Solvatomorphism in a series of copper(II) complexes with the 5-phenyl­imidazole/perchlorate system as ligands

In the course of an investigation of the supramolecular behaviour of copper(II) complexes with the 5-phenyl­imidazole/perchlorate ligand system (`blend') remarkable solvatomorphism has been observed. By employing a variety of crystallization solvents (polar protic, polar/non-polar aprotic), a series of 12 crystalline solvatomorphs with the general formula [Cu(ClO₄)₂(LH)₄]·x(solvent) have been obtained [LH = 5-phenyl­imidazole, x(solvent) = 3.3(H₂O) (1), 2(methanol) (2), 2(ethanol) (3), 2(1-propanol) (4), 2(2-propanol) (5), 2(2-butanol) (6), 2(di­methyl­formamide) (7), 2(acetone) (8), 2(tetra­hydro­furane) (9), 2(1,4-dioxane) (10), 2(ethyl acetate) (11) and 1(di­ethyl ether) (12)]. The structures have been solved using single-crystal X-ray diffraction and the complexes were characterized by thermal analysis and infrared spectroscopy. The solvatomorphs are isostructural (triclinic, P1), with the exception of compound 9 (monoclinic, P2₁/n). The supramolecular structures and the role of the various solvents is discussed. All potential hydrogen-bond functionalities, both of the [Cu(ClO₄)₂(LH)₄] units and of the solvents, are utilized in the course of the crystallization process. The supramolecular assembly in all structures is directed by strong recurring N_imidazole–H⋯O_perchlorate motifs leading to robust scaffolds composed of the [Cu(ClO₄)₂(LH)₄] host complexes. The solvents are located in channels and, with the exception of the disordered waters in 1 and the di­ethyl ether in 12, participate in hydrogen-bonding formation with the [Cu(ClO₄)₂(LH)₄] complexes, serving as both hydrogen-bond acceptors and donors (for the polar protic solvents in 2–6), or solely as hydrogen-bond acceptors (for the polar/non-polar aprotic solvents in 7–11), linking the complexes and contributing to the stability of the crystalline compounds.

1. Introduction

The term solvatomorphism (often called pseudopolymorphism) is used for designating solvate diversity of a particular host compound (Ibragimov, 2007), or in other words, refers to the ability of a compound to yield crystal structures with unit cells that differ in their elemental composition through the inclusion of various amounts or types of solvent molecules (Brittain, 2012). In the past, a number of scientific arguments have been put forward by experts in the field regarding the use of the terms solvatomorph and pseudopolymorph (also including terms such as supramolecular isomer, false polymorph or quasipolymorph) that could describe the above category of crystalline structures (Threlfall, 1995; Nangia & Desiraju, 1999; Seddon, 2004; Desiraju, 2004; Bernstein, 2005, 2011; Nangia, 2006; Brittain, 2012; Stöger et al., 2012; du Plessis & Barbour, 2012). It seems that the term pseudopolymorphism is more widely used in the literature; however, in the present study the term solvatomorphism is used to emphasize that the crystal structures differ in the type of solvent used in their synthesis reactions. Polymorphism (Sarma & Desiraju, 1999) and solvatomorphism are interesting topics in crystal engineering in relation to the implications on the crystal packing and the potential impact on the properties (chemical, physical etc.) of crystalline solids (Nangia & Desiraju, 2019; Ranjan et al., 2020). With respect to solvatomorphism, the effect of the solvent on the organization of supramolecular systems (by forming synthons based on solute–solvent specific interactions) is of great interest, both for academic studies and practical applications (Görbitz & Hersleth, 2000; Hao et al., 2005; Mondal & Howard, 2005). For example, for some active pharmaceutical ingredients (APIs) solvatomorphs could be the ultimate pharmaceutical form for clinical use because of their advantages in improving the solubility or stability of APIs and, therefore, the performance of the drug (Yuan et al., 2020); in biological systems where a modification of the protein solvent environment by denaturation results in changes in their biological activities; in the self-assembly of MOFs (Köppen et al., 2018; Seetharaj et al., 2019); in organic and inorganic functional nanomaterials (Yamada et al., 2006; Bernard et al., 2018) etc. However, solvate/hydrate formation is a rather unpredictable process, as we are not able to tell in advance whether a solvent or a water molecule will crystallize with the solute molecule (Juarez-Garrido et al., 2022; Glasser, 2019; Li & Du, 2011).

In recent years we have studied a series of 3d metal complexes with substituted imidazole ligands to investigate the patterns followed in the assembly process of these materials, with particular interest in the intermolecular – both strong and weak – interactions (Kounavi et al., 2009, 2012a,b, 2015; Kitos et al., 2016; Duros et al., 2019). With respect to this, we sought in the present study to use the relatively small and versatile 4-phenyl­imidazole ligand (L′H) in combination with the perchlorate salt of copper(II). Copper(II) is a special metal ion in coordination chemistry with a flexible coordination sphere. It has been proven popular in metallo­supra­molecular chemistry as it favours a variety of coordination numbers and geometries (Cotton et al., 1999; Reinen, 1983) that can be realized by properly selected ligands and reaction conditions. Due to its 3d⁹ configuration, square planar or distorted tetrahedral (four-coordinate), square pyramidal or trigonal bipyramidal (five-coordinate), as well as distorted octahedral (six-coordinate) geometries characterize the coordination chemistry of copper(II). Imidazole and its derivatives have played an important role in coordination chemistry (Constable, 1996; Chen, 2016). They are also interesting ligands in bioinorganic (Lippard & Berg, 1994; Roat-Malone, 2002) and metallosupramolecular chemistry, employed, for example, in the synthesis of clusters, coordination polymers and MOFs (Desiraju, 1995; Steed & Atwood, 2009). The L′H ligand coordinates via its pyridine-type N3 atom towards mononuclear species (Fig. 1), has a hydrogen-bond donor (the pyrrolic-type N1 atom) enabling the formation of strong supramolecular motifs (Schmidt, 1971; Desiraju, 1995; Steiner, 2002; Aakeröy et al., 2010; Dunitz & Gavezzotti, 2012) and is also capable of forming π⋯π stackings (Hunter & Sanders, 1990; Janiak, 2000; Nishio et al., 2012) through its five- and six-membered aromatic rings. The perchlorate ion has been considered as a rather weak ligand to the transition metal ions (Sekizaki, 1981). However, it sometimes acts as a unidentate ligand (thus excluding the possibility of forming coordination polymers) in the presence of organic ligands. It seemed therefore interesting to study its coordination ability with regard to the present synthetic system, as well as its spatial role in the motif formation and packing organization of the complexes produced.

Figure 1 The 4-phenyl­imidazole (L′H) ligand and the crystallographically determined formulae of the isolated solvatomorphs with the general composition [Cu(ClO4)2(LH)4]·x(solvent). The initially used 4-phenyl­imidazole ligand is present in all complexes as its 5-phenyl­imidazole tautomeric form (LH). MeOH = methanol, EtOH = ethanol, 1-PrOH = 1-propanol, 2-PrOH = 2-propanol, 2-BuOH = 2-butanol, DMF = dimethylformamide, Me2CO = acetone, THF = tetrahydrofuran, EtOAc = ethyl acetate, Et2O = diethyl ether .

Remarkable solvatomorphism was obtained during crystallization experiments for the above general reaction system. Utilizing a variety of crystallization solvents (polar protic, polar/non-polar aprotic), a series of 12 crystalline solvato­morphs with the general formula [Cu(ClO₄)₂(LH)₄]·x(solvent) (Fig. 1) have been isolated and structurally characterized. Their molecular and supramolecular structures have been studied and compared to understand the effect of the solvent molecules properties, such as size, shape and intermolecular interactions, in the solvatomorph formation.

2. Experimental

All reagents and starting materials were reagent grade, purchased from Aldrich and used as received. All manipulations were performed under aerobic conditions. Microanalyses (C, H, N) were performed by the University of Patras microanalytical service. FT-IR spectra (4000–400 cm⁻¹) were recorded using a Perkin–Elmer PC 16FT-IR spectrometer with samples prepared as KBr pellets; the spectra were recorded on analytically pure, well dried samples, and not on the as-isolated crystals. Thermogravimetric analysis (TGA) studies were performed with a Shimadzu TGA 50 thermogravimetric analyser at a 10°C min⁻¹ increase rate under air.

Safety note: Perchlorate salts are potentially explosive; such compounds should be synthesized and used in small quantities, and treated with utmost care at all times.

2.1. Preparation of complexes

2.1.1. [Cu(ClO₄)₂(LH)₄]·3.3(H₂O) [1·3.3(H₂O)]

L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) were dissolved in a mixture of CH₂Cl₂ (25 ml) and MeCN (5 ml) and stirred for 30 min. The resultant turquoise solution was filtered and then layered with 50 ml of n-hexane/Et₂O (1:2 v/v ratio) to produce purple prismatic crystals after two days. The crystals were collected by filtration and dried in a vacuum desiccator over silica gel. The overall yield was 35% (based on Cu^II). Analysis calculated for C₃₆H_38.6Cl₂CuN₈O_11.3 [1·3.3(H₂O)] (found values in parentheses): C 48.01 (48.35), H 4.35 (4.22), N 12.45 (12.30)%. Selected IR bands (KBr, cm⁻¹): 3430s, 3320m, 3140s, 3018w, 1637w, 1612w, 1592m, 1486m, 1450m, 1427w, 1350w, 1269w, 1245w, 1119s, 1088s, 965m, 956m, 840m, 758s, 690s, 644m, 622s, 514w, 450w.

2.1.2. [Cu(ClO₄)₂(LH)₄]·2MeOH (2·2MeOH)

A solution of L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) in MeOH (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered and then layered with 50 ml of Et₂O (1:2 v/v ratio) to produce red prismatic crystals after two days in a 65% yield (based on Cu^II). The crystals were collected by filtration and dried in a vacuum desiccator over silica gel. Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (2) (found values in parentheses): C 51.53 (51.77), H 3.84 (3.72), N 13.35 (13.50)%. Selected IR bands (KBr, cm⁻¹): 3300m, 3144m, 3022w, 1654w, 1636w, 1614w, 1590m, 1488m, 1452m, 1424w, 1356w, 1274w, 1246w, 1122s, 1090s, 966m, 952m, 838m, 760s, 692s, 648m, 624s, 512w, 452w.

2.1.3. [Cu(ClO₄)₂(LH)₄]·2EtOH (3·2EtOH)

A solution of L′H (0.180 g, 1.25 mmol) and Cu(ClO₄)₂·6H₂O (0.185 g, 0.5 mmol) in EtOH (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered, then layered with 50 ml of n-hexane (1:2 v/v ratio) to produce purple prismatic crystals after two days in a 55% yield (based on LH). The crystals were collected by filtration and dried in a vacuum desiccator over silica gel. Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (3) (found values in parentheses): C 51.53 (51.82), H 3.84 (3.71), N 13.35 (13.58)%. Selected IR bands (KBr, cm⁻¹): 3420mb, 3314m, 3142s, 3022w, 1612w, 1590w, 1490m, 1456w, 1424w, 1358w, 1274w, 1234w, 1122s, 1088s, 966m, 952m, 840m, 762s, 692m, 648m, 626s, 508w, 452w.

2.1.4. [Cu(ClO₄)₂(LH)₄]·2(1-PrOH) [4·2(1-PrOH)]

A solution of L′H (0.180 g, 1.25 mmol) and Cu(ClO₄)₂·6H₂O (0.185 g, 0.5 mmol) in 1-PrOH (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered. Upon slow evaporation of the filtrate, purple prismatic crystals were obtained after four days, collected by filtration and dried in a vacuum desiccator over anhydrous CaCl₂; the yield was 60% (based on the LH available). Analysis calculated for C₄₂H₄₈Cl₂CuN₈O₁₀ [4·2(1-PrOH)] (found values in parentheses): C 52.58 (52.30), H 5.04 (4.79), N 11.68 (11.79)%. Selected IR bands (KBr, cm⁻¹): 3308m, 3142m, 3022w, 1616w, 1590m, 1488s, 1452m, 1424w, 1274w, 1162s, 1126s, 1088s, 966m, 952m, 836m, 760s, 692s, 624s, 510w, 446w.

2.1.5. [Cu(ClO₄)₂(LH)₄]·2(2-PrOH) [5·2(2-PrOH)]

A solution of L′H (0.180 g, 1.25 mmol) and Cu(ClO₄)₂·6H₂O (0.185 g, 0.5 mmol) in 2-PrOH (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered and then layered with 50 ml of n-hexane/Et₂O (1:2 v/v ratio) to produce light-purple prismatic crystals after two days. The crystals were collected by filtration and dried in a vacuum desiccator over anhydrous CaCl₂; the yield was 55% (based on the LH available). Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (5) (found values in parentheses): C 51.53 (51.28), H 3.84 (3.60), N 13.35 (13.51)%. Selected IR bands (KBr, cm⁻¹): 3320m, 3132s, 3017w, 1615w, 1593m, 1496m, 1458w, 1421w, 1361w, 1274w, 1160s, 1229w, 1117s, 1093s, 964m, 949m, 838m, 758s, 696m, 649m, 624s, 511w, 450w.

2.1.6. [Cu(ClO₄)₂(LH)₄]·2(2-BuOH) [6·2(2-BuOH)]

A solution of L′H (0.058 g, 0.4 mmol) and Cu(ClO₄)₂·6H₂O (0.037 g, 0.1 mmol) in 2-BuOH (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered and then layered with 50 ml of n-hexane (1:2 v/v ratio) to produce purple prismatic crystals after four days; the crystals were collected by filtration and dried in a vacuum desiccator over anhydrous CaCl₂. The overall yield was 30% (based on Cu^II). Analysis calculated for C₄₄H₅₂Cl₂CuN₈O₁₀ [6·2(2-BuOH)] (found values in parentheses): C 53.52 (53.25), H 5.31 (5.41), N 11.35 (11.50)%. Selected IR bands (KBr, cm⁻¹): 3410mb, 3318m, 3150s, 3027w, 1608w, 1587w, 1496m, 1451w, 1419w, 1353w, 1277w, 1233w, 1120s, 1086s, 964m, 952m, 837m, 764s, 692m, 651m.

2.1.7. [Cu(ClO₄)₂(LH)₄]·2DMF (7·2DMF)

L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) were dissolved in a mixture of CH₂Cl₂ (25 ml) and DMF (2 ml), and stirred for 30 min. The resultant blue solution was filtered and then layered with 50 ml of n-hexane (1:2 v/v ratio) to produce purple prismatic crystals after two days; the crystals were collected by filtration and dried in a vacuum desiccator over anhydrous CaCl₂. The overall yield was 30%. Analysis calculated for C₄₂H₄₆Cl₂CuN₁₀O₁₀ (7·2DMF) (found values in parentheses): C 51.20 (51.50), H 4.71 (4.48), N 14.22 (14.39)%. Selected IR bands (KBr, cm⁻¹): 3151m, 3027w, 1660s, 1609w, 1588m, 1496s, 1441m, 1422w, 1360w, 1254w, 1221w, 1176w, 1130s, 1086s, 1058m, 977w, 968m, 952m, 833m, 777m, 757s, 688s, 628s, 508w, 453w.

2.1.8. [Cu(ClO₄)₂(LH)₄]·2Me₂CO (8·2Me₂CO)

A solution of L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) in Me₂CO (25 ml) was stirred for 30 min. The resultant blue solution was filtered and then layered with 50 ml of n-hexane (1:2 v/v ratio) to produce purple prismatic crystals after one day; the crystals were collected by filtration and dried in air. The yield was 75% (based on Cu^II). Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (8) (found values in parentheses): C 51.53 (51.80), H 3.84 (3.71), N 13.35 (13.11)%. Selected IR bands (KBr, cm⁻¹): 3146m, 3022w, 1614w, 1590m, 1492s, 1444m, 1424w, 1364w, 1256w, 1224w, 1176w, 1126s, 1088s, 1055m, 980w, 966m, 954m, 836m, 774m, 760s, 692s, 626s, 510w, 448w.

2.1.9. [Cu(ClO₄)₂(LH)₄]·2THF (9·2THF)

A solution of L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) in THF (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered and then layered with 50 ml of Et₂O (1:2 v/v ratio) to produce pink prismatic crystals after three days; the crystals were collected by filtration and dried in a vacuum desiccator over silica gel. The yield was 35% (based on Cu^II). Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (9) (found values in parentheses): C 51.53 (51.84), H 3.84 (3.97), N 13.35 (13.06)%. Selected IR bands (KBr, cm⁻¹): 3150m, 3026w, 1611w, 1588m, 1494s, 1442m, 1420w, 1361w, 1258w, 1222w, 1174w, 1122s, 1089s, 1058m, 977w, 965m, 952m, 833m, 774m, 758s, 690s, 625s, 512w, 446w.

2.1.10. [Cu(ClO₄)₂(LH)₄]·2(1,4-dioxane) [10·2(1,4-dioxane)]

A solution of L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) in 1,4-dioxane (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered and then layered with 50 ml of Et₂O (1:2 v/v ratio) to produce pink prismatic crystals after three days; the crystals were collected by filtration and dried in a vacuum desiccator over silica gel. The yield was 15% [based on Cu^II]. Analysis calculated for C₄₄H₄₈Cl₂CuN₈O₁₂ [10·2(1,4-dioxane)] (found values in parentheses): C 52.05 (51.68), H 4.76 (4.50), N 11.04 (11.32)%. Selected IR bands (KBr, cm⁻¹): 3146m, 3028w, 1608w, 1589m, 1491s, 1445m, 1421w, 1358w, 1257w, 1218w, 1177w, 1124s, 1091s, 1057m, 980w, 963m, 950w, 830m, 772m, 761s, 688s, 626s, 512w, 445w.

2.1.11. [Cu(ClO₄)₂(LH)₄]·2EtOAc (11·2EtOAc)

A solution of L′H (0.180 g, 1.25 mmol) and Cu(ClO₄)₂·6H₂O (0.185 g, 0.5 mmol) in EtOAc (25 ml) was stirred for 30 min. The resultant turquoise solution was filtered and then stored at low temperature (5°C) to produce orange prismatic crystals after 15 days; the crystals were collected by filtration and dried in a vacuum desiccator over anhydrous CaCl₂. The yield was 25% (based on Cu^II). Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (11) (found values in parentheses): C 51.53 (51.79), H 3.84 (3.70), N 13.35 (13.19)%. Selected IR bands (KBr, cm⁻¹): 3146m, 3022w, 2980m, 1612w, 1577m, 1490s, 1448m, 1424w, 1364w, 1250w, 1168w, 1126s, 1094s, 1055m, 980w, 968m, 954m, 912w, 838m, 774m, 762s, 692s, 626s, 508w, 452w.

2.1.12. [Cu(ClO₄)₂(LH)₄]·Et₂O (12·Et₂O)

A solution of L′H (0.173 g, 1.2 mmol) and Cu(ClO₄)₂·6H₂O (0.111 g, 0.3 mmol) in MeCN (25 ml) was stirred for 30 min. The resultant blue solution was filtered and then layered with 50 ml of Et₂O (1:2 v/v ratio) to produce blue blocks after three days; the crystals were collected by filtration and dried in a vacuum desiccator over silica gel. The yield was 40% (based on Cu^II). Analysis calculated for C₃₆H₃₂Cl₂CuN₈O₈ (12) (found values in parentheses): C 51.53 (51.76), H 3.84 (3.72), N 13.35 (13.20)%. Selected IR bands (KBr, cm⁻¹): 3148m, 3022w, 1616w, 1590w, 1488s, 1445m, 1428w, 1364w, 1256w, 1224w, 1188w, 1126s, 1104m, 1088s, 1055m, 980w, 966m, 954m, 902w, 834m, 774m, 760s, 692s, 626s, 510w, 446w.

