5)
C6—C7—C8—O2	4.7 (8)	C22—N4—C19—O10	1.2 (8)
C6—C7—C8—C9	−174.4 (5)	C22—N4—C19—N3	−178.8 (5)
C7—C8—C9—C1	−1.4 (8)	C22—N4—C20—N1	0.1 (8)
C9—C1—C2—C3	0.1 (8)	C22—N4—C20—C17	−179.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O10^i	0.84	1.80	2.639 (4)	173
O2—H2···O4	0.84	1.89	2.631 (5)	147
O5—H5···O9^ii	0.84	2.00	2.720 (4)	143
O6—H6···N1	0.84	1.95	2.764 (5)	163
O7—H7···O1^iii	0.84	2.27	2.834 (5)	125
O8—H8···O6^iv	0.84	1.93	2.720 (5)	156
N2—H2B···O5^i	0.88	1.97	2.738 (5)	145

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