2.2. Crystallography

Suitable single crystals of the compounds, coated with paratone-N oil, were attached in cryo-loops at the end of a copper pin. Diffraction data were collected by the ω-scan technique on a Rigaku Oxford Diffraction SuperNova diffractometer under a stream of nitro­gen gas at 100 (2) K using Mo Kα radiation (λ = 0.7107 Å), except for compound 6·2(2-BuOH) where Cu Kα radiation (λ = 1.5418 Å) was used. Data were collected and processed by the CrysAlis CCD and CrysAlis RED (Rigaku Oxford Diffraction, 2015) software, respectively ; an empirical absorption correction using spherical harmonics, implemented in the SCALE3 ABSPACK scaling algorithm, was applied to the intensities of the collected reflections. The structures were solved using direct methods with SIR92 (Altomare et al., 1994) and SHELXT (Sheldrick, 2015a) and refined by full-matrix least-squares on F² with SHELXL-2014/7 (Sheldrick, 2015b). All non-H atoms were refined anisotropically; carbon-bound H atoms were included in calculated positions (riding model). All imidazole H atoms on the pyrrolic-type N1 atom of the ligands, together with the H atoms of the solvent water molecule O5 in 1·3.3(H₂O) and the hydroxyl H atoms of the methanol, ethanol, 1-propanol and 2-butanol solvent molecules in compounds 2·2MeOH, 3·2EtOH, 4·2(1-PrOH) and 6·2(2-BuOH), respectively, were located in difference Fourier maps and refined isotropically applying soft distance restraints (DFIX); however, the water O6A/O6B solvent molecule in 1·3.3(H₂O) was disordered and its hydrogen atoms could not be reliably located. Non-routine aspects of structure refinement are as follows: a phenyl ring of the ligands in complexes 2·2MeOH, 3·2EtOH and 12·Et₂O is positionally disordered and has been modelled over two sites (domain ratio: 65:35, 55:45 and 50:50, respectively); the coordinated perchlorate ions in complexes 2·2MeOH and 3·2EtOH are similarly disordered (70:30 and 56:46, respectively); disorder also affects the O6A/O6B water molecule in 1·3.3(H₂O), the MeOH solvent molecule in 2·2MeOH (65:35), the EtOH solvent in 3·2EtOH (50:50) and the di­ethyl ether solvent in 12·Et₂O (orientational disorder about a centre of symmetry). Geometric/crystallographic calculations were carried out using PLATON (Spek, 2009), OLEX2 (Dolomanov, 2009), and WinGX (Farrugia, 2012) packages; molecular/packing graphics were prepared with Mercury (Macrae et al., 2020). Experimental details are listed in Table 1.

Table 1
Experimental details for compounds 1–4 and 6–12†

Experiments were carried out at 100 K using a Rigaku Oxford Diffraction SuperNova diffractometer with an Atlas CCD detector. Absorption was corrected for by multi-scan methods (CrysAlis PRO; Rigaku Oxford Diffraction, 2015). H atoms were treated by a mixture of independent and constrained refinement.

	1	2	3	4
Crystal data
Chemical formula	C36H32Cl2CuN8O8·3.3(H2O)	C36H32Cl2CuN8O8·2(CH4O)	C36H32Cl2CuN8O8·2(C2H6O)	C36H32Cl2CuN8O8·2(C3H8O)
Mr	898.59	903.22	931.27	959.32
Crystal system, space group	Triclinic, P	Triclinic, P	Triclinic, P	Triclinic, P
a, b, c (Å)	8.8398 (6), 9.9196 (8), 12.8239 (10)	9.3557 (7), 9.838 (1), 13.0238 (10)	9.3377 (3), 9.7888 (4), 12.9870 (6)	9.1329 (6), 10.0787 (7), 13.0825 (8)
α, β, γ (°)	97.633 (6), 93.948 (6), 107.385 (7)	75.710 (8), 89.649 (6), 69.657 (8)	103.114 (5), 90.344 (5), 109.408 (4)	103.496 (6), 94.562 (5), 105.229 (6)
V (Å^3)	1056.59 (14)	1084.99 (17)	1086.13 (8)	1117.04 (13)
Z	1	1	1	1
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	0.71	0.69	0.69	0.67
Crystal size (mm)	0.25 × 0.16 × 0.15	0.20 × 0.17 × 0.13	0.17 × 0.12 × 0.10	0.21 × 0.15 × 0.11
Data collection
Tmin, Tmax	0.838, 1.000	0.896, 1.000	0.890, 1.000	0.803, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7899, 3692, 3323	15902, 3791, 3516	12262, 3812, 3397	10056, 4829, 4106
Rint	0.026	0.035	0.027	0.025
(sin θ/λ)max (Å^−1)	0.595	0.595	0.595	0.639
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.057, 0.167, 1.11	0.065, 0.172, 1.05	0.066, 0.176, 1.07	0.036, 0.094, 1.07
No. of reflections	3692	3791	3812	4829
No. of parameters	283	334	365	296
No. of restraints	19	82	423	3
Δρmax, Δρmin (e Å^−3)	1.52, −0.48	1.39, −0.96	1.12, −1.33	0.38, −0.46

	6	7	8	9
Crystal data
Chemical formula	C36H32Cl2CuN8O8·2(C4H10O)	C36H32Cl2CuN8O8·2(C3H7NO)	C36H32Cl2CuN8O8·2(C3H6O)	C36H32Cl2CuN8O8·2(C4H8O)
Mr	987.37	985.33	955.29	983.34
Crystal system, space group	Triclinic, P	Triclinic, P	Triclinic, P	Monoclinic, P21/n
a, b, c (Å)	9.4157 (5), 9.9855 (6), 13.6726 (7)	9.1544 (4), 9.8343 (5), 14.2557 (8)	9.4814 (4), 9.7136 (5), 13.3146 (9)	9.0943 (5), 25.0287 (17), 10.0253 (5)
α, β, γ (°)	106.181 (5), 96.455 (4), 106.527 (5)	91.493 (4), 107.948 (5), 109.075 (5)	69.117 (6), 80.660 (5), 68.833 (5)	90, 107.509 (6), 90
V (Å^3)	1157.64 (12)	1142.38 (11)	1067.61 (11)	2176.2 (2)
Z	1	1	1	2
Radiation type	Cu Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	2.28	0.66	0.71	0.69
Crystal size (mm)	0.16 × 0.09 × 0.09	0.25 × 0.15 × 0.15	0.16 × 0.11 × 0.10	0.23 × 0.13 × 0.13
Data collection
Tmin, Tmax	0.815, 1.000	0.757, 1.000	0.586, 1.000	0.503, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7216, 4229, 3607	8820, 4905, 4337	8762, 4579, 3483	8871, 3808, 2800
Rint	0.035	0.022	0.045	0.089
(sin θ/λ)max (Å^−1)	0.605	0.639	0.639	0.595
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.059, 0.156, 1.06	0.037, 0.095, 1.06	0.052, 0.135, 1.06	0.062, 0.157, 1.18
No. of reflections	4229	4905	4579	3808
No. of parameters	306	303	294	301
No. of restraints	3	2	1	3
Δρmax, Δρmin (e Å^−3)	1.55, −0.51	0.61, −0.46	0.86, −0.86	0.87, −0.59

	10	11	12
Crystal data
Chemical formula	C36H32Cl2CuN8O8·2(C4H8O2)	C36H32Cl2CuN8O8·2(C4H8O2)	C36H32Cl2CuN8O8·C4H10O
Mr	1015.34	1015.34	913.25
Crystal system, space group	Triclinic, P	Triclinic, P	Triclinic, P
a, b, c (Å)	9.3679 (9), 10.2347 (8), 12.5311 (15)	10.0363 (5), 10.1867 (6), 11.9902 (6)	8.6577 (4), 9.8396 (4), 12.8200 (6)
α, β, γ (°)	79.661 (8), 84.578 (9), 73.249 (8)	83.078 (5), 82.032 (4), 70.015 (5)	97.084 (4), 93.897 (4), 108.096 (4)
V (Å^3)	1130.6 (2)	1137.37 (11)	1023.61 (8)
Z	1	1	1
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm^−1)	0.67	0.67	0.73
Crystal size (mm)	0.22 × 0.10 × 0.10	0.16 × 0.13 × 0.10	0.18 × 0.11 × 0.09
Data collection
Tmin, Tmax	0.489, 1.000	0.703, 1.000	0.812, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10186, 4867, 3144	9285, 4877, 4265	7915, 4386, 4098
Rint	0.083	0.033	0.023
(sin θ/λ)max (Å^−1)	0.639	0.639	0.639
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.069, 0.184, 1.06	0.042, 0.113, 1.07	0.031, 0.083, 1.05
No. of reflections	4867	4877	4386
No. of parameters	310	312	330
No. of restraints	2	2	10
Δρmax, Δρmin (e Å^−3)	0.99, −0.59	0.66, −0.51	0.37, −0.46

†Data for 5-2(2-PrOH) are not listed.

3. Results and discussion

3.1. Comments on synthesis

Various reactions were initially explored, aimed at preparing the largest possible number of Cu^II complexes of the L′H ligand; our efforts included differing reagent ratios and concentrations, solvents, temperatures and crystallization conditions. It was soon identified that the reaction system yielded solvatomorphic compounds with the general form [Cu(ClO₄)₂(LH)₄]·x(solvent). Utilizing a variety of crystallization solvents (polar protic, polar aprotic and non-polar) a series of 12 crystalline solvatomorphs have been isolated (Fig. 1). Copper(II) is air stable and the synthetic work was thus performed under aerobic conditions in the normal laboratory atmosphere. The compounds were obtained by reactions with a metal-to-ligand ratio of 1:4 or 1:2.5 and have an octahedral geometry for the metal centre; their colour is blue. The complexes are insoluble in Et₂O, n-hexane, CH₂Cl₂ and CHCl₃, moderately soluble in alcohols, and readily soluble in DMF and DMSO. The very good solubility in the latter two solvents might indicate reactions (and therefore decomposition) of the complexes with the solvents which are strong donors, probably replacing the perchlorato groups and/or LH ligands from the coordination sphere of Cu^II. Crystals grown with 1-butanol as well as MeNO₂ solvents were of poor diffraction quality. Attempts with other solvents such as MeCN, CH₂Cl₂, CHCl₃, DMSO and pyridine did not produce the anticipated solvatomorphs. Crystals of the solvatomorph 5 with 2-propanol, [Cu(ClO₄)₂(LH)₄]·2(2-propanol), were also grown and its crystal structure was unambiguously determined allowing a description of the intermolecular association between the complex molecules and the solvent; however, due to its poor refinement indices (R₁ = 13.9%), the structure has not been deposited with the CCDC database and not listed in Tables 1 and 2. Moreover, the crystal structure is not discussed. As mentioned in the caption of Fig. 1, the initially used 4-phenyl­imidazole (L′H) has been transformed to its 5-phenyl­imidazole (LH) when coordinated to copper(II) in the present complexes. Tautomerism occurs when two (or more) constitutional isomers of different connectivity exist in a dynamic equilibrium with each other. The most often observed case of tautomerism is the prototropic tautomerism which involves a transfer of a proton from one position in a molecule to another. For cyclic compounds, the H atom can be exchanged between ring atoms (annular tautomerism) or between a ring and side-chain atoms (side-chain tautomerism). Thus, the L′H → LH transformation observed in complexes 1−12 is annular tautomerism. Two polymorphs of L′H have been characterized by single-crystal X-ray crystallography (Claramunt et al., 2002). Solid state ¹³C and ¹⁵N NMR studies have revealed that L′H is the only tautomer that exists as free compound in the solid state. In solution, both tautomers exist. Since the complexes were formed in solution, it appears that LH is the thermodynamically stable tautomer when it is coordinated to copper(II). A possible reason for the observed preference is the position of the donor atom, i.e. N3. This would be close enough to the phenyl ring in complexes of L′H creating a steric hindrance, but far from the phenyl ring in the 5-tautomer (LH) relieving the hindrance. The preference should also be associated with subtle supramolecular characteristics in the crystal structures of the copper(II) complexes of LH and especially with the strength of the hydrogen bonds. Various trials to obtain crystals of the solvent-free form (including solvothermal reactions, tri­ethyl orthoformate as a drying agent, and solvent mixtures) were in vain. The crystalline products were characterized by IR spectroscopy, microanalyses, single-crystal X-ray diffraction and TGA experiments for selected compounds. It should be mentioned at this point that some complexes, i.e. 2·2MeOH, 3·2EtOH, 5·2(2-PrOH), 8·2Me₂CO, 9·2THF, 11·2EtOAc and 12·Et₂O, were analysed as lattice solvent-free (2, 3, 5, 8, 9, 11 and 12), while for the rest, the crystallographic formula appears the same as the analytical formula (as obtained from C, H and N microanalyses).

Table 2
The dihedral angles (°) between the least-squares calculated planes through the atoms of the imidazole (I) and phenyl rings (R) A and B of the [Cu(ClO₄)₂(LH)₄] molecules for the 11 solvatomorphs studied†‡§

Compound	IA/IB	IA/RA	IB/RB
1	83.0 (2)	17.4 (2)	27.5 (2)
2	81.3 (2)	13.9 (2)	27.3 (6)
3	82.4 (2)	12.8 (2)	31.9 (5)
4	89.6 (1)	20.1 (1)	13.2 (1)
6	84.3 (1)	18.0 (2)	11.4 (2)
7	72.5 (1)	2.7 (1)	22.3 (1)
8	73.7 (1)	18.4 (2)	35.1 (1)
9	87.3 (2)	11.9 (2)	31.2 (2)
10	85.1 (2)	11.5 (2)	21.6 (3)
11	88.6 (1)	10.5 (1)	6.5 (2)
12	80.3 (1)	16.3 (1)	22.2 (2)

†IA: Imidazole ring N1A/C2A/N3A/C4A/C5A; IB: Imidazole ring N1B/C2B/N3B/C4B/C5B; RA: Phenyl ring C6A/C7A/C8A/C9A/C10A/C11A; RB: Phenyl ring C6B/C7B/C8B/C9B/C10B/C11B.
‡Data for compound 5·2(2-PrOH) are not listed.
§The numbering scheme of the complexes does not include the solvent molecules.

3.2. Description of the structures

To facilitate discussion and comparison, the exact same numbering scheme has been assigned (where applicable) to the LH ligand atoms and the coordinated perchlorate ions for all compounds presented herein (Fig. 2 and S1–S10).

Figure 2 A view of the structure of solvatomorph 1·3.3(H2O). Displacement ellipsoids are drawn at the 50% probability level. Atoms generated by symmetry through the inversion centre located on the copper atom are not labelled. Both orientations of the disordered water solvent molecule O6 are shown.

The compounds crystallize in the space group , with the exception of 9·2THF which crystallizes in P2₁/n (Table 1). The asymmetric unit of all compounds contains half a [Cu(ClO₄)₂(LH)₄] host complex (Z′ = ½), with the copper(II) atom situated on an inversion centre. Each copper centre has a slightly distorted octahedral N₄O₂ coordination involving a pyridine-type nitro­gen atom from each ligand in the equatorial positions and an oxygen atom from each terminal perchlorate in the axial positions. The Cu^II—O_perchlorato bonds are weak (2.49–2.73 Å) and thus the metal centre is in an axially elongated octahedral environment (4+2); this is a consequence of the Jahn–Teller effect, typical for 3d⁹ systems. The bond lengths and angles observed for the current complexes are similar. To compare the conformation of the [Cu(ClO₄)₂(LH)₄] complexes in the 12 solvatomorphs, Table 2 lists the relative orientation of the imidazole rings within each complex, as well as the orientation of the phenyl ring relative to the imidazole ring in each LH ligand. It can be seen that the conformation of the complexes is similar, with some differences that presumably help to minimize steric hindrance among the ligands, accommodate the incorporated solvents (taking into account their size and molecular shape) and allow them to engage in strong hydrogen-bonding patterns. The deviation in the orientation between the imidazole rings A and B in the complexes is 17.1° (89.6–72.5°), while that between the phenyl rings and the imidazole to which each ring is attached is, as expected, higher: 17.4° (20.1–2.7°) for ligands A, and 28.6° (35.1–6.5°) for ligands B. We could postulate that since the phenyl rings are further away from the core and are not engaged as strong synthons, they are more flexible to orient themselves and accommodate better within the crystal space. In view of the similarities in the space group, the unit-cell dimensions/volumes and the conformation of the [Cu(ClO₄)₂(LH)₄] host complexes, the compounds can be described as isostructural (Bombicz, 2024). However, the different hydrogen-bonding capabilities of the solvent molecules lead to variations in the structurally significant intermolecular interactions (see below).

The observed solvatomorphs were sorted into three categories on the basis of the type of solvent incorporated and the subsequent hydrogen-bonding patterns formed. There are two solvent molecules per centrosymmetric [Cu(ClO₄)₂(LH)₄] complex, with the exception of the hydrate 1 (3.3 disordered water molecules) and the solvate 12 (one di­ethyl ether molecule lying on an inversion centre).

3.2.1. Polar protic solvents: compounds 1–6

The solvents contained in these compounds are water (1), methanol (MeOH) (2), ethanol (EtOH) (3), 1-propanol (1-PrOH) (4), 2-propanol (2-PrOH) (5) and 2-butanol (2-BuOH) (6). These solvents have an effective donor–acceptor capability and are therefore expected to participate in multi-point recognition, e.g. in solute–solvent hydrogen bonding. At the same time, the [Cu(ClO₄)₂(LH)₄] molecule itself possesses classic hydrogen-bond donors (the imidazole N—H group) and acceptors (the perchlorate oxygen atoms) which in turn could be involved in solute–solute bonding. In all, except in the water-containing compound 1, the packing organization is the same. Packing diagrams of compounds 1·3.3(H₂O) and 2·2MeOH are shown in Figs. 3 and 4, respectively, and that of compound 6·2(2-BuOH) in Fig. S11. The main hydrogen-bonding motifs in the compounds are listed in Table 3. The [Cu(ClO₄)₂(LH)₄] molecules are directly linked via robust N1A—H1A⋯O4_perchlorate synthons along the b axis. The second donor group N1B—H1B of the complex is bridged to another perchlorate by the incorporated alcohol along the a axis. The solvents act both as donors and as acceptors forming doubly hydrogen-bonded synthons N1B—H1B⋯O5_alcohol—H⋯O2_perchlorate. Thus, the linked molecules form rigid 2D layers parallel with the ab plane, with the solvents situated on either side of the layers. In the hydrated compound 1, the water molecules are highly disordered, they occupy almost the same position in the unit cell as the solvents in compounds 2–6, but do not bridge neighbouring [Cu(ClO₄)₂(LH)₄] complexes. Instead, the N1B—H1B donor and the O2_perchlorate acceptor are directly linked through the N1B—H1B⋯O2_perchlorate interaction, compensating for the absence of the bridging solvent by proper rotations of the imidazole and perchlorate groups involved. There is a notable number of aromatic rings in the complexes; however, only a few π⋯π interactions have been identified in their crystal structures (Table S1) between rings of adjacent layers contributing to the structure extension and stabilization in 3D. It seems that these weak interactions only occur when they are sterically allowed and certainly not at the expense of the structure-directing synthons which are fully exploited.

Table 3
Geometry (Å, °) of the strong hydrogen-bonding motifs in compounds 1–4 and 6–12†

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
1
N1A—H11A⋯O4^i	0.84 (2)	2.06 (4)	2.836 (4)	154 (5)
N1B—H1B⋯O2^ii	0.83 (2)	2.22 (3)	2.993 (5)	156 (4)
O5—H5A⋯O6A	0.89 (4)	2.04 (3)	2.721 (17)	133 (5)
O5—H5A⋯O6B	0.89 (4)	2.04 (4)	2.925 (15)	176 (6)
2
N1A—H11A⋯O4B^iii	0.86 (3)	1.98 (4)	2.763 (9)	152 (5)
N1B—H1B⋯O5^iii	0.86 (4)	1.95 (4)	2.796 (8)	168 (5)
O5—H5⋯O2A^iv	0.89 (11)	1.87 (11)	2.727 (19)	163 (9)
3
N1A—H11A⋯O4B^i	0.86 (2)	2.09 (4)	2.777 (8)	136 (5)
N1B—H1B⋯O5^i	0.86 (2)	1.94 (2)	2.801 (6)	176 (6)
O5–H5A⋯O2A^v	0.84 (2)	1.91 (2)	2.719 (13)	162 (8)
4
N1A—H11A⋯O4^vi	0.86 (2)	1.97 (2)	2.789 (3)	160 (2)
N1B—H1B⋯O5^vii	0.86 (2)	1.95 (2)	2.804 (3)	175 (2)
O5—H5⋯O2^viii	0.84 (3)	2.00 (3)	2.839 (3)	173 (3)
6
N1A—H11A⋯O4^iii	0.85 (4)	1.96 (4)	2.787 (5)	164 (5)
N1B—H1B⋯O5^ix	0.86 (3)	1.96 (3)	2.808 (4)	172 (3)
O5—H5⋯O2^x	0.83 (5)	2.03 (6)	2.854 (5)	170 (5)
7
N1A—H11A⋯O4^i	0.85 (2)	2.00 (2)	2.821 (3)	162 (2)
N1B—H1B⋯O5	0.85 (3)	1.95 (3)	2.776 (3)	164 (3)
8
N1A—H11A⋯O4^x	0.85 (2)	2.20 (3)	2.944 (4)	146 (3)
N1B—H1B⋯O5	0.87 (4)	2.01 (4)	2.854 (4)	164 (3)
9
N1A—H11A⋯O4^xi	0.85 (2)	2.05 (3)	2.859 (5)	160 (5)
N1B—H1B⋯O5^xii	0.86 (3)	2.06 (4)	2.869 (6)	157 (4)
10
N1A—H11A⋯O4^i	0.85 (2)	1.98 (3)	2.810 (5)	163 (4)
N1B—H1B⋯O5	0.86 (4)	2.01 (4)	2.848 (6)	164 (5)
11
N1A—H11A⋯O4^xiii	0.85 (2)	2.35 (2)	2.946 (3)	128 (2)
N1B—H1B⋯O5^xiv	0.86 (3)	1.98 (3)	2.827 (3)	170 (3)
12
N1A—H11A⋯O4^iii	0.85 (2)	2.01 (2)	2.804 (2)	154 (2)
N1B—H1B⋯O2^xv	0.85 (2)	2.24 (2)	2.968 (2)	144 (2)
Symmetry codes: (i) x, y + 1, z; (ii) x − 1, y, z; (iii) x, y − 1, z; (iv) −x + 1, −y + 1, −z; (v) x, y − 1, z; (vi) −x, −y − 1, −z; (vii) −x, −y, − z; (viii) − x + 1, − y, − z; (ix) x − 1, y − 1, y − 1; (x) − x, −y + 1, −z + 1; (xi) x, y, y − 1; (xii) x + 1, y, z; (xiii) −x + 1, − y + 1, −z + 2; (xiv) −x + 2, −y + 1, −z + 2; (xv) −x, − y + 1, −z.

†The numbering scheme of the complexes does not include the solvent molecules.

Figure 3 View of a 2D layer of the crystal structure of solvatomorph 1·3.3(H2O) organized by hydrogen-bonding motifs. The water molecules are labelled as O5 and O6A/O6B. Hanging contacts are represented by dotted lines in red. Only the H atoms involved in strong intermolecular interactions are drawn. Atoms generated by symmetry operations have been included, but have been labelled identically to the asymmetric unit.

Figure 4 View of a 2D layer of the crystal structure of solvatomorph 2·2MeOH organized by hydrogen-bonding motifs. The atoms of the methanol molecule are labelled as O5 and C12A. Only the H atoms involved in strong intermolecular interactions are drawn. For clarity, only the major components of the disordered groups of the structure are shown. The MeOH molecules are directed along the a axis of the unit cell. Hanging contacts are represented by dotted lines in red. Atoms generated by symmetry operations have been included, but have been labelled identically to the asymmetric unit.

3.2.2. Polar aprotic solvents: compounds 7–10

The solvents involved in this group are di­methyl­formamide (DMF) (7), acetone (Me₂CO) (8), tetra­hydro­furan (THF) (9) and 1,4-dioxane (10), featuring only hydrogen-bond acceptors. The supramolecular self-assembly in 7, 8 and 9 is based on the same pattern observed in compounds 2−6: the [Cu(ClO₄)₂(LH)₄] molecules are linked via N1A—H1A⋯O4_perchlorate synthons forming 1D tapes along the b axis (for 7 and 8) and along the c axis (for 9 in the space group P2₁/n). The solvents are only terminally hydrogen bonded to the second donor group of the structure, namely N1B—H1B⋯O5_solvent. A view of the packing of compound 7·2DMF is shown in Fig. 5 and those of 8·2Me₂CO and 9·2THF in Fig. S12. The pattern of π⋯π interactions observed in compounds 1–6 is also present in 7–9 (Table S1). However, some of these interactions are disrupted in compound 9 due to the interference of THF solvents between aromatic rings. In compound 10 the asymmetric unit contains two halves of 1,4-dioxane solvent molecules and the supramolecular arrangement is somewhat different. Due to their special position within the unit cell, the two dioxane molecules are arranged alternately in channels along the b-axis direction [Fig. 6(a)]. As in all previous structures 1–9, the [Cu(ClO₄)₂(LH)₄] molecules are directly linked via the N1A—H1A⋯O4_perchlorate pattern along the b axis. The first 1,4-dioxane molecule (O5) is doubly hydrogen bonded, via its two centrosymmetrically related oxygen atoms (O5 and O5*), connecting two neighbouring [Cu(ClO₄)₂(LH)₄] molecules in the [101] direction: N1B—H1B⋯O5–//–O5*⋯H1B*—N1B*. Thus, the structure is organized in 2D layers parallel with the plane [Fig. 6(b)]. Some weak π⋯π interactions between these layers help to organize the structure into a 3D assembly. Similar to compound 9, the positioning of the 1,4-dioxane molecules within the layers prevents the formation of some π⋯π interactions as was the case in some of the previously discussed structures 1–8. The second 1,4-dioxane molecule (O6) is not involved in any major bonding pattern, except for two weak C12—H12B⋯O6 interactions with the first dioxane molecule (O5) on either side and running within the solvent channel along the b axis.

Figure 5 1D tape in the crystal structure of solvatomorph 7·2DMF formed by the [Cu(ClO4)2(LH)4] molecules via N1A—H1A⋯O4perchlorate synthons along the b axis. The DMF solvents are only terminally hydrogen-bonded to the host complexes. Atoms generated by symmetry operations have been included, but have been labelled identically to the asymmetric unit.

Figure 6 (a) The dioxane molecules in compound 10·2(1,4-dioxane) filling the channels along the b axis in the middle of the unit cell. Only the H atoms involved in the interactions are shown. (b) The 2D layer formed by N1A—H1A⋯O4 interactions between the LH ligands and the perchlorate ions along b, and N1B—H1B⋯O5 interactions between the ligands and the 1,4-dioxane molecules in the [101] direction. Hanging contacts are drawn by red dotted lines. The dioxane molecules are highlighted.

3.2.3. Non-polar solvents: compounds 11 and 12

The solvatomorph with ethyl acetate (EtOAc) (compound 11) has been included in this category; EtOAc is commonly referred to as a non-polar to weak polar aprotic solvent. The supramolecular self-assembly in 11 (Fig. S13) is based on the same pattern as in compounds 7 and 8. Namely, the [Cu(ClO₄)₂(LH)₄] molecules are linked via N1A—H1A⋯O4_perchlorate synthons forming 1D tapes and the ethyl acetate solvents are only terminally hydrogen bonded through their carbonyl oxygen atom to the second donor group of the structure: N1B—H1B⋯O5_solvent. However, the 1D tapes spread along the a axis, not b as in compounds 7 and 8. All aromatic rings of the [Cu(ClO₄)₂(LH)₄] molecule are involved in π⋯π interactions (Table S1), adding to the stability of the resulting 3D structure. There is one di­ethyl ether (Et₂O) molecule in the unit cell of compound 12 lying on an inversion centre (Fig. 7). The Et₂O molecule links two adjacent [Cu(ClO₄)₂(LH)₄] units via weak sp³ C—H⋯O_perchlorate interactions, but it is not involved in any hydrogen-bonding motif. Consequently, the structure-organizing pattern is based on synthons between the donor and acceptor groups of the [Cu(ClO₄)₂(LH)₄] complex itself, the same as those observed in the structure of solvatomorph 1, in which the disordered water solvents do not participate in the hydrogen-bonding scheme. This means that the [Cu(ClO₄)₂(LH)₄] complexes are linked via strong hydrogen bonds between the N1A—H1A and N1B—H1B donor groups and the perchlorate ions of neighbouring complexes along b and a axes, respectively, thus forming 2D layers parallel with the ab plane. As with the previous structures, some weak π⋯π interactions between aromatic rings of adjacent layers help to extend and stabilize the structure in 3D (Table S1).

Figure 7 View of a 2D layer of the crystal structure of solvatomorph 12·Et2O organized by hydrogen-bonding motifs. For clarity, only one orientation of the disordered groups of the structure is shown. The atoms of the di­ethyl ether solvent are labelled as O5, C12A C13A. Only the H atoms involved in strong intermolecular interactions are drawn. The di­ethyl ether molecules are directed along the a axis of the unit cell. Hanging contacts are represented by dotted lines in red.

A number of weak C—H⋯O intra- and intermolecular contacts that enhance the stability of the supramolecular assembly are also present in the 12 structures discussed. A few C—H⋯π interactions were also observed for each structure and a complete list of these, with the relevant geometrical parameters, is presented in Table S2. These interactions (Nishio et al., 1998, 2009) are the weakest hydrogen bonds that operate between a soft acid CH and a soft or intermediate base π system and it has been recognized that this type of weak interaction plays a role in crystal packing, host–guest chemistry, self-assembly and chiral recognition. As can be seen in Table S2, most of these interactions are of the C(aromatic)—H⋯π type, along with a few C(sp³)—H⋯π (originating from the methyl/methyl­ene groups of the solvents).

3.2.4. Location of the solvents in the crystal structures

Inspection of the solvatomorphs shows that the solvent molecules are situated in channels (Gallagher & Mocilac, 2021) within their crystal structures. Based on PLATON analysis, the calculated void space of the channels (after the removal of the solvent molecules of the structures) ranges from 15.9% to 26.9% of the unit-cell volume. That is, 20.7% for 1·3.3(H₂O), 18.1% for 2·2MeOH, 15.9% for 3·2EtOH, 24.7% for 4·2(1-PrOH), 26.6% for 6·2(2-BuOH), 26.9% for 7·2DMF, 19.7% for 8·2Me₂CO, 22.2% for 9·2THF, 24.4% for 10·2(1,4-dioxane), 26.6% for 11·2EtOAc and 16.3% for 12·Et₂O (with one Et₂O molecule in the unit cell). The solvent channels of the structures in (except 10) are directed along the a axis of the unit cell (e.g. see Fig. 4 for 2·2MeOH). As previously reported, the asymmetric unit of 10 contains two half 1,4-dioxane molecules lying in special positions of symmetry and this results in somewhat different solvent packing, with the two dioxane molecules arranged alternately in channels along the b-axis direction [Fig. 6(b) and S14]. In the solvatomorph 9·2THF, crystallizing in P2₁/n, the solvent channels run parallel to the direction [101] (Fig. 8).

Figure 8 The crystal structure of solvatomorph 9·2THF showing the solvent channels running parallel to the direction [101]. (a) The THF solvent molecules are highlighted. (b) The solvents have been removed and the channels containing them are drawn in yellow (VOIDS option in MERCURY software; Macrae et al., 2020).

3.2.5. Brief discussion on TGA and IR results

The TGA patterns of selected complexes (Fig. S15) in the 25–800 °C region indicate similar decomposition schemes. The measurements were performed on freshly (i.e. not dried) microcrystalline samples of the complexes. Upon heating the solvent molecules are gradually lost at temperatures up to ∼160 °C depending on the solvent that is present in the compound. Then a plateau appears up to ∼280 °C indicating that the unsolvated complexes are thermally stable below this temperature. Two points deserve a comment here. First, complex 12 is thermally stable because the volatile Et₂O solvent is readily lost in the air during the grinding of the crystals before the measurement. Second, the experimental mass loss due to the removal of the solvents is lower than the theoretical one. For example, the experimental mass loss for 3·2EtOH in the 25–145 °C region is 6.9%, while the theoretical one (for the removal of two moles of EtOH per mole of the complex) is 9.9%. This can be attributed to the fact that an amount of solvent has been already lost at room temperature from the microcrystalline powder before the measurement; this observation is reinforced by the fact that the crystals gradually transform to crystalline powders at room temperature (presumably because of a partial solvent loss).

In the IR spectra of the well dried complexes, the medium-intensity bands in the 3320−3100 cm⁻¹ range are attributed to the stretching vibration of the N—H bond, v(H). In the spectrum of 1·3.3(H₂O), the v(OH)_water vibration appears at ∼3430 cm⁻¹. The v(OH) bands of 1-PrOH and 2-BuOH appear at ∼ 3415 cm⁻¹ in the spectra of the corresponding complexes. The rather low wavenumber and broadness of these bands are indicative of hydrogen bonds which are present in the crystal structures. Such bands do not appear in 2·2MeOH, 3·2EtOH and 5·2(2-PrOH) because the samples used were solvent-free (see Section 2.1). For the same reason, the characteristic v(CO) modes of Me₂CO and EtOAc do not appear in the spectra of 8·2Me₂CO and 11·2EtOAc. In contrast, the spectrum of 7·2DMF exhibits the characteristic carbonyl stretch, v(CO), of DMF because this solvent is retained in the sample after drying and hence when recording the IR spectrum. A characteristic feature of all spectra is the appearance of bands due to the perchlorate ligands. The free ClO₄⁻ ion belongs to the high-symmetry point group T_d. Of the four vibration fundamentals, only v₃(F₂)[v_d(ClO)] and v₄(F₂)[δ_d(ClO)] are IR-active. If the symmetry of the ion is lowered by coordination, the degenerate vibrations split and Raman-active modes appear in the IR spectrum. The lowering of symmetry caused by coordination is different for complexes containing monodentate (C_3v) and bidentate (C_2v) perchlorato groups (Nakamoto, 1986). For the former the v₁(A₁), v₂(E), v₃(A₁), v₃(E), v₄(A₁) and v₄(E) should appear in the IR spectrum. These bands are clearly visible at ∼965, ∼450, ∼1090, ∼1120, ∼645 and ∼625 cm⁻¹, respectively. The v₃ bands show signs of further splitting (appearance of a band at ∼950 cm⁻¹) which might be an indication of a further symmetry lowering to C_2v. This spectral observation can be explained by the involvement of the uncoordinated perchlorate oxygen atoms in hydrogen bonding which creates a pseudobridging (bidentate or even tridentate) ClO₄⁻.

4. Conclusions

The complex of copper(II) with the 5-phenyl­imidazole/perchlorate ligand system exhibits a remarkable ability to form solvatomorphs and has been crystallized as a solvated form from a large number of polar protic, polar aprotic and non-polar solvents. It includes H₂O (1), MeOH (2), EtOH (3), 1-PrOH (4), 2-PrOH (5), 2-BuOH (6), DMF (7), Me₂CO (8), THF (9), 1,4-dioxane (10), EtOAc (11) and Et₂O (12). There are two solvent molecules per [Cu(ClO₄)₂(LH)₄] unit, except for the hydrate 1 (containing 3.3 disordered H₂O molecules) and the solvate 12 (with one Et₂O molecule). The complexes are isostructural and crystallize in the space group , whereas the THF solvate 9 crystallizes in the space group P2₁/n. The [Cu(ClO₄)₂(LH)₄] host molecules in the solvatomorphs have similar conformations with small differences in the orientation of the aromatic rings, possibly to comply with steric hindrance, facilitate the formation of hydrogen-bonding synthons and accommodate the various incorporated solvents.

The [Cu(ClO₄)₂(LH)₄] complexes form a host framework and the solvent molecules reside in channels along the a axis of the unit cell, except for the 1,4-dioxane molecules in 10 which are in special positions and are arranged in channels along the b axis, and the THF molecules in 9 (in the P2₁/n) which are located in channels along [101]. The calculated void space of the channels, after the removal of the solvent molecules, ranges from 15.9% to 26.9% of the unit-cell volume. That is, solvent molecules containing two to six light non-H atoms (C, O, N) have been found to be readily incorporated into the channels of the complexes' structure.

All potential hydrogen-bond functionalities of the [Cu(ClO₄)₂(LH)₄] units and the solvents are utilized in the course of the crystallization process. Analysis of the crystal packing shows that the supramolecular assembly is directed by strong recurring N—H⋯ motifs among the [Cu(ClO₄)₂(LH)₄] host molecules. The solvents are located in channels and, with the exception of the disordered waters in 1 and the di­ethyl ether molecule in 12, are involved in the formation of hydrogen bonds with the [Cu(ClO₄)₂(LH)₄] units, serving as both hydrogen-bond acceptors and donors by bridging the complexes (for the polar protic solvents in 2–6), or solely as hydrogen-bond acceptors terminally linked to the complex molecules (for the polar/non-polar aprotic solvents in 7–11). Since the molecules of the complexes are bridged by the guest solvent molecules (but not only by them), the latter can be considered as having a type of templating behaviour.

Work is in progress in our laboratories to: (a) extend this type of chemistry in analogous systems with other, non-Jahn–Teller distorted divalent metals, e.g. Mn^II, Fe^II, Co^II, Ni^II and Zn^II and to understand if the supramolecular characteristics of octahedral [M(ClO₄)₂(5-phenyl­imidazole)₄] complexes depend on the metal ion; (b) prepare and study Cu^II complexes with the 5-phenyl­imidazole/X⁻ `blends' where X⁻ is the nitrate, tetra­fluoro­borate, trifluoromethanesulfonate and sulfate ion in order to investigate their molecular structures and supramolecular motifs of the products; and (c) synthesize 3d-metal complexes containing the 4-phenyl­imidazole tautomer (Fig. 1). Also, we have in mind to support selected experimental data with DFT calculations.

Supporting information

Computing details

(1)

Crystal data

C36H32Cl2CuN8O8·3.3(H2O)	Z = 1
Mr = 898.59	F(000) = 464
Triclinic, P1	Dx = 1.412 Mg m^−3
a = 8.8398 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9196 (8) Å	Cell parameters from 4296 reflections
c = 12.8239 (10) Å	θ = 4.2–29.1°
α = 97.633 (6)°	µ = 0.71 mm^−1
β = 93.948 (6)°	T = 100 K
γ = 107.385 (7)°	Block, purple
V = 1056.59 (14) Å^3	0.25 × 0.16 × 0.15 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	3692 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3323 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.026
ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→10
Tmin = 0.838, Tmax = 1.000	k = −11→11
7899 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: mixed
wR(F^2) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0898P)^2 + 2.5027P] where P = (Fo^2 + 2Fc^2)/3
3692 reflections	(Δ/σ)max < 0.001
283 parameters	Δρmax = 1.52 e Å^−3
19 restraints	Δρmin = −0.48 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu	0.0000	0.0000	0.0000	0.0141 (2)
N1A	0.2544 (4)	0.3929 (3)	−0.0718 (3)	0.0182 (7)
H1A	0.261 (5)	0.4794 (17)	−0.069 (4)	0.027*
C2A	0.1320 (4)	0.3015 (4)	−0.0354 (3)	0.0182 (8)
H2A	0.0443	0.3255	−0.0084	0.022*
N3A	0.1508 (4)	0.1730 (3)	−0.0425 (2)	0.0158 (6)
C4A	0.2929 (4)	0.1841 (4)	−0.0853 (3)	0.0169 (7)
H4A	0.3369	0.1081	−0.0999	0.020*
C5A	0.3604 (4)	0.3213 (4)	−0.1032 (3)	0.0161 (7)
C6A	0.5095 (4)	0.3868 (4)	−0.1462 (3)	0.0168 (7)
C7A	0.5389 (5)	0.5155 (4)	−0.1861 (3)	0.0249 (9)
H7A	0.4604	0.5634	−0.1856	0.030*
C8A	0.6809 (5)	0.5739 (4)	−0.2263 (4)	0.0301 (10)
H8A	0.7003	0.6624	−0.2519	0.036*
C9A	0.7961 (5)	0.5033 (4)	−0.2294 (3)	0.0271 (9)
H9A	0.8929	0.5426	−0.2582	0.032*
C10A	0.7681 (5)	0.3757 (4)	−0.1902 (3)	0.0238 (8)
H10A	0.8460	0.3272	−0.1921	0.029*
C11A	0.6261 (5)	0.3179 (4)	−0.1480 (3)	0.0198 (8)
H11A	0.6085	0.2310	−0.1203	0.024*
N1B	−0.3739 (4)	−0.0806 (3)	−0.2365 (3)	0.0197 (7)
H1B	−0.4731 (13)	−0.103 (5)	−0.242 (4)	0.030*
C2B	−0.3095 (4)	−0.0665 (4)	−0.1371 (3)	0.0186 (8)
H2B	−0.3689	−0.0903	−0.0795	0.022*
N3B	−0.1521 (4)	−0.0150 (3)	−0.1289 (2)	0.0166 (6)
C4B	−0.1152 (5)	0.0046 (4)	−0.2297 (3)	0.0210 (8)
H4B	−0.0104	0.0416	−0.2486	0.025*
C5B	−0.2521 (5)	−0.0370 (4)	−0.2985 (3)	0.0212 (8)
C6B	−0.2824 (5)	−0.0466 (5)	−0.4140 (3)	0.0281 (9)
C7B	−0.4178 (6)	−0.1482 (5)	−0.4710 (4)	0.0385 (11)
H7B	−0.4911	−0.2114	−0.4349	0.046*
C8B	−0.4463 (7)	−0.1579 (6)	−0.5798 (4)	0.0470 (14)
H8B	−0.5388	−0.2273	−0.6182	0.056*
C9B	−0.3403 (7)	−0.0669 (7)	−0.6316 (4)	0.0497 (15)
H9B	−0.3596	−0.0733	−0.7061	0.060*
C10B	−0.2067 (7)	0.0332 (8)	−0.5768 (4)	0.0558 (16)
H10B	−0.1341	0.0960	−0.6136	0.067*
C11B	−0.1767 (6)	0.0436 (7)	−0.4675 (4)	0.0445 (13)
H11B	−0.0835	0.1129	−0.4299	0.053*
Cl	0.22971 (10)	−0.22173 (9)	−0.13429 (7)	0.0176 (2)
O1	0.1021 (3)	−0.1595 (3)	−0.1400 (2)	0.0241 (6)
O2	0.2815 (4)	−0.2450 (3)	−0.2376 (2)	0.0324 (7)
O3	0.3620 (3)	−0.1267 (3)	−0.0618 (2)	0.0258 (6)
O4	0.1729 (3)	−0.3566 (3)	−0.0967 (2)	0.0273 (7)
O5	0.1278 (4)	0.3709 (4)	0.6721 (3)	0.0465 (9)
H5A	0.173 (6)	0.399 (6)	0.616 (2)	0.070*
H5B	0.169 (6)	0.445 (4)	0.718 (3)	0.070*
O6A	0.099 (2)	0.3508 (16)	0.4575 (13)	0.075 (3)	0.3
O6B	0.2741 (18)	0.4773 (14)	0.4891 (12)	0.075 (3)	0.35

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0148 (3)	0.0139 (3)	0.0131 (3)	0.0038 (2)	−0.0003 (2)	0.0031 (2)
N1A	0.0202 (16)	0.0126 (15)	0.0237 (16)	0.0077 (13)	0.0033 (13)	0.0031 (13)
C2A	0.0185 (18)	0.0183 (18)	0.0183 (18)	0.0063 (15)	0.0008 (14)	0.0036 (14)
N3A	0.0190 (15)	0.0153 (15)	0.0130 (15)	0.0054 (12)	0.0007 (12)	0.0021 (12)
C4A	0.0194 (18)	0.0174 (18)	0.0155 (17)	0.0086 (14)	0.0015 (14)	0.0019 (14)
C5A	0.0182 (18)	0.0152 (17)	0.0153 (17)	0.0073 (14)	−0.0016 (14)	0.0004 (14)
C6A	0.0184 (18)	0.0163 (18)	0.0134 (17)	0.0043 (14)	−0.0006 (14)	−0.0016 (14)
C7A	0.023 (2)	0.0204 (19)	0.034 (2)	0.0093 (16)	0.0053 (17)	0.0061 (17)
C8A	0.029 (2)	0.023 (2)	0.040 (2)	0.0063 (17)	0.0086 (19)	0.0119 (18)
C9A	0.020 (2)	0.029 (2)	0.028 (2)	0.0031 (17)	0.0045 (16)	0.0007 (17)
C10A	0.0181 (19)	0.028 (2)	0.024 (2)	0.0093 (16)	−0.0020 (16)	−0.0010 (16)
C11A	0.0244 (19)	0.0177 (18)	0.0168 (18)	0.0082 (15)	−0.0024 (15)	−0.0001 (14)
N1B	0.0143 (15)	0.0232 (16)	0.0208 (17)	0.0071 (13)	−0.0024 (13)	0.0002 (13)
C2B	0.0192 (18)	0.0209 (18)	0.0171 (18)	0.0080 (15)	0.0029 (15)	0.0035 (15)
N3B	0.0187 (15)	0.0162 (15)	0.0158 (15)	0.0072 (12)	0.0011 (12)	0.0021 (12)
C4B	0.0214 (19)	0.030 (2)	0.0148 (18)	0.0112 (16)	0.0020 (15)	0.0066 (15)
C5B	0.026 (2)	0.026 (2)	0.0156 (19)	0.0144 (16)	0.0019 (15)	0.0019 (15)
C6B	0.034 (2)	0.044 (3)	0.016 (2)	0.027 (2)	−0.0006 (17)	0.0036 (17)
C7B	0.050 (3)	0.040 (3)	0.025 (2)	0.021 (2)	−0.011 (2)	−0.003 (2)
C8B	0.066 (4)	0.057 (3)	0.022 (2)	0.035 (3)	−0.012 (2)	−0.007 (2)
C9B	0.064 (4)	0.086 (4)	0.017 (2)	0.056 (3)	−0.003 (2)	−0.003 (2)
C10B	0.050 (3)	0.105 (5)	0.028 (3)	0.040 (3)	0.014 (2)	0.026 (3)
C11B	0.032 (3)	0.080 (4)	0.023 (2)	0.018 (3)	0.0013 (19)	0.015 (2)
Cl	0.0170 (4)	0.0143 (4)	0.0222 (5)	0.0064 (3)	0.0017 (3)	0.0017 (3)
O1	0.0200 (13)	0.0202 (14)	0.0355 (16)	0.0113 (11)	0.0013 (12)	0.0053 (12)
O2	0.0301 (16)	0.0406 (18)	0.0251 (15)	0.0106 (14)	0.0067 (13)	−0.0008 (13)
O3	0.0187 (13)	0.0233 (14)	0.0318 (16)	0.0062 (11)	−0.0028 (12)	−0.0039 (12)
O4	0.0230 (14)	0.0190 (14)	0.0440 (18)	0.0092 (11)	0.0050 (13)	0.0125 (12)
O5	0.045 (2)	0.048 (2)	0.0366 (19)	0.0122 (17)	−0.0064 (16)	−0.0190 (16)
O6A	0.096 (6)	0.057 (4)	0.084 (5)	0.028 (4)	0.033 (5)	0.037 (4)
O6B	0.096 (6)	0.057 (4)	0.084 (5)	0.028 (4)	0.033 (5)	0.037 (4)

Geometric parameters (Å, º)

Cu—N3A	2.000 (3)	N1B—H1B	0.833 (10)
Cu—N3A^i	2.000 (3)	C2B—N3B	1.322 (5)
Cu—N3B^i	2.018 (3)	C2B—H2B	0.9500
Cu—N3B	2.018 (3)	N3B—C4B	1.380 (5)
N1A—C2A	1.345 (5)	C4B—C5B	1.367 (5)
N1A—C5A	1.385 (5)	C4B—H4B	0.9500
N1A—H1A	0.839 (10)	C5B—C6B	1.472 (5)
C2A—N3A	1.326 (5)	C6B—C11B	1.377 (7)
C2A—H2A	0.9500	C6B—C7B	1.395 (7)
N3A—C4A	1.385 (5)	C7B—C8B	1.386 (7)
C4A—C5A	1.370 (5)	C7B—H7B	0.9500
C4A—H4A	0.9500	C8B—C9B	1.369 (9)
C5A—C6A	1.465 (5)	C8B—H8B	0.9500
C6A—C11A	1.396 (5)	C9B—C10B	1.369 (9)
C6A—C7A	1.398 (5)	C9B—H9B	0.9500
C7A—C8A	1.383 (6)	C10B—C11B	1.393 (7)
C7A—H7A	0.9500	C10B—H10B	0.9500
C8A—C9A	1.398 (6)	C11B—H11B	0.9500
C8A—H8A	0.9500	Cl—O1	1.441 (3)
C9A—C10A	1.384 (6)	Cl—O3	1.441 (3)
C9A—H9A	0.9500	Cl—O4	1.441 (3)
C10A—C11A	1.394 (6)	Cl—O2	1.443 (3)
C10A—H10A	0.9500	O5—H5A	0.885 (15)
C11A—H11A	0.9500	O5—H5B	0.847 (14)
N1B—C2B	1.331 (5)	O6A—O6B	1.66 (2)
N1B—C5B	1.382 (5)
N3A—Cu—N3A^i	180.0	C2B—N1B—H1B	113 (3)
N3A—Cu—N3B^i	90.99 (12)	C5B—N1B—H1B	138 (3)
N3A^i—Cu—N3B^i	89.01 (12)	N3B—C2B—N1B	111.2 (3)
N3A—Cu—N3B	89.01 (12)	N3B—C2B—H2B	124.4
N3A^i—Cu—N3B	90.99 (12)	N1B—C2B—H2B	124.4
N3B^i—Cu—N3B	180.0	C2B—N3B—C4B	105.7 (3)
C2A—N1A—C5A	108.7 (3)	C2B—N3B—Cu	126.1 (3)
C2A—N1A—H1A	121 (3)	C4B—N3B—Cu	127.6 (2)
C5A—N1A—H1A	130 (3)	C5B—C4B—N3B	109.8 (3)
N3A—C2A—N1A	110.4 (3)	C5B—C4B—H4B	125.1
N3A—C2A—H2A	124.8	N3B—C4B—H4B	125.1
N1A—C2A—H2A	124.8	C4B—C5B—N1B	104.9 (3)
C2A—N3A—C4A	106.2 (3)	C4B—C5B—C6B	132.9 (4)
C2A—N3A—Cu	125.8 (3)	N1B—C5B—C6B	122.2 (4)
C4A—N3A—Cu	128.0 (2)	C11B—C6B—C7B	119.0 (4)
C5A—C4A—N3A	109.7 (3)	C11B—C6B—C5B	120.5 (4)
C5A—C4A—H4A	125.1	C7B—C6B—C5B	120.5 (4)
N3A—C4A—H4A	125.1	C8B—C7B—C6B	120.6 (5)
C4A—C5A—N1A	104.9 (3)	C8B—C7B—H7B	119.7
C4A—C5A—C6A	130.7 (3)	C6B—C7B—H7B	119.7
N1A—C5A—C6A	124.5 (3)	C9B—C8B—C7B	119.5 (5)
C11A—C6A—C7A	118.8 (3)	C9B—C8B—H8B	120.2
C11A—C6A—C5A	119.0 (3)	C7B—C8B—H8B	120.2
C7A—C6A—C5A	122.3 (3)	C10B—C9B—C8B	120.6 (4)
C8A—C7A—C6A	120.6 (4)	C10B—C9B—H9B	119.7
C8A—C7A—H7A	119.7	C8B—C9B—H9B	119.7
C6A—C7A—H7A	119.7	C9B—C10B—C11B	120.4 (6)
C7A—C8A—C9A	120.3 (4)	C9B—C10B—H10B	119.8
C7A—C8A—H8A	119.9	C11B—C10B—H10B	119.8
C9A—C8A—H8A	119.9	C6B—C11B—C10B	119.9 (5)
C10A—C9A—C8A	119.5 (4)	C6B—C11B—H11B	120.1
C10A—C9A—H9A	120.2	C10B—C11B—H11B	120.1
C8A—C9A—H9A	120.2	O1—Cl—O3	109.46 (17)
C9A—C10A—C11A	120.3 (4)	O1—Cl—O4	108.85 (16)
C9A—C10A—H10A	119.9	O3—Cl—O4	109.49 (17)
C11A—C10A—H10A	119.9	O1—Cl—O2	110.20 (18)
C10A—C11A—C6A	120.5 (4)	O3—Cl—O2	109.37 (17)
C10A—C11A—H11A	119.7	O4—Cl—O2	109.44 (18)
C6A—C11A—H11A	119.7	H5A—O5—H5B	101 (4)
C2B—N1B—C5B	108.4 (3)

Symmetry code: (i) −x, −y, −z.

(2)

Crystal data

C36H32Cl2CuN8O8·2(CH4O)	Z = 1
Mr = 903.22	F(000) = 467
Triclinic, P1	Dx = 1.382 Mg m^−3
a = 9.3557 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.838 (1) Å	Cell parameters from 8876 reflections
c = 13.0238 (10) Å	θ = 3.1–28.8°
α = 75.710 (8)°	µ = 0.69 mm^−1
β = 89.649 (6)°	T = 100 K
γ = 69.657 (8)°	Prism, red
V = 1084.99 (17) Å^3	0.20 × 0.17 × 0.13 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	3791 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3516 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.035
ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.896, Tmax = 1.000	k = −11→11
15902 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: mixed
wR(F^2) = 0.172	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0915P)^2 + 2.8379P] where P = (Fo^2 + 2Fc^2)/3
3791 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 1.39 e Å^−3
82 restraints	Δρmin = −0.96 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu	0.0000	0.0000	0.0000	0.0244 (2)
N1A	0.2751 (4)	−0.3818 (3)	−0.0779 (2)	0.0286 (7)
H1A	0.285 (5)	−0.469 (3)	−0.085 (4)	0.043*
C2A	0.1511 (4)	−0.2971 (4)	−0.0415 (3)	0.0288 (8)
H2A	0.0653	−0.3249	−0.0213	0.035*
N3A	0.1644 (3)	−0.1685 (3)	−0.0374 (2)	0.0250 (6)
C4A	0.3046 (4)	−0.1738 (4)	−0.0718 (3)	0.0251 (7)
H4A	0.3458	−0.0970	−0.0767	0.030*
C5A	0.3766 (4)	−0.3063 (4)	−0.0982 (3)	0.0249 (7)
C6A	0.5236 (4)	−0.3638 (4)	−0.1405 (3)	0.0295 (8)
C7A	0.5616 (5)	−0.4865 (4)	−0.1835 (3)	0.0378 (9)
H7A	0.4904	−0.5351	−0.1860	0.045*
C8A	0.7026 (6)	−0.5382 (5)	−0.2227 (4)	0.0473 (11)
H8A	0.7273	−0.6222	−0.2519	0.057*
C9A	0.8067 (6)	−0.4703 (6)	−0.2199 (4)	0.0542 (13)
H9A	0.9032	−0.5067	−0.2472	0.065*
C10A	0.7710 (6)	−0.3475 (6)	−0.1769 (4)	0.0561 (13)
H10A	0.8432	−0.3000	−0.1749	0.067*
C11A	0.6310 (5)	−0.2944 (5)	−0.1373 (4)	0.0432 (10)
H11A	0.6073	−0.2106	−0.1079	0.052*
N1B	0.2795 (4)	−0.1090 (5)	0.2767 (3)	0.0461 (9)
H1B	0.370 (3)	−0.129 (7)	0.304 (4)	0.069*
C2B	0.2518 (5)	−0.0680 (5)	0.1700 (3)	0.0414 (10)
H2B	0.3250	−0.0550	0.1213	0.050*
N3B	0.1095 (4)	−0.0484 (3)	0.1424 (2)	0.0284 (7)
C4B	0.0435 (4)	−0.0801 (4)	0.2355 (3)	0.0343 (9)
H4B	−0.0596	−0.0750	0.2401	0.041*
C5B	0.1487 (5)	−0.1202 (5)	0.3209 (3)	0.0422 (11)
C6B	0.1625 (17)	−0.1359 (14)	0.4335 (5)	0.043 (5)	0.357 (18)
C7B	0.2580 (18)	−0.1080 (15)	0.5006 (8)	0.056 (5)	0.357 (18)
H7B	0.3277	−0.0610	0.4715	0.067*	0.357 (18)
C8B	0.2514 (19)	−0.1489 (16)	0.6100 (7)	0.068 (6)	0.357 (18)
H8B	0.3166	−0.1299	0.6559	0.082*	0.357 (18)
C9B	0.1494 (19)	−0.2177 (17)	0.6525 (5)	0.052 (6)	0.357 (18)
H9B	0.1450	−0.2457	0.7274	0.062*	0.357 (18)
C10B	0.0540 (16)	−0.2456 (17)	0.5855 (8)	0.062 (5)	0.357 (18)
H10B	−0.0157	−0.2926	0.6145	0.074*	0.357 (18)
C11B	0.0605 (15)	−0.2047 (15)	0.4760 (7)	0.053 (5)	0.357 (18)
H11B	−0.0047	−0.2237	0.4302	0.064*	0.357 (18)
C6C	0.1275 (8)	−0.1807 (9)	0.4350 (3)	0.032 (2)	0.643 (18)
C7C	0.2057 (8)	−0.1521 (8)	0.5128 (4)	0.043 (2)	0.643 (18)
H7C	0.2708	−0.0961	0.4929	0.051*	0.643 (18)
C8C	0.1887 (8)	−0.2056 (10)	0.6196 (3)	0.051 (4)	0.643 (18)
H8C	0.2421	−0.1861	0.6728	0.061*	0.643 (18)
C9C	0.0935 (8)	−0.2875 (12)	0.6487 (3)	0.064 (3)	0.643 (18)
H9C	0.0818	−0.3241	0.7217	0.076*	0.643 (18)
C10C	0.0153 (8)	−0.3161 (12)	0.5709 (5)	0.078 (3)	0.643 (18)
H10C	−0.0498	−0.3721	0.5908	0.094*	0.643 (18)
C11C	0.0323 (8)	−0.2627 (11)	0.4641 (4)	0.059 (3)	0.643 (18)
H11C	−0.0211	−0.2822	0.4110	0.070*	0.643 (18)
Cl	0.23884 (13)	0.24685 (13)	−0.13218 (8)	0.0438 (3)
O1	0.1628 (4)	0.1711 (4)	−0.0620 (3)	0.0501 (8)
O2A	0.239 (2)	0.2079 (19)	−0.2377 (15)	0.044 (4)	0.3
O3A	0.3777 (16)	0.261 (2)	−0.1141 (11)	0.068 (4)	0.3
O4A	0.1474 (16)	0.3971 (12)	−0.1072 (13)	0.061 (4)	0.3
O2B	0.1839 (9)	0.2611 (12)	−0.2371 (8)	0.072 (3)	0.7
O3B	0.4006 (6)	0.1590 (7)	−0.1004 (5)	0.0598 (15)	0.7
O4B	0.2095 (10)	0.3943 (8)	−0.1380 (7)	0.079 (2)	0.7
O5	0.5622 (7)	0.8036 (8)	0.3920 (5)	0.127 (2)
H5	0.621 (12)	0.820 (11)	0.340 (7)	0.191*
C12A	0.6285 (17)	0.6510 (15)	0.4651 (12)	0.127 (2)	0.65
H12A	0.7399	0.6129	0.4628	0.191*	0.65
H12B	0.5856	0.5838	0.4431	0.191*	0.65
H12C	0.6040	0.6553	0.5377	0.191*	0.65
C12B	0.657 (3)	0.730 (4)	0.4822 (19)	0.127 (2)	0.35
H12D	0.7297	0.7810	0.4871	0.191*	0.35
H12E	0.7138	0.6265	0.4805	0.191*	0.35
H12F	0.5972	0.7309	0.5441	0.191*	0.35

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0246 (3)	0.0307 (4)	0.0176 (3)	−0.0089 (3)	−0.0007 (2)	−0.0071 (2)
N1A	0.0394 (18)	0.0243 (15)	0.0243 (15)	−0.0141 (14)	−0.0001 (13)	−0.0063 (12)
C2A	0.0340 (19)	0.0348 (19)	0.0217 (17)	−0.0181 (16)	−0.0001 (14)	−0.0058 (15)
N3A	0.0304 (16)	0.0261 (15)	0.0185 (14)	−0.0107 (13)	−0.0022 (12)	−0.0047 (11)
C4A	0.0280 (18)	0.0227 (17)	0.0243 (17)	−0.0096 (14)	−0.0013 (14)	−0.0047 (13)
C5A	0.0309 (18)	0.0231 (16)	0.0185 (16)	−0.0099 (14)	−0.0041 (13)	−0.0011 (13)
C6A	0.0340 (19)	0.0234 (17)	0.0234 (18)	−0.0031 (15)	−0.0018 (14)	−0.0029 (14)
C7A	0.043 (2)	0.0283 (19)	0.035 (2)	−0.0039 (17)	−0.0013 (17)	−0.0085 (16)
C8A	0.051 (3)	0.035 (2)	0.041 (2)	0.004 (2)	0.002 (2)	−0.0131 (19)
C9A	0.041 (3)	0.061 (3)	0.045 (3)	0.002 (2)	0.011 (2)	−0.016 (2)
C10A	0.041 (3)	0.069 (3)	0.062 (3)	−0.021 (2)	0.013 (2)	−0.023 (3)
C11A	0.038 (2)	0.048 (2)	0.048 (3)	−0.016 (2)	0.0102 (19)	−0.020 (2)
N1B	0.040 (2)	0.058 (2)	0.0356 (19)	−0.0081 (18)	−0.0169 (16)	−0.0170 (17)
C2B	0.036 (2)	0.060 (3)	0.033 (2)	−0.021 (2)	−0.0038 (17)	−0.0135 (19)
N3B	0.0289 (16)	0.0347 (17)	0.0206 (15)	−0.0084 (13)	−0.0016 (12)	−0.0100 (12)
C4B	0.0302 (19)	0.040 (2)	0.0202 (18)	0.0016 (16)	−0.0007 (15)	−0.0072 (15)
C5B	0.039 (2)	0.046 (2)	0.026 (2)	0.0081 (19)	−0.0052 (17)	−0.0150 (18)
C6B	0.045 (9)	0.030 (8)	0.047 (10)	−0.003 (6)	−0.007 (7)	−0.015 (6)
C7B	0.086 (13)	0.065 (10)	0.035 (7)	−0.047 (9)	−0.012 (7)	−0.015 (7)
C8B	0.094 (15)	0.059 (10)	0.048 (9)	−0.022 (10)	−0.022 (9)	−0.015 (8)
C9B	0.067 (12)	0.066 (11)	0.013 (7)	−0.020 (9)	−0.006 (8)	0.003 (7)
C10B	0.069 (8)	0.065 (8)	0.039 (7)	−0.012 (6)	0.005 (6)	−0.008 (6)
C11B	0.073 (13)	0.052 (9)	0.020 (7)	−0.006 (9)	−0.011 (7)	−0.007 (7)
C6C	0.033 (4)	0.038 (5)	0.014 (4)	0.002 (4)	−0.007 (3)	−0.009 (3)
C7C	0.043 (5)	0.054 (5)	0.029 (4)	−0.011 (3)	−0.013 (3)	−0.016 (3)
C8C	0.058 (6)	0.066 (7)	0.017 (4)	−0.012 (5)	−0.006 (4)	−0.008 (4)
C9C	0.060 (5)	0.103 (8)	0.017 (4)	−0.025 (5)	−0.005 (3)	0.000 (4)
C10C	0.085 (6)	0.117 (8)	0.040 (4)	−0.061 (6)	−0.002 (4)	0.001 (4)
C11C	0.067 (5)	0.086 (6)	0.030 (4)	−0.043 (5)	−0.002 (3)	−0.006 (4)
Cl	0.0465 (6)	0.0568 (7)	0.0348 (5)	−0.0335 (5)	0.0004 (4)	−0.0016 (5)
O1	0.064 (2)	0.0514 (19)	0.0496 (19)	−0.0350 (17)	0.0183 (16)	−0.0175 (15)
O2A	0.067 (11)	0.058 (8)	0.036 (7)	−0.043 (8)	0.021 (8)	−0.032 (7)
O3A	0.048 (7)	0.111 (10)	0.052 (7)	−0.042 (8)	0.010 (5)	−0.015 (7)
O4A	0.075 (7)	0.061 (7)	0.061 (7)	−0.056 (6)	−0.016 (5)	0.007 (5)
O2B	0.051 (5)	0.126 (8)	0.037 (3)	−0.031 (5)	0.001 (3)	−0.016 (5)
O3B	0.024 (2)	0.069 (4)	0.096 (4)	−0.012 (3)	0.012 (2)	−0.045 (4)
O4B	0.094 (5)	0.056 (4)	0.091 (6)	−0.048 (4)	−0.033 (4)	0.004 (3)
O5	0.092 (3)	0.155 (4)	0.114 (4)	−0.022 (3)	−0.052 (3)	−0.028 (3)
C12A	0.092 (3)	0.155 (4)	0.114 (4)	−0.022 (3)	−0.052 (3)	−0.028 (3)
C12B	0.092 (3)	0.155 (4)	0.114 (4)	−0.022 (3)	−0.052 (3)	−0.028 (3)

Geometric parameters (Å, º)

Cu—N3B^i	1.991 (3)	C7B—C8B	1.3900
Cu—N3B	1.991 (3)	C7B—H7B	0.9500
Cu—N3A	1.992 (3)	C8B—C9B	1.3900
Cu—N3A^i	1.992 (3)	C8B—H8B	0.9500
N1A—C2A	1.335 (5)	C9B—C10B	1.3900
N1A—C5A	1.383 (5)	C9B—H9B	0.9500
N1A—H1A	0.857 (10)	C10B—C11B	1.3900
C2A—N3A	1.327 (5)	C10B—H10B	0.9500
C2A—H2A	0.9500	C11B—H11B	0.9500
N3A—C4A	1.371 (5)	C6C—C7C	1.3900
C4A—C5A	1.370 (5)	C6C—C11C	1.3900
C4A—H4A	0.9500	C7C—C8C	1.3900
C5A—C6A	1.456 (5)	C7C—H7C	0.9500
C6A—C7A	1.390 (5)	C8C—C9C	1.3900
C6A—C11A	1.403 (6)	C8C—H8C	0.9500
C7A—C8A	1.383 (6)	C9C—C10C	1.3900
C7A—H7A	0.9500	C9C—H9C	0.9500
C8A—C9A	1.365 (8)	C10C—C11C	1.3900
C8A—H8A	0.9500	C10C—H10C	0.9500
C9A—C10A	1.391 (8)	C11C—H11C	0.9500
C9A—H9A	0.9500	Cl—O4B	1.362 (7)
C10A—C11A	1.380 (7)	Cl—O3A	1.384 (13)
C10A—H10A	0.9500	Cl—O1	1.386 (3)
C11A—H11A	0.9500	Cl—O2B	1.420 (10)
N1B—C2B	1.348 (6)	Cl—O3B	1.459 (5)
N1B—C5B	1.376 (6)	Cl—O2A	1.515 (17)
N1B—H1B	0.857 (10)	Cl—O4A	1.542 (9)
C2B—N3B	1.315 (5)	O5—C12B	1.357 (16)
C2B—H2B	0.9500	O5—C12A	1.483 (11)
N3B—C4B	1.374 (5)	O5—H5	0.89 (2)
C4B—C5B	1.375 (4)	C12A—H12A	0.9800
C4B—H4B	0.9500	C12A—H12B	0.9800
C5B—C6B	1.438 (6)	C12A—H12C	0.9800
C5B—C6C	1.498 (5)	C12B—H12D	0.9800
C6B—C7B	1.3900	C12B—H12E	0.9800
C6B—C11B	1.3900	C12B—H12F	0.9800
N3B^i—Cu—N3B	180.0	C6B—C7B—C8B	120.0
N3B^i—Cu—N3A	89.00 (12)	C6B—C7B—H7B	120.0
N3B—Cu—N3A	91.01 (12)	C8B—C7B—H7B	120.0
N3B^i—Cu—N3A^i	91.00 (12)	C9B—C8B—C7B	120.0
N3B—Cu—N3A^i	89.00 (12)	C9B—C8B—H8B	120.0
N3A—Cu—N3A^i	180.00 (14)	C7B—C8B—H8B	120.0
C2A—N1A—C5A	108.7 (3)	C8B—C9B—C10B	120.0
C2A—N1A—H1A	122 (3)	C8B—C9B—H9B	120.0
C5A—N1A—H1A	129 (3)	C10B—C9B—H9B	120.0
N3A—C2A—N1A	110.5 (3)	C11B—C10B—C9B	120.0
N3A—C2A—H2A	124.7	C11B—C10B—H10B	120.0
N1A—C2A—H2A	124.7	C9B—C10B—H10B	120.0
C2A—N3A—C4A	106.2 (3)	C10B—C11B—C6B	120.0
C2A—N3A—Cu	124.6 (3)	C10B—C11B—H11B	120.0
C4A—N3A—Cu	129.1 (2)	C6B—C11B—H11B	120.0
C5A—C4A—N3A	110.0 (3)	C7C—C6C—C11C	120.0
C5A—C4A—H4A	125.0	C7C—C6C—C5B	118.1 (4)
N3A—C4A—H4A	125.0	C11C—C6C—C5B	121.9 (4)
C4A—C5A—N1A	104.5 (3)	C6C—C7C—C8C	120.0
C4A—C5A—C6A	131.3 (3)	C6C—C7C—H7C	120.0
N1A—C5A—C6A	124.1 (3)	C8C—C7C—H7C	120.0
C7A—C6A—C11A	118.8 (4)	C9C—C8C—C7C	120.0
C7A—C6A—C5A	121.9 (4)	C9C—C8C—H8C	120.0
C11A—C6A—C5A	119.3 (3)	C7C—C8C—H8C	120.0
C8A—C7A—C6A	120.3 (4)	C10C—C9C—C8C	120.0
C8A—C7A—H7A	119.9	C10C—C9C—H9C	120.0
C6A—C7A—H7A	119.9	C8C—C9C—H9C	120.0
C9A—C8A—C7A	120.9 (4)	C11C—C10C—C9C	120.0
C9A—C8A—H8A	119.5	C11C—C10C—H10C	120.0
C7A—C8A—H8A	119.5	C9C—C10C—H10C	120.0
C8A—C9A—C10A	119.7 (4)	C10C—C11C—C6C	120.0
C8A—C9A—H9A	120.2	C10C—C11C—H11C	120.0
C10A—C9A—H9A	120.2	C6C—C11C—H11C	120.0
C11A—C10A—C9A	120.3 (5)	O4B—Cl—O1	118.5 (5)
C11A—C10A—H10A	119.8	O3A—Cl—O1	128.5 (6)
C9A—C10A—H10A	119.8	O4B—Cl—O2B	99.4 (6)
C10A—C11A—C6A	120.1 (4)	O1—Cl—O2B	107.9 (5)
C10A—C11A—H11A	120.0	O4B—Cl—O3B	110.4 (4)
C6A—C11A—H11A	120.0	O1—Cl—O3B	104.2 (3)
C2B—N1B—C5B	108.4 (3)	O2B—Cl—O3B	117.1 (4)
C2B—N1B—H1B	119 (4)	O3A—Cl—O2A	107.6 (9)
C5B—N1B—H1B	132 (4)	O1—Cl—O2A	109.6 (6)
N3B—C2B—N1B	110.8 (4)	O3A—Cl—O4A	92.6 (10)
N3B—C2B—H2B	124.6	O1—Cl—O4A	91.9 (6)
N1B—C2B—H2B	124.6	O2A—Cl—O4A	127.6 (10)
C2B—N3B—C4B	106.2 (3)	C12B—O5—H5	106 (9)
C2B—N3B—Cu	131.1 (3)	C12A—O5—H5	113 (7)
C4B—N3B—Cu	122.5 (2)	O5—C12A—H12A	109.5
N3B—C4B—C5B	109.9 (3)	O5—C12A—H12B	109.5
N3B—C4B—H4B	125.1	H12A—C12A—H12B	109.5
C5B—C4B—H4B	125.1	O5—C12A—H12C	109.5
C4B—C5B—N1B	104.7 (3)	H12A—C12A—H12C	109.5
C4B—C5B—C6B	142.8 (7)	H12B—C12A—H12C	109.5
N1B—C5B—C6B	110.5 (7)	O5—C12B—H12D	109.5
C4B—C5B—C6C	126.2 (4)	O5—C12B—H12E	109.5
N1B—C5B—C6C	128.7 (4)	H12D—C12B—H12E	109.5
C7B—C6B—C11B	120.0	O5—C12B—H12F	109.5
C7B—C6B—C5B	134.1 (8)	H12D—C12B—H12F	109.5
C11B—C6B—C5B	105.7 (7)	H12E—C12B—H12F	109.5

Symmetry code: (i) −x, −y, −z.

(3)

Crystal data

C36H32Cl2CuN8O8·2(C2H6O)	Z = 1
Mr = 931.27	F(000) = 483
Triclinic, P1	Dx = 1.424 Mg m^−3
a = 9.3377 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7888 (4) Å	Cell parameters from 6342 reflections
c = 12.9870 (6) Å	θ = 2.9–28.8°
α = 103.114 (5)°	µ = 0.69 mm^−1
β = 90.344 (5)°	T = 100 K
γ = 109.408 (4)°	Prism, purple
V = 1086.13 (8) Å^3	0.17 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	3812 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3397 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.027
ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.890, Tmax = 1.000	k = −11→11
12262 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.066	Hydrogen site location: mixed
wR(F^2) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0851P)^2 + 2.6183P] where P = (Fo^2 + 2Fc^2)/3
3812 reflections	(Δ/σ)max < 0.001
365 parameters	Δρmax = 1.12 e Å^−3
423 restraints	Δρmin = −1.33 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu	0.0000	0.0000	0.5000	0.0294 (2)
Cl	0.23383 (15)	−0.24826 (17)	0.36963 (9)	0.0597 (4)
O1	0.1642 (5)	−0.1719 (4)	0.4419 (3)	0.0610 (9)
O2A	0.2214 (14)	−0.1930 (10)	0.2702 (7)	0.060 (3)	0.44
O3A	0.3902 (10)	−0.2390 (16)	0.3890 (8)	0.089 (3)	0.44
O4A	0.2077 (11)	−0.3924 (10)	0.3429 (7)	0.058 (2)	0.44
O2B	0.1766 (10)	−0.2726 (12)	0.2643 (6)	0.081 (3)	0.56
O3B	0.3923 (7)	−0.1525 (7)	0.4034 (7)	0.0557 (18)	0.56
O4B	0.1582 (12)	−0.4023 (8)	0.3912 (7)	0.090 (3)	0.56
N1A	0.2757 (4)	0.3830 (4)	0.4230 (3)	0.0391 (8)
H1A	0.292 (6)	0.473 (2)	0.420 (4)	0.059*
C2A	0.1504 (5)	0.2980 (4)	0.4580 (3)	0.0362 (9)
H2A	0.0652	0.3272	0.4780	0.043*
N3A	0.1621 (4)	0.1678 (3)	0.4607 (2)	0.0321 (7)
C4A	0.3022 (4)	0.1722 (4)	0.4261 (3)	0.0332 (8)
H4A	0.3426	0.0938	0.4202	0.040*
C5A	0.3750 (5)	0.3052 (4)	0.4014 (3)	0.0329 (8)
C6A	0.5224 (5)	0.3622 (4)	0.3594 (3)	0.0385 (9)
C7A	0.5624 (6)	0.4887 (5)	0.3198 (4)	0.0495 (11)
H7A	0.4931	0.5412	0.3201	0.059*
C8A	0.7019 (7)	0.5392 (5)	0.2798 (4)	0.0604 (14)
H8A	0.7276	0.6256	0.2524	0.073*
C9A	0.8034 (7)	0.4652 (6)	0.2796 (4)	0.0655 (16)
H9A	0.8992	0.5001	0.2520	0.079*
C10A	0.7659 (6)	0.3395 (7)	0.3197 (5)	0.0644 (14)
H10A	0.8365	0.2886	0.3202	0.077*
C11A	0.6259 (6)	0.2878 (6)	0.3591 (4)	0.0510 (11)
H11A	0.6003	0.2010	0.3861	0.061*
N1B	−0.2872 (5)	−0.1037 (5)	0.2275 (3)	0.0561 (11)
H1B	−0.377 (3)	−0.126 (7)	0.198 (5)	0.084*
C2B	−0.2556 (6)	−0.0664 (6)	0.3331 (4)	0.0513 (12)
H2B	−0.3274	−0.0557	0.3831	0.062*
N3B	−0.1120 (4)	−0.0466 (3)	0.3587 (2)	0.0336 (7)
C4B	−0.0497 (5)	−0.0731 (5)	0.2637 (3)	0.0419 (10)
H4B	0.0534	−0.0664	0.2566	0.050*
C5B	−0.1573 (6)	−0.1103 (5)	0.1815 (3)	0.0511 (12)
C6B	−0.1358 (14)	−0.1748 (13)	0.0644 (4)	0.051 (3)	0.45
C7B	−0.2193 (12)	−0.1513 (12)	−0.0147 (6)	0.064 (3)	0.45
H7B	−0.2888	−0.0993	0.0038	0.076*	0.45
C8B	−0.2012 (12)	−0.2038 (13)	−0.1208 (5)	0.063 (3)	0.45
H8B	−0.2583	−0.1878	−0.1748	0.076*	0.45
C9B	−0.0996 (12)	−0.2798 (13)	−0.1479 (5)	0.074 (3)	0.45
H9B	−0.0873	−0.3157	−0.2204	0.089*	0.45
C10B	−0.0161 (12)	−0.3033 (14)	−0.0688 (7)	0.093 (4)	0.45
H10B	0.0534	−0.3552	−0.0873	0.112*	0.45
C11B	−0.0342 (14)	−0.2508 (14)	0.0373 (6)	0.079 (4)	0.45
H11B	0.0229	−0.2668	0.0914	0.095*	0.45
C6C	−0.1628 (12)	−0.1333 (10)	0.0683 (3)	0.052 (3)	0.55
C7C	−0.2657 (10)	−0.1092 (10)	0.0029 (5)	0.060 (3)	0.55
H7C	−0.3389	−0.0676	0.0330	0.072*	0.55
C8C	−0.2614 (9)	−0.1461 (9)	−0.1066 (5)	0.066 (3)	0.55
H8C	−0.3317	−0.1296	−0.1513	0.079*	0.55
C9C	−0.1543 (9)	−0.2070 (9)	−0.1507 (3)	0.058 (3)	0.55
H9C	−0.1514	−0.2322	−0.2256	0.069*	0.55
C10C	−0.0515 (9)	−0.2311 (8)	−0.0853 (5)	0.066 (3)	0.55
H10C	0.0217	−0.2728	−0.1154	0.079*	0.55
C11C	−0.0557 (10)	−0.1943 (9)	0.0242 (4)	0.058 (2)	0.55
H11C	0.0146	−0.2107	0.0689	0.069*	0.55
O5	0.4253 (7)	0.8213 (7)	0.1209 (5)	0.1168 (19)
H5A	0.370 (11)	0.838 (8)	0.170 (8)	0.175*	0.5
H5B	0.353 (9)	0.826 (17)	0.158 (6)	0.175*	0.5
C12A	0.350 (2)	0.7459 (19)	0.0205 (10)	0.112 (5)	0.5
H12A	0.4240	0.7419	−0.0333	0.134*	0.5
H12B	0.2824	0.7965	−0.0003	0.134*	0.5
C13A	0.259 (3)	0.5930 (19)	0.0296 (16)	0.135 (7)	0.5
H13A	0.2030	0.5342	−0.0391	0.202*	0.5
H13B	0.3274	0.5448	0.0505	0.202*	0.5
H13C	0.1866	0.5991	0.0833	0.202*	0.5
C12B	0.3667 (16)	0.6783 (14)	0.0444 (12)	0.094 (4)	0.5
H12C	0.3906	0.6959	−0.0267	0.113*	0.5
H12D	0.2543	0.6419	0.0442	0.113*	0.5
C13B	0.421 (2)	0.5568 (19)	0.0575 (17)	0.130 (6)	0.5
H13D	0.3715	0.4676	0.0002	0.195*	0.5
H13E	0.5313	0.5882	0.0548	0.195*	0.5
H13F	0.3944	0.5339	0.1261	0.195*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0354 (4)	0.0299 (4)	0.0218 (4)	0.0123 (3)	−0.0043 (3)	0.0025 (3)
Cl	0.0557 (7)	0.0900 (10)	0.0389 (6)	0.0466 (7)	−0.0042 (5)	−0.0057 (6)
O1	0.086 (3)	0.053 (2)	0.057 (2)	0.0419 (19)	0.0102 (19)	0.0113 (17)
O2A	0.095 (7)	0.055 (5)	0.040 (4)	0.036 (5)	−0.009 (5)	0.014 (4)
O3A	0.064 (5)	0.178 (9)	0.058 (5)	0.083 (6)	0.015 (4)	0.031 (7)
O4A	0.074 (5)	0.074 (6)	0.037 (5)	0.035 (4)	0.011 (4)	0.018 (4)
O2B	0.058 (5)	0.135 (8)	0.037 (4)	0.028 (5)	−0.007 (3)	0.003 (5)
O3B	0.044 (3)	0.047 (3)	0.091 (5)	0.027 (3)	0.011 (3)	0.030 (3)
O4B	0.147 (7)	0.056 (4)	0.072 (5)	0.064 (4)	−0.047 (5)	−0.015 (4)
N1A	0.064 (2)	0.0261 (16)	0.0272 (17)	0.0183 (16)	−0.0042 (16)	0.0031 (14)
C2A	0.053 (2)	0.033 (2)	0.0233 (19)	0.0183 (18)	−0.0034 (17)	0.0034 (16)
N3A	0.0440 (19)	0.0262 (16)	0.0237 (16)	0.0130 (14)	−0.0078 (13)	0.0001 (12)
C4A	0.036 (2)	0.0244 (18)	0.035 (2)	0.0089 (15)	−0.0088 (16)	0.0016 (15)
C5A	0.043 (2)	0.0248 (18)	0.0251 (18)	0.0082 (16)	−0.0111 (16)	0.0010 (15)
C6A	0.047 (2)	0.0261 (19)	0.030 (2)	0.0001 (17)	−0.0111 (17)	0.0001 (16)
C7A	0.062 (3)	0.030 (2)	0.043 (3)	0.002 (2)	−0.005 (2)	0.0051 (19)
C8A	0.074 (4)	0.036 (2)	0.050 (3)	−0.009 (2)	−0.002 (3)	0.009 (2)
C9A	0.061 (3)	0.061 (3)	0.050 (3)	−0.010 (3)	0.005 (2)	0.011 (3)
C10A	0.056 (3)	0.072 (4)	0.062 (3)	0.016 (3)	0.005 (3)	0.020 (3)
C11A	0.052 (3)	0.048 (3)	0.052 (3)	0.012 (2)	0.004 (2)	0.019 (2)
N1B	0.061 (3)	0.061 (3)	0.042 (2)	0.018 (2)	−0.025 (2)	0.0096 (19)
C2B	0.058 (3)	0.063 (3)	0.036 (2)	0.034 (2)	−0.013 (2)	−0.001 (2)
N3B	0.0427 (19)	0.0309 (16)	0.0262 (16)	0.0126 (14)	−0.0046 (14)	0.0052 (13)
C4B	0.046 (2)	0.039 (2)	0.025 (2)	−0.0064 (18)	−0.0022 (17)	0.0081 (17)
C5B	0.056 (3)	0.047 (3)	0.030 (2)	−0.012 (2)	−0.010 (2)	0.0150 (19)
C6B	0.059 (7)	0.051 (7)	0.017 (5)	−0.014 (5)	−0.011 (4)	0.009 (4)
C7B	0.077 (7)	0.069 (7)	0.026 (5)	0.005 (5)	−0.006 (5)	0.005 (5)
C8B	0.075 (7)	0.072 (7)	0.022 (5)	0.003 (5)	−0.005 (5)	0.006 (5)
C9B	0.075 (7)	0.100 (8)	0.024 (5)	0.008 (6)	−0.003 (5)	0.002 (6)
C10B	0.101 (8)	0.126 (9)	0.041 (6)	0.038 (7)	−0.001 (6)	0.001 (7)
C11B	0.090 (7)	0.103 (9)	0.030 (5)	0.023 (6)	0.000 (5)	0.006 (6)
C6C	0.064 (6)	0.039 (5)	0.031 (4)	−0.008 (4)	−0.006 (4)	0.007 (3)
C7C	0.085 (7)	0.054 (5)	0.029 (4)	0.013 (4)	−0.012 (4)	0.007 (4)
C8C	0.089 (7)	0.058 (6)	0.036 (5)	0.008 (5)	−0.019 (5)	0.011 (4)
C9C	0.077 (6)	0.057 (5)	0.019 (4)	−0.001 (5)	−0.006 (4)	0.006 (4)
C10C	0.086 (6)	0.069 (6)	0.022 (4)	0.003 (5)	0.004 (4)	0.009 (4)
C11C	0.085 (6)	0.055 (5)	0.022 (4)	0.004 (5)	−0.006 (4)	0.017 (4)
O5	0.094 (4)	0.149 (4)	0.092 (3)	0.028 (3)	−0.039 (3)	0.021 (3)
C12A	0.104 (9)	0.131 (8)	0.090 (7)	0.024 (7)	−0.019 (6)	0.031 (6)
C13A	0.165 (13)	0.112 (9)	0.100 (11)	0.022 (8)	0.020 (10)	0.009 (7)
C12B	0.055 (6)	0.121 (7)	0.078 (7)	0.000 (5)	0.001 (5)	0.018 (6)
C13B	0.097 (10)	0.121 (9)	0.134 (13)	0.002 (7)	−0.029 (9)	0.015 (8)

Geometric parameters (Å, º)

Cu—N3B^i	1.987 (3)	C5B—C6B	1.551 (6)
Cu—N3B	1.987 (3)	C6B—C7B	1.3900
Cu—N3A^i	1.997 (3)	C6B—C11B	1.3900
Cu—N3A	1.997 (3)	C7B—C8B	1.3900
Cl—O4A	1.311 (9)	C7B—H7B	0.9500
Cl—O1	1.369 (3)	C8B—C9B	1.3900
Cl—O2B	1.405 (7)	C8B—H8B	0.9500
Cl—O3A	1.449 (8)	C9B—C10B	1.3900
Cl—O3B	1.465 (6)	C9B—H9B	0.9500
Cl—O2A	1.527 (8)	C10B—C11B	1.3900
Cl—O4B	1.529 (8)	C10B—H10B	0.9500
N1A—C2A	1.341 (6)	C11B—H11B	0.9500
N1A—C5A	1.376 (5)	C6C—C7C	1.3900
N1A—H1A	0.858 (10)	C6C—C11C	1.3900
C2A—N3A	1.323 (5)	C7C—C8C	1.3900
C2A—H2A	0.9500	C7C—H7C	0.9500
N3A—C4A	1.376 (5)	C8C—C9C	1.3900
C4A—C5A	1.365 (5)	C8C—H8C	0.9500
C4A—H4A	0.9500	C9C—C10C	1.3900
C5A—C6A	1.463 (6)	C9C—H9C	0.9500
C6A—C7A	1.386 (6)	C10C—C11C	1.3900
C6A—C11A	1.389 (7)	C10C—H10C	0.9500
C7A—C8A	1.381 (8)	C11C—H11C	0.9500
C7A—H7A	0.9500	O5—C12A	1.396 (9)
C8A—C9A	1.370 (9)	O5—C12B	1.449 (9)
C8A—H8A	0.9500	O5—H5A	0.841 (10)
C9A—C10A	1.384 (8)	O5—H5B	0.841 (11)
C9A—H9A	0.9500	C12A—C13A	1.487 (10)
C10A—C11A	1.384 (7)	C12A—H12A	0.9900
C10A—H10A	0.9500	C12A—H12B	0.9900
C11A—H11A	0.9500	C13A—H13A	0.9800
N1B—C2B	1.341 (6)	C13A—H13B	0.9800
N1B—C5B	1.369 (7)	C13A—H13C	0.9800
N1B—H1B	0.858 (10)	C12B—C13B	1.478 (10)
C2B—N3B	1.318 (6)	C12B—H12C	0.9900
C2B—H2B	0.9500	C12B—H12D	0.9900
N3B—C4B	1.375 (5)	C13B—H13D	0.9800
C4B—C5B	1.360 (6)	C13B—H13E	0.9800
C4B—H4B	0.9500	C13B—H13F	0.9800
C5B—C6C	1.434 (5)
N3B^i—Cu—N3B	180.0	N1B—C5B—C6C	116.6 (5)
N3B^i—Cu—N3A^i	89.29 (13)	C4B—C5B—C6B	124.0 (6)
N3B—Cu—N3A^i	90.71 (13)	N1B—C5B—C6B	129.6 (6)
N3B^i—Cu—N3A	90.71 (13)	C7B—C6B—C11B	120.0
N3B—Cu—N3A	89.29 (13)	C7B—C6B—C5B	117.9 (6)
N3A^i—Cu—N3A	180.0	C11B—C6B—C5B	122.1 (6)
O4A—Cl—O1	128.1 (4)	C8B—C7B—C6B	120.0
O1—Cl—O2B	113.1 (4)	C8B—C7B—H7B	120.0
O4A—Cl—O3A	83.6 (6)	C6B—C7B—H7B	120.0
O1—Cl—O3A	122.2 (5)	C7B—C8B—C9B	120.0
O1—Cl—O3B	98.5 (3)	C7B—C8B—H8B	120.0
O2B—Cl—O3B	119.1 (5)	C9B—C8B—H8B	120.0
O4A—Cl—O2A	109.6 (5)	C8B—C9B—C10B	120.0
O1—Cl—O2A	103.5 (4)	C8B—C9B—H9B	120.0
O3A—Cl—O2A	108.4 (6)	C10B—C9B—H9B	120.0
O1—Cl—O4B	97.6 (4)	C9B—C10B—C11B	120.0
O2B—Cl—O4B	101.5 (5)	C9B—C10B—H10B	120.0
O3B—Cl—O4B	125.0 (4)	C11B—C10B—H10B	120.0
C2A—N1A—C5A	108.9 (3)	C10B—C11B—C6B	120.0
C2A—N1A—H1A	124 (4)	C10B—C11B—H11B	120.0
C5A—N1A—H1A	127 (4)	C6B—C11B—H11B	120.0
N3A—C2A—N1A	110.5 (4)	C7C—C6C—C11C	120.0
N3A—C2A—H2A	124.8	C7C—C6C—C5B	127.2 (5)
N1A—C2A—H2A	124.8	C11C—C6C—C5B	112.7 (5)
C2A—N3A—C4A	105.7 (3)	C6C—C7C—C8C	120.0
C2A—N3A—Cu	125.3 (3)	C6C—C7C—H7C	120.0
C4A—N3A—Cu	128.9 (2)	C8C—C7C—H7C	120.0
C5A—C4A—N3A	110.4 (3)	C9C—C8C—C7C	120.0
C5A—C4A—H4A	124.8	C9C—C8C—H8C	120.0
N3A—C4A—H4A	124.8	C7C—C8C—H8C	120.0
C4A—C5A—N1A	104.4 (4)	C8C—C9C—C10C	120.0
C4A—C5A—C6A	131.5 (4)	C8C—C9C—H9C	120.0
N1A—C5A—C6A	124.1 (3)	C10C—C9C—H9C	120.0
C7A—C6A—C11A	118.8 (4)	C11C—C10C—C9C	120.0
C7A—C6A—C5A	122.0 (4)	C11C—C10C—H10C	120.0
C11A—C6A—C5A	119.2 (4)	C9C—C10C—H10C	120.0
C8A—C7A—C6A	120.7 (5)	C10C—C11C—C6C	120.0
C8A—C7A—H7A	119.7	C10C—C11C—H11C	120.0
C6A—C7A—H7A	119.7	C6C—C11C—H11C	120.0
C9A—C8A—C7A	120.3 (5)	C12A—O5—H5A	116 (9)
C9A—C8A—H8A	119.9	C12B—O5—H5B	105 (10)
C7A—C8A—H8A	119.9	O5—C12A—C13A	105.7 (13)
C8A—C9A—C10A	119.8 (5)	O5—C12A—H12A	110.6
C8A—C9A—H9A	120.1	C13A—C12A—H12A	110.6
C10A—C9A—H9A	120.1	O5—C12A—H12B	110.6
C9A—C10A—C11A	120.1 (6)	C13A—C12A—H12B	110.6
C9A—C10A—H10A	119.9	H12A—C12A—H12B	108.7
C11A—C10A—H10A	119.9	C12A—C13A—H13A	109.5
C10A—C11A—C6A	120.3 (5)	C12A—C13A—H13B	109.5
C10A—C11A—H11A	119.9	H13A—C13A—H13B	109.5
C6A—C11A—H11A	119.9	C12A—C13A—H13C	109.5
C2B—N1B—C5B	107.9 (4)	H13A—C13A—H13C	109.5
C2B—N1B—H1B	123 (5)	H13B—C13A—H13C	109.5
C5B—N1B—H1B	129 (5)	O5—C12B—C13B	118.7 (13)
N3B—C2B—N1B	111.3 (5)	O5—C12B—H12C	107.6
N3B—C2B—H2B	124.4	C13B—C12B—H12C	107.6
N1B—C2B—H2B	124.4	O5—C12B—H12D	107.6
C2B—N3B—C4B	105.4 (4)	C13B—C12B—H12D	107.6
C2B—N3B—Cu	130.4 (3)	H12C—C12B—H12D	107.1
C4B—N3B—Cu	124.1 (3)	C12B—C13B—H13D	109.5
C5B—C4B—N3B	110.1 (4)	C12B—C13B—H13E	109.5
C5B—C4B—H4B	125.0	H13D—C13B—H13E	109.5
N3B—C4B—H4B	125.0	C12B—C13B—H13F	109.5
C4B—C5B—N1B	105.4 (4)	H13D—C13B—H13F	109.5
C4B—C5B—C6C	137.5 (6)	H13E—C13B—H13F	109.5

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O4A^ii	0.86 (1)	2.15 (4)	2.877 (10)	143 (5)
N1A—H1A···O4B^ii	0.86 (1)	2.09 (4)	2.777 (8)	136 (5)
C2A—H2A···O1^i	0.95	2.56	3.196 (6)	124
C4A—H4A···O1	0.95	2.66	3.238 (5)	120
C4A—H4A···O3B	0.95	2.57	3.501 (7)	168
N1B—H1B···O5^iii	0.86 (1)	1.94 (1)	2.801 (6)	176 (6)
C2B—H2B···O3A^iv	0.95	2.66	3.346 (12)	129
C2B—H2B···O3B^iv	0.95	2.51	3.301 (8)	141
C4B—H4B···O2A	0.95	2.33	3.132 (12)	142
O5—H5A···O2A^ii	0.84 (1)	1.91 (2)	2.719 (13)	162 (8)
O5—H5B···O2B^ii	0.84 (1)	2.26 (6)	3.018 (11)	150 (11)

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

(4)

Crystal data

C36H32Cl2CuN8O8·2(C3H8O)	Z = 1
Mr = 959.32	F(000) = 499
Triclinic, P1	Dx = 1.426 Mg m^−3
a = 9.1329 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0787 (7) Å	Cell parameters from 4307 reflections
c = 13.0825 (8) Å	θ = 6.5–29.4°
α = 103.496 (6)°	µ = 0.67 mm^−1
β = 94.562 (5)°	T = 100 K
γ = 105.229 (6)°	Prism, purple
V = 1117.04 (13) Å^3	0.21 × 0.15 × 0.11 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4829 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4106 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.025
ω scans	θmax = 27.0°, θmin = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.803, Tmax = 1.000	k = −12→12
10056 measured reflections	l = −14→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: mixed
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0337P)^2 + 1.0475P] where P = (Fo^2 + 2Fc^2)/3
4829 reflections	(Δ/σ)max < 0.001
296 parameters	Δρmax = 0.38 e Å^−3
3 restraints	Δρmin = −0.46 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	0.0000	0.0000	0.0000	0.01401 (10)
N1A	−0.2226 (2)	−0.34109 (18)	0.10577 (14)	0.0196 (4)
H1A	−0.224 (3)	−0.4223 (16)	0.116 (2)	0.029*
N1B	−0.34454 (19)	−0.12484 (19)	−0.25864 (14)	0.0198 (4)
H1B	−0.4329 (16)	−0.127 (3)	−0.2875 (19)	0.030*
C2A	−0.1046 (2)	−0.2594 (2)	0.07341 (17)	0.0199 (4)
H2A	−0.0098	−0.2797	0.0648	0.024*
C2B	−0.2825 (2)	−0.0552 (2)	−0.15812 (16)	0.0190 (4)
H2B	−0.3325	−0.0055	−0.1082	0.023*
N3A	−0.13802 (18)	−0.14695 (17)	0.05517 (13)	0.0168 (3)
N3B	−0.14208 (18)	−0.06484 (17)	−0.13743 (13)	0.0164 (3)
C4A	−0.2854 (2)	−0.1585 (2)	0.07592 (16)	0.0179 (4)
H4A	−0.3404	−0.0921	0.0695	0.021*
C4B	−0.1143 (2)	−0.1442 (2)	−0.23054 (16)	0.0172 (4)
H4B	−0.0213	−0.1677	−0.2404	0.021*
C5A	−0.3408 (2)	−0.2803 (2)	0.10730 (16)	0.0174 (4)
C5B	−0.2398 (2)	−0.1843 (2)	−0.30669 (16)	0.0174 (4)
C6A	−0.4900 (2)	−0.3438 (2)	0.13585 (16)	0.0190 (4)
C6B	−0.2711 (2)	−0.2765 (2)	−0.41500 (16)	0.0199 (4)
C7A	−0.5393 (2)	−0.4884 (2)	0.13122 (16)	0.0217 (4)
H7A	−0.4754	−0.5473	0.1095	0.026*
C7B	−0.3981 (3)	−0.2875 (2)	−0.48579 (17)	0.0236 (4)
H7B	−0.4662	−0.2330	−0.4645	0.028*
C8A	−0.6815 (3)	−0.5468 (3)	0.15819 (18)	0.0291 (5)
H8A	−0.7138	−0.6452	0.1558	0.035*
C8B	−0.4258 (3)	−0.3780 (3)	−0.58761 (18)	0.0287 (5)
H8B	−0.5132	−0.3854	−0.6355	0.034*
C9A	−0.7762 (3)	−0.4631 (3)	0.18840 (18)	0.0317 (5)
H9A	−0.8737	−0.5035	0.2064	0.038*
C9B	−0.3275 (3)	−0.4569 (3)	−0.61955 (19)	0.0322 (5)
H9B	−0.3463	−0.5181	−0.6895	0.039*
C10A	−0.7281 (3)	−0.3195 (3)	0.19229 (19)	0.0302 (5)
H10A	−0.7931	−0.2614	0.2129	0.036*
C10B	−0.2014 (3)	−0.4467 (3)	−0.5494 (2)	0.0357 (6)
H10B	−0.1337	−0.5015	−0.5711	0.043*
C11A	−0.5859 (2)	−0.2600 (2)	0.16633 (18)	0.0248 (5)
H11A	−0.5538	−0.1614	0.1694	0.030*
C11B	−0.1729 (3)	−0.3574 (3)	−0.44760 (19)	0.0290 (5)
H11B	−0.0859	−0.3513	−0.3998	0.035*
Cl	0.22978 (5)	−0.25601 (5)	−0.12266 (4)	0.01921 (12)
O1	0.15430 (19)	−0.16512 (17)	−0.06170 (12)	0.0276 (4)
O2	0.17607 (19)	−0.28164 (19)	−0.23395 (13)	0.0314 (4)
O3	0.39081 (19)	−0.1914 (2)	−0.10117 (16)	0.0480 (5)
O4	0.1909 (3)	−0.38821 (19)	−0.09421 (17)	0.0471 (5)
C12	0.6765 (3)	0.0001 (3)	0.3723 (2)	0.0360 (6)
H12A	0.6907	−0.0649	0.3067	0.043*
H12B	0.5931	−0.0549	0.4030	0.043*
C13	0.8222 (3)	0.0494 (3)	0.4503 (2)	0.0365 (6)
H13A	0.8496	−0.0350	0.4624	0.044*
H13B	0.9062	0.1031	0.4192	0.044*
C14	0.8095 (4)	0.1422 (4)	0.5549 (2)	0.0596 (9)
H14A	0.9067	0.1696	0.6029	0.089*
H14B	0.7269	0.0896	0.5863	0.089*
H14C	0.7866	0.2279	0.5438	0.089*
O5	0.63091 (19)	0.1137 (2)	0.34474 (14)	0.0366 (4)
H5	0.695 (3)	0.164 (3)	0.316 (2)	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01325 (17)	0.01377 (17)	0.01510 (18)	0.00413 (13)	0.00192 (12)	0.00377 (13)
N1A	0.0195 (8)	0.0164 (8)	0.0255 (9)	0.0069 (7)	0.0042 (7)	0.0085 (7)
N1B	0.0161 (8)	0.0248 (9)	0.0196 (9)	0.0094 (7)	−0.0003 (7)	0.0048 (7)
C2A	0.0182 (10)	0.0195 (10)	0.0236 (11)	0.0069 (8)	0.0029 (8)	0.0072 (8)
C2B	0.0190 (10)	0.0195 (10)	0.0196 (10)	0.0084 (8)	0.0036 (8)	0.0036 (8)
N3A	0.0153 (8)	0.0157 (8)	0.0183 (8)	0.0036 (7)	0.0017 (6)	0.0039 (7)
N3B	0.0154 (8)	0.0176 (8)	0.0167 (8)	0.0050 (7)	0.0021 (6)	0.0054 (7)
C4A	0.0162 (9)	0.0168 (9)	0.0208 (10)	0.0061 (8)	0.0022 (8)	0.0040 (8)
C4B	0.0152 (9)	0.0191 (10)	0.0184 (10)	0.0068 (8)	0.0049 (8)	0.0044 (8)
C5A	0.0176 (9)	0.0171 (9)	0.0168 (10)	0.0058 (8)	0.0009 (8)	0.0029 (8)
C5B	0.0165 (9)	0.0177 (10)	0.0189 (10)	0.0050 (8)	0.0046 (8)	0.0060 (8)
C6A	0.0183 (10)	0.0219 (10)	0.0153 (10)	0.0023 (8)	0.0010 (8)	0.0063 (8)
C6B	0.0192 (10)	0.0211 (10)	0.0190 (10)	0.0046 (8)	0.0039 (8)	0.0053 (8)
C7A	0.0253 (11)	0.0204 (10)	0.0158 (10)	0.0021 (9)	0.0019 (8)	0.0036 (8)
C7B	0.0254 (11)	0.0257 (11)	0.0201 (11)	0.0098 (9)	0.0026 (9)	0.0042 (9)
C8A	0.0294 (12)	0.0276 (12)	0.0216 (11)	−0.0059 (10)	0.0018 (9)	0.0066 (9)
C8B	0.0291 (12)	0.0349 (13)	0.0199 (11)	0.0104 (10)	−0.0026 (9)	0.0038 (10)
C9A	0.0190 (11)	0.0447 (14)	0.0227 (12)	−0.0045 (10)	0.0030 (9)	0.0077 (10)
C9B	0.0410 (14)	0.0339 (13)	0.0187 (11)	0.0141 (11)	0.0017 (10)	−0.0014 (10)
C10A	0.0213 (11)	0.0431 (14)	0.0257 (12)	0.0115 (10)	0.0041 (9)	0.0056 (10)
C10B	0.0365 (13)	0.0431 (15)	0.0274 (13)	0.0217 (12)	0.0037 (10)	−0.0021 (11)
C11A	0.0217 (11)	0.0265 (11)	0.0262 (12)	0.0073 (9)	0.0029 (9)	0.0071 (9)
C11B	0.0257 (11)	0.0358 (13)	0.0253 (12)	0.0152 (10)	0.0003 (9)	0.0020 (10)
Cl	0.0178 (2)	0.0193 (2)	0.0235 (3)	0.00990 (19)	0.00553 (19)	0.00534 (19)
O1	0.0343 (9)	0.0282 (8)	0.0254 (8)	0.0206 (7)	0.0077 (7)	0.0026 (7)
O2	0.0316 (9)	0.0411 (10)	0.0222 (8)	0.0167 (8)	0.0057 (7)	0.0018 (7)
O3	0.0162 (8)	0.0836 (16)	0.0440 (11)	0.0084 (9)	0.0047 (8)	0.0232 (11)
O4	0.0707 (14)	0.0235 (9)	0.0565 (13)	0.0233 (9)	0.0124 (10)	0.0167 (9)
C12	0.0304 (13)	0.0418 (15)	0.0347 (14)	0.0134 (11)	0.0005 (10)	0.0060 (11)
C13	0.0275 (12)	0.0491 (16)	0.0361 (14)	0.0139 (12)	0.0012 (10)	0.0159 (12)
C14	0.0510 (19)	0.083 (2)	0.0316 (16)	0.0109 (18)	−0.0013 (13)	0.0016 (16)
O5	0.0246 (9)	0.0572 (12)	0.0399 (10)	0.0205 (9)	0.0082 (7)	0.0247 (9)

Geometric parameters (Å, º)

Cu—N3A	1.9915 (16)	C8A—C9A	1.377 (4)
Cu—N3A^i	1.9916 (16)	C8A—H8A	0.9500
Cu—N3B	1.9946 (16)	C8B—C9B	1.376 (3)
Cu—N3B^i	1.9946 (16)	C8B—H8B	0.9500
N1A—C2A	1.337 (3)	C9A—C10A	1.385 (4)
N1A—C5A	1.374 (3)	C9A—H9A	0.9500
N1A—H1A	0.855 (10)	C9B—C10B	1.380 (3)
N1B—C2B	1.336 (3)	C9B—H9B	0.9500
N1B—C5B	1.375 (3)	C10A—C11A	1.384 (3)
N1B—H1B	0.857 (10)	C10A—H10A	0.9500
C2A—N3A	1.315 (3)	C10B—C11B	1.383 (3)
C2A—H2A	0.9500	C10B—H10B	0.9500
C2B—N3B	1.323 (3)	C11A—H11A	0.9500
C2B—H2B	0.9500	C11B—H11B	0.9500
N3A—C4A	1.375 (3)	Cl—O3	1.4184 (17)
N3B—C4B	1.374 (3)	Cl—O1	1.4243 (15)
C4A—C5A	1.369 (3)	Cl—O4	1.4296 (18)
C4A—H4A	0.9500	Cl—O2	1.4392 (17)
C4B—C5B	1.363 (3)	C12—O5	1.427 (3)
C4B—H4B	0.9500	C12—C13	1.503 (3)
C5A—C6A	1.463 (3)	C12—H12A	0.9900
C5B—C6B	1.461 (3)	C12—H12B	0.9900
C6A—C11A	1.388 (3)	C13—C14	1.498 (4)
C6A—C7A	1.393 (3)	C13—H13A	0.9900
C6B—C7B	1.389 (3)	C13—H13B	0.9900
C6B—C11B	1.391 (3)	C14—H14A	0.9800
C7A—C8A	1.388 (3)	C14—H14B	0.9800
C7A—H7A	0.9500	C14—H14C	0.9800
C7B—C8B	1.389 (3)	O5—H5	0.844 (10)
C7B—H7B	0.9500
N3A—Cu—N3A^i	180.0	C9A—C8A—H8A	119.8
N3A—Cu—N3B	90.47 (7)	C7A—C8A—H8A	119.8
N3A^i—Cu—N3B	89.53 (7)	C9B—C8B—C7B	120.4 (2)
N3A—Cu—N3B^i	89.53 (7)	C9B—C8B—H8B	119.8
N3A^i—Cu—N3B^i	90.47 (7)	C7B—C8B—H8B	119.8
N3B—Cu—N3B^i	180.0	C8A—C9A—C10A	119.5 (2)
C2A—N1A—C5A	108.71 (17)	C8A—C9A—H9A	120.2
C2A—N1A—H1A	122.8 (17)	C10A—C9A—H9A	120.2
C5A—N1A—H1A	128.0 (17)	C8B—C9B—C10B	119.6 (2)
C2B—N1B—C5B	108.31 (17)	C8B—C9B—H9B	120.2
C2B—N1B—H1B	124.4 (18)	C10B—C9B—H9B	120.2
C5B—N1B—H1B	127.2 (18)	C9A—C10A—C11A	120.4 (2)
N3A—C2A—N1A	110.58 (18)	C9A—C10A—H10A	119.8
N3A—C2A—H2A	124.7	C11A—C10A—H10A	119.8
N1A—C2A—H2A	124.7	C9B—C10B—C11B	120.5 (2)
N3B—C2B—N1B	110.96 (18)	C9B—C10B—H10B	119.7
N3B—C2B—H2B	124.5	C11B—C10B—H10B	119.7
N1B—C2B—H2B	124.5	C10A—C11A—C6A	120.3 (2)
C2A—N3A—C4A	106.34 (16)	C10A—C11A—H11A	119.8
C2A—N3A—Cu	124.63 (14)	C6A—C11A—H11A	119.8
C4A—N3A—Cu	128.94 (13)	C10B—C11B—C6B	120.2 (2)
C2B—N3B—C4B	105.65 (16)	C10B—C11B—H11B	119.9
C2B—N3B—Cu	129.79 (14)	C6B—C11B—H11B	119.9
C4B—N3B—Cu	124.28 (13)	O3—Cl—O1	109.91 (12)
C5A—C4A—N3A	109.54 (17)	O3—Cl—O4	110.66 (13)
C5A—C4A—H4A	125.2	O1—Cl—O4	107.82 (11)
N3A—C4A—H4A	125.2	O3—Cl—O2	109.92 (11)
C5B—C4B—N3B	110.00 (17)	O1—Cl—O2	109.30 (10)
C5B—C4B—H4B	125.0	O4—Cl—O2	109.19 (12)
N3B—C4B—H4B	125.0	O5—C12—C13	113.6 (2)
C4A—C5A—N1A	104.83 (17)	O5—C12—H12A	108.9
C4A—C5A—C6A	131.69 (18)	C13—C12—H12A	108.9
N1A—C5A—C6A	123.46 (18)	O5—C12—H12B	108.9
C4B—C5B—N1B	105.06 (17)	C13—C12—H12B	108.9
C4B—C5B—C6B	130.88 (18)	H12A—C12—H12B	107.7
N1B—C5B—C6B	123.96 (18)	C14—C13—C12	113.0 (2)
C11A—C6A—C7A	119.03 (19)	C14—C13—H13A	109.0
C11A—C6A—C5A	119.88 (19)	C12—C13—H13A	109.0
C7A—C6A—C5A	121.07 (19)	C14—C13—H13B	109.0
C7B—C6B—C11B	119.0 (2)	C12—C13—H13B	109.0
C7B—C6B—C5B	121.69 (19)	H13A—C13—H13B	107.8
C11B—C6B—C5B	119.25 (19)	C13—C14—H14A	109.5
C8A—C7A—C6A	120.2 (2)	C13—C14—H14B	109.5
C8A—C7A—H7A	119.9	H14A—C14—H14B	109.5
C6A—C7A—H7A	119.9	C13—C14—H14C	109.5
C8B—C7B—C6B	120.2 (2)	H14A—C14—H14C	109.5
C8B—C7B—H7B	119.9	H14B—C14—H14C	109.5
C6B—C7B—H7B	119.9	C12—O5—H5	115 (2)
C9A—C8A—C7A	120.5 (2)

Symmetry code: (i) −x, −y, −z.

(6)

Crystal data

C36H32Cl2CuN8O8·2(C4H10O)	Z = 1
Mr = 987.37	F(000) = 515
Triclinic, P1	Dx = 1.416 Mg m^−3
a = 9.4157 (5) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.9855 (6) Å	Cell parameters from 3159 reflections
c = 13.6726 (7) Å	θ = 4.9–74.1°
α = 106.181 (5)°	µ = 2.28 mm^−1
β = 96.455 (4)°	T = 100 K
γ = 106.527 (5)°	Block, purple
V = 1157.64 (12) Å^3	0.16 × 0.09 × 0.09 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4229 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3607 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.035
ω scans	θmax = 69.0°, θmin = 3.4°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→9
Tmin = 0.815, Tmax = 1.000	k = −8→11
7216 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: mixed
wR(F^2) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0681P)^2 + 2.4911P] where P = (Fo^2 + 2Fc^2)/3
4229 reflections	(Δ/σ)max = 0.001
306 parameters	Δρmax = 1.55 e Å^−3
3 restraints	Δρmin = −0.51 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	0.0000	0.0000	0.0000	0.01616 (19)
N1B	−0.3501 (3)	−0.1331 (3)	−0.2577 (2)	0.0228 (6)
H1B	−0.437 (3)	−0.138 (5)	−0.288 (3)	0.034*
C2B	−0.2871 (4)	−0.0627 (4)	−0.1561 (3)	0.0207 (7)
H2B	−0.3346	−0.0139	−0.1068	0.025*
N3B	−0.1511 (3)	−0.0708 (3)	−0.1345 (2)	0.0190 (6)
C4B	−0.1252 (4)	−0.1514 (4)	−0.2265 (3)	0.0198 (7)
H4B	−0.0353	−0.1748	−0.2344	0.024*
C5B	−0.2491 (4)	−0.1922 (4)	−0.3044 (3)	0.0209 (7)
C6B	−0.2794 (4)	−0.2814 (4)	−0.4139 (3)	0.0250 (7)
C7B	−0.4042 (5)	−0.2930 (5)	−0.4852 (3)	0.0375 (10)
H7B	−0.4709	−0.2405	−0.4629	0.045*
C8B	−0.4317 (6)	−0.3808 (6)	−0.5884 (3)	0.0456 (11)
H8B	−0.5178	−0.3890	−0.6361	0.055*
C9B	−0.3351 (5)	−0.4557 (5)	−0.6220 (3)	0.0428 (11)
H9B	−0.3534	−0.5143	−0.6930	0.051*
C10B	−0.2114 (5)	−0.4457 (5)	−0.5523 (3)	0.0408 (10)
H10B	−0.1449	−0.4980	−0.5754	0.049*
C11B	−0.1841 (4)	−0.3597 (5)	−0.4491 (3)	0.0328 (9)
H11B	−0.0992	−0.3541	−0.4016	0.039*
N1A	−0.2190 (3)	−0.3371 (3)	0.1025 (2)	0.0232 (6)
H1A	−0.219 (5)	−0.414 (3)	0.119 (4)	0.035*
C2A	−0.1037 (4)	−0.2568 (4)	0.0722 (3)	0.0228 (7)
H2A	−0.0117	−0.2769	0.0660	0.027*
N3A	−0.1358 (3)	−0.1457 (3)	0.0520 (2)	0.0188 (6)
C4A	−0.2790 (4)	−0.1564 (4)	0.0700 (3)	0.0195 (7)
H4A	−0.3321	−0.0912	0.0613	0.023*
C5A	−0.3327 (4)	−0.2753 (4)	0.1022 (2)	0.0194 (7)
C6A	−0.4780 (4)	−0.3365 (4)	0.1297 (3)	0.0212 (7)
C7A	−0.5286 (4)	−0.4809 (4)	0.1310 (3)	0.0241 (7)
H7A	−0.4679	−0.5421	0.1144	0.029*
C8A	−0.6664 (5)	−0.5361 (4)	0.1562 (3)	0.0314 (9)
H8A	−0.6991	−0.6346	0.1577	0.038*
C9A	−0.7573 (4)	−0.4494 (5)	0.1792 (3)	0.0330 (9)
H9A	−0.8528	−0.4883	0.1954	0.040*
C10A	−0.7076 (5)	−0.3052 (5)	0.1784 (4)	0.0387 (10)
H10A	−0.7692	−0.2447	0.1943	0.046*
C11A	−0.5681 (4)	−0.2490 (5)	0.1545 (3)	0.0330 (9)
H11A	−0.5341	−0.1496	0.1551	0.040*
Cl	−0.21727 (9)	0.26311 (9)	0.13288 (7)	0.0245 (2)
O1	−0.1434 (3)	0.1819 (3)	0.0647 (2)	0.0311 (6)
O2	−0.1656 (3)	0.2691 (4)	0.2382 (2)	0.0433 (8)
O3	−0.3760 (3)	0.1947 (4)	0.1031 (3)	0.0518 (9)
O4	−0.1747 (5)	0.4106 (4)	0.1304 (4)	0.0629 (11)
C12	0.1393 (10)	0.8326 (10)	0.3981 (6)	0.095 (3)
H12A	0.0964	0.7445	0.3362	0.142*
H12B	0.2153	0.9087	0.3818	0.142*
H12C	0.0584	0.8703	0.4198	0.142*
C13	0.2106 (8)	0.7945 (9)	0.4825 (5)	0.0720 (19)
H13A	0.2796	0.7412	0.4559	0.086*
H13B	0.1309	0.7264	0.5039	0.086*
C14	0.3055 (6)	0.9361 (7)	0.5838 (4)	0.0518 (13)
H14	0.3884	1.0044	0.5637	0.062*
C15	0.2024 (7)	1.0162 (7)	0.6278 (4)	0.0603 (15)
H15A	0.1658	1.0587	0.5778	0.091*
H15B	0.2580	1.0953	0.6930	0.091*
H15C	0.1161	0.9467	0.6414	0.091*
O5	0.3701 (3)	0.8788 (4)	0.6566 (2)	0.0396 (7)
H5	0.306 (5)	0.829 (6)	0.680 (4)	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0162 (3)	0.0152 (3)	0.0177 (3)	0.0046 (3)	0.0034 (2)	0.0068 (3)
N1B	0.0214 (14)	0.0263 (15)	0.0203 (14)	0.0117 (12)	0.0024 (11)	0.0040 (11)
C2B	0.0216 (16)	0.0210 (16)	0.0208 (16)	0.0100 (13)	0.0049 (13)	0.0054 (13)
N3B	0.0214 (14)	0.0173 (13)	0.0177 (13)	0.0053 (11)	0.0028 (11)	0.0066 (11)
C4B	0.0182 (15)	0.0234 (17)	0.0204 (16)	0.0091 (13)	0.0050 (13)	0.0084 (13)
C5B	0.0211 (16)	0.0211 (16)	0.0226 (17)	0.0087 (13)	0.0070 (13)	0.0079 (13)
C6B	0.0240 (17)	0.0285 (18)	0.0230 (17)	0.0108 (15)	0.0040 (14)	0.0074 (14)
C7B	0.038 (2)	0.053 (3)	0.0225 (19)	0.025 (2)	0.0020 (16)	0.0041 (17)
C8B	0.045 (3)	0.062 (3)	0.024 (2)	0.027 (2)	−0.0040 (18)	0.0010 (19)
C9B	0.049 (3)	0.054 (3)	0.0196 (18)	0.021 (2)	0.0053 (17)	−0.0010 (18)
C10B	0.041 (2)	0.050 (3)	0.031 (2)	0.025 (2)	0.0086 (18)	−0.0001 (18)
C11B	0.0282 (19)	0.042 (2)	0.0256 (18)	0.0159 (17)	0.0035 (15)	0.0034 (16)
N1A	0.0248 (15)	0.0186 (14)	0.0284 (15)	0.0057 (12)	0.0038 (12)	0.0131 (12)
C2A	0.0192 (16)	0.0202 (17)	0.0299 (18)	0.0049 (13)	0.0038 (14)	0.0116 (14)
N3A	0.0170 (13)	0.0175 (13)	0.0218 (13)	0.0037 (11)	0.0031 (11)	0.0086 (11)
C4A	0.0171 (15)	0.0188 (16)	0.0224 (16)	0.0055 (13)	0.0024 (12)	0.0074 (13)
C5A	0.0187 (16)	0.0192 (16)	0.0185 (15)	0.0056 (13)	−0.0001 (12)	0.0057 (12)
C6A	0.0208 (16)	0.0215 (17)	0.0191 (15)	0.0030 (13)	0.0017 (13)	0.0085 (13)
C7A	0.0279 (18)	0.0215 (17)	0.0173 (15)	0.0021 (14)	0.0038 (13)	0.0042 (13)
C8A	0.035 (2)	0.0258 (19)	0.0214 (17)	−0.0067 (16)	0.0056 (15)	0.0067 (14)
C9A	0.0203 (17)	0.042 (2)	0.031 (2)	−0.0003 (16)	0.0054 (15)	0.0136 (17)
C10A	0.0249 (19)	0.044 (2)	0.055 (3)	0.0133 (18)	0.0122 (18)	0.024 (2)
C11A	0.0237 (18)	0.032 (2)	0.052 (2)	0.0099 (16)	0.0102 (17)	0.0242 (18)
Cl	0.0239 (4)	0.0237 (4)	0.0324 (4)	0.0136 (3)	0.0105 (3)	0.0111 (3)
O1	0.0402 (15)	0.0319 (14)	0.0283 (13)	0.0217 (12)	0.0127 (11)	0.0084 (11)
O2	0.0380 (16)	0.069 (2)	0.0283 (14)	0.0288 (15)	0.0109 (12)	0.0108 (14)
O3	0.0216 (15)	0.083 (3)	0.057 (2)	0.0141 (15)	0.0085 (14)	0.0337 (19)
O4	0.066 (2)	0.0317 (18)	0.108 (3)	0.0301 (17)	0.023 (2)	0.0313 (19)
C12	0.113 (6)	0.125 (7)	0.062 (4)	0.070 (6)	0.018 (4)	0.022 (4)
C13	0.071 (4)	0.116 (6)	0.058 (3)	0.067 (4)	0.025 (3)	0.031 (4)
C14	0.037 (2)	0.085 (4)	0.052 (3)	0.028 (3)	0.014 (2)	0.040 (3)
C15	0.066 (4)	0.064 (3)	0.047 (3)	0.040 (3)	−0.008 (3)	0.002 (2)
O5	0.0283 (15)	0.061 (2)	0.0373 (16)	0.0223 (14)	0.0059 (12)	0.0202 (14)

Geometric parameters (Å, º)

Cu—N3A^i	1.995 (3)	C4A—H4A	0.9500
Cu—N3A	1.995 (3)	C5A—C6A	1.468 (5)
Cu—N3B	2.005 (3)	C6A—C11A	1.385 (6)
Cu—N3B^i	2.005 (3)	C6A—C7A	1.389 (5)
N1B—C2B	1.344 (4)	C7A—C8A	1.380 (5)
N1B—C5B	1.381 (4)	C7A—H7A	0.9500
N1B—H1B	0.858 (10)	C8A—C9A	1.382 (6)
C2B—N3B	1.311 (4)	C8A—H8A	0.9500
C2B—H2B	0.9500	C9A—C10A	1.385 (6)
N3B—C4B	1.380 (4)	C9A—H9A	0.9500
C4B—C5B	1.368 (5)	C10A—C11A	1.389 (6)
C4B—H4B	0.9500	C10A—H10A	0.9500
C5B—C6B	1.460 (5)	C11A—H11A	0.9500
C6B—C11B	1.392 (5)	Cl—O3	1.412 (3)
C6B—C7B	1.395 (5)	Cl—O4	1.423 (3)
C7B—C8B	1.388 (6)	Cl—O1	1.433 (3)
C7B—H7B	0.9500	Cl—O2	1.446 (3)
C8B—C9B	1.374 (7)	C12—C13	1.465 (9)
C8B—H8B	0.9500	C12—H12A	0.9800
C9B—C10B	1.380 (6)	C12—H12B	0.9800
C9B—H9B	0.9500	C12—H12C	0.9800
C10B—C11B	1.384 (6)	C13—C14	1.622 (9)
C10B—H10B	0.9500	C13—H13A	0.9900
C11B—H11B	0.9500	C13—H13B	0.9900
N1A—C2A	1.337 (5)	C14—O5	1.438 (5)
N1A—C5A	1.380 (5)	C14—C15	1.499 (7)
N1A—H1A	0.858 (10)	C14—H14	1.0000
C2A—N3A	1.319 (5)	C15—H15A	0.9800
C2A—H2A	0.9500	C15—H15B	0.9800
N3A—C4A	1.378 (4)	C15—H15C	0.9800
C4A—C5A	1.363 (5)	O5—H5	0.827 (10)
N3A^i—Cu—N3A	180.0	C4A—C5A—C6A	131.4 (3)
N3A^i—Cu—N3B	89.10 (11)	N1A—C5A—C6A	123.5 (3)
N3A—Cu—N3B	90.90 (11)	C11A—C6A—C7A	118.8 (3)
N3A^i—Cu—N3B^i	90.90 (11)	C11A—C6A—C5A	119.4 (3)
N3A—Cu—N3B^i	89.10 (11)	C7A—C6A—C5A	121.8 (3)
N3B—Cu—N3B^i	180.0	C8A—C7A—C6A	120.6 (4)
C2B—N1B—C5B	108.2 (3)	C8A—C7A—H7A	119.7
C2B—N1B—H1B	125 (3)	C6A—C7A—H7A	119.7
C5B—N1B—H1B	127 (3)	C7A—C8A—C9A	120.6 (4)
N3B—C2B—N1B	110.8 (3)	C7A—C8A—H8A	119.7
N3B—C2B—H2B	124.6	C9A—C8A—H8A	119.7
N1B—C2B—H2B	124.6	C8A—C9A—C10A	119.3 (4)
C2B—N3B—C4B	106.5 (3)	C8A—C9A—H9A	120.4
C2B—N3B—Cu	131.9 (2)	C10A—C9A—H9A	120.4
C4B—N3B—Cu	121.5 (2)	C9A—C10A—C11A	120.1 (4)
C5B—C4B—N3B	109.4 (3)	C9A—C10A—H10A	119.9
C5B—C4B—H4B	125.3	C11A—C10A—H10A	119.9
N3B—C4B—H4B	125.3	C6A—C11A—C10A	120.7 (4)
C4B—C5B—N1B	105.1 (3)	C6A—C11A—H11A	119.7
C4B—C5B—C6B	130.5 (3)	C10A—C11A—H11A	119.7
N1B—C5B—C6B	124.4 (3)	O3—Cl—O4	110.8 (2)
C11B—C6B—C7B	118.3 (3)	O3—Cl—O1	110.5 (2)
C11B—C6B—C5B	119.9 (3)	O4—Cl—O1	109.0 (2)
C7B—C6B—C5B	121.8 (3)	O3—Cl—O2	109.75 (19)
C8B—C7B—C6B	120.5 (4)	O4—Cl—O2	107.8 (2)
C8B—C7B—H7B	119.8	O1—Cl—O2	108.92 (17)
C6B—C7B—H7B	119.8	C13—C12—H12A	109.5
C9B—C8B—C7B	120.4 (4)	C13—C12—H12B	109.5
C9B—C8B—H8B	119.8	H12A—C12—H12B	109.5
C7B—C8B—H8B	119.8	C13—C12—H12C	109.5
C8B—C9B—C10B	119.8 (4)	H12A—C12—H12C	109.5
C8B—C9B—H9B	120.1	H12B—C12—H12C	109.5
C10B—C9B—H9B	120.1	C12—C13—C14	113.8 (6)
C9B—C10B—C11B	120.1 (4)	C12—C13—H13A	108.8
C9B—C10B—H10B	119.9	C14—C13—H13A	108.8
C11B—C10B—H10B	119.9	C12—C13—H13B	108.8
C10B—C11B—C6B	120.9 (4)	C14—C13—H13B	108.8
C10B—C11B—H11B	119.6	H13A—C13—H13B	107.7
C6B—C11B—H11B	119.6	O5—C14—C15	111.9 (4)
C2A—N1A—C5A	108.6 (3)	O5—C14—C13	106.1 (4)
C2A—N1A—H1A	124 (3)	C15—C14—C13	109.9 (4)
C5A—N1A—H1A	128 (3)	O5—C14—H14	109.6
N3A—C2A—N1A	110.3 (3)	C15—C14—H14	109.6
N3A—C2A—H2A	124.9	C13—C14—H14	109.6
N1A—C2A—H2A	124.9	C14—C15—H15A	109.5
C2A—N3A—C4A	106.6 (3)	C14—C15—H15B	109.5
C2A—N3A—Cu	124.5 (2)	H15A—C15—H15B	109.5
C4A—N3A—Cu	128.8 (2)	C14—C15—H15C	109.5
C5A—C4A—N3A	109.3 (3)	H15A—C15—H15C	109.5
C5A—C4A—H4A	125.3	H15B—C15—H15C	109.5
N3A—C4A—H4A	125.3	C14—O5—H5	113 (4)
C4A—C5A—N1A	105.1 (3)

Symmetry code: (i) −x, −y, −z.

(7)

Crystal data

C36H32Cl2CuN8O8·2(C3H7NO)	Z = 1
Mr = 985.33	F(000) = 511
Triclinic, P1	Dx = 1.432 Mg m^−3
a = 9.1544 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8343 (5) Å	Cell parameters from 4143 reflections
c = 14.2557 (8) Å	θ = 4.4–28.9°
α = 91.493 (4)°	µ = 0.66 mm^−1
β = 107.948 (5)°	T = 100 K
γ = 109.075 (5)°	Block, purple
V = 1142.38 (11) Å^3	0.25 × 0.15 × 0.15 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4905 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4337 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.022
ω scans	θmax = 27.0°, θmin = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.757, Tmax = 1.000	k = −10→12
8820 measured reflections	l = −17→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: mixed
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 1.107P] where P = (Fo^2 + 2Fc^2)/3
4905 reflections	(Δ/σ)max < 0.001
303 parameters	Δρmax = 0.61 e Å^−3
2 restraints	Δρmin = −0.46 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	0.5000	0.5000	0.5000	0.01613 (10)
N1B	0.6099 (2)	0.41667 (19)	0.24823 (12)	0.0206 (3)
H1B	0.670 (3)	0.397 (3)	0.2187 (17)	0.031*
C2B	0.6479 (2)	0.4455 (2)	0.34702 (15)	0.0204 (4)
H2B	0.7496	0.4519	0.3948	0.024*
N3B	0.52469 (19)	0.46387 (17)	0.36893 (12)	0.0176 (3)
C4B	0.4023 (2)	0.4462 (2)	0.27900 (14)	0.0189 (4)
H4B	0.2983	0.4532	0.2712	0.023*
C5B	0.4535 (2)	0.4171 (2)	0.20304 (15)	0.0194 (4)
C6B	0.3668 (3)	0.3892 (2)	0.09512 (15)	0.0221 (4)
C7B	0.4091 (3)	0.3127 (3)	0.03085 (16)	0.0283 (5)
H7B	0.4991	0.2805	0.0560	0.034*
C8B	0.3192 (3)	0.2832 (3)	−0.07055 (17)	0.0352 (5)
H8B	0.3481	0.2301	−0.1141	0.042*
C9B	0.1890 (3)	0.3300 (3)	−0.10851 (17)	0.0351 (5)
H9B	0.1276	0.3084	−0.1777	0.042*
C10B	0.1485 (3)	0.4085 (3)	−0.04507 (17)	0.0336 (5)
H10B	0.0601	0.4425	−0.0709	0.040*
C11B	0.2362 (3)	0.4380 (3)	0.05616 (16)	0.0285 (5)
H11B	0.2072	0.4917	0.0993	0.034*
N1A	0.8173 (2)	0.92475 (18)	0.57926 (12)	0.0191 (3)
H1A	0.831 (3)	1.0142 (13)	0.5911 (18)	0.029*
C2A	0.6699 (2)	0.8184 (2)	0.54604 (14)	0.0199 (4)
H2A	0.5681	0.8329	0.5323	0.024*
N3A	0.6856 (2)	0.69092 (17)	0.53513 (12)	0.0179 (3)
C4A	0.8516 (2)	0.7179 (2)	0.56183 (14)	0.0182 (4)
H4A	0.8997	0.6460	0.5608	0.022*
C5A	0.9366 (2)	0.8634 (2)	0.59000 (14)	0.0183 (4)
C6A	1.1128 (2)	0.9470 (2)	0.62694 (14)	0.0192 (4)
C7A	1.1738 (3)	1.0970 (2)	0.65597 (15)	0.0222 (4)
H7A	1.1000	1.1477	0.6511	0.027*
C8A	1.3420 (3)	1.1724 (2)	0.69201 (16)	0.0270 (5)
H8A	1.3823	1.2746	0.7111	0.032*
C9A	1.4513 (3)	1.1004 (3)	0.70042 (17)	0.0312 (5)
H9A	1.5661	1.1526	0.7258	0.037*
C10A	1.3917 (3)	0.9511 (3)	0.67148 (18)	0.0324 (5)
H10A	1.4660	0.9008	0.6769	0.039*
C11A	1.2237 (3)	0.8752 (2)	0.63465 (17)	0.0267 (5)
H11A	1.1839	0.7732	0.6145	0.032*
Cl	0.84244 (6)	0.34590 (5)	0.62943 (4)	0.02129 (12)
O1	0.69153 (19)	0.35784 (18)	0.56906 (12)	0.0321 (4)
O2	0.8987 (3)	0.4350 (2)	0.72287 (14)	0.0566 (6)
O3	0.9597 (2)	0.3927 (2)	0.5795 (2)	0.0617 (6)
O4	0.8185 (2)	0.19824 (19)	0.64519 (14)	0.0428 (5)
N2	0.8939 (2)	0.1620 (2)	0.09945 (16)	0.0338 (5)
C12	0.8756 (3)	0.2478 (2)	0.16407 (16)	0.0249 (4)
H12	0.9553	0.2742	0.2289	0.030*
C13	0.7800 (4)	0.1220 (3)	−0.0032 (2)	0.0506 (7)
H13A	0.6996	0.1705	−0.0121	0.076*
H13B	0.7230	0.0165	−0.0169	0.076*
H13C	0.8412	0.1524	−0.0492	0.076*
C14	1.0252 (3)	0.1026 (3)	0.1280 (2)	0.0435 (7)
H14A	1.0973	0.1449	0.1963	0.065*
H14B	1.0888	0.1262	0.0827	0.065*
H14C	0.9780	−0.0032	0.1241	0.065*
O5	0.7639 (2)	0.29644 (19)	0.14732 (12)	0.0345 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01511 (17)	0.01507 (17)	0.01618 (17)	0.00399 (13)	0.00430 (12)	−0.00271 (12)
N1B	0.0211 (8)	0.0242 (9)	0.0199 (8)	0.0110 (7)	0.0084 (7)	0.0002 (7)
C2B	0.0188 (9)	0.0204 (10)	0.0208 (9)	0.0076 (8)	0.0048 (8)	−0.0006 (7)
N3B	0.0157 (8)	0.0166 (8)	0.0180 (8)	0.0041 (6)	0.0042 (6)	−0.0023 (6)
C4B	0.0172 (9)	0.0178 (9)	0.0202 (9)	0.0055 (7)	0.0051 (7)	−0.0008 (7)
C5B	0.0201 (9)	0.0170 (9)	0.0206 (9)	0.0067 (8)	0.0064 (8)	0.0007 (7)
C6B	0.0226 (10)	0.0224 (10)	0.0195 (10)	0.0055 (8)	0.0073 (8)	0.0020 (8)
C7B	0.0285 (11)	0.0341 (12)	0.0217 (10)	0.0115 (10)	0.0078 (9)	−0.0007 (9)
C8B	0.0378 (13)	0.0439 (15)	0.0222 (11)	0.0132 (11)	0.0096 (10)	−0.0026 (10)
C9B	0.0356 (13)	0.0421 (14)	0.0176 (10)	0.0075 (11)	0.0021 (9)	0.0027 (9)
C10B	0.0307 (12)	0.0396 (14)	0.0276 (12)	0.0142 (10)	0.0036 (9)	0.0088 (10)
C11B	0.0304 (12)	0.0322 (12)	0.0246 (11)	0.0141 (10)	0.0081 (9)	0.0038 (9)
N1A	0.0199 (8)	0.0145 (8)	0.0228 (8)	0.0073 (7)	0.0058 (7)	−0.0013 (7)
C2A	0.0183 (9)	0.0190 (10)	0.0206 (9)	0.0057 (8)	0.0053 (8)	−0.0010 (7)
N3A	0.0188 (8)	0.0170 (8)	0.0173 (8)	0.0063 (7)	0.0056 (6)	−0.0013 (6)
C4A	0.0191 (9)	0.0174 (9)	0.0189 (9)	0.0072 (8)	0.0067 (7)	0.0003 (7)
C5A	0.0199 (10)	0.0183 (10)	0.0183 (9)	0.0083 (8)	0.0071 (7)	0.0026 (7)
C6A	0.0205 (10)	0.0191 (10)	0.0167 (9)	0.0046 (8)	0.0071 (7)	0.0025 (7)
C7A	0.0249 (10)	0.0201 (10)	0.0202 (10)	0.0052 (8)	0.0086 (8)	0.0011 (8)
C8A	0.0276 (11)	0.0215 (11)	0.0243 (10)	−0.0013 (9)	0.0094 (9)	0.0007 (8)
C9A	0.0193 (10)	0.0374 (13)	0.0305 (12)	0.0008 (9)	0.0096 (9)	0.0048 (10)
C10A	0.0222 (11)	0.0356 (13)	0.0415 (13)	0.0109 (10)	0.0130 (10)	0.0075 (10)
C11A	0.0233 (11)	0.0219 (11)	0.0357 (12)	0.0081 (9)	0.0109 (9)	0.0024 (9)
Cl	0.0170 (2)	0.0201 (2)	0.0251 (2)	0.00840 (18)	0.00321 (18)	−0.00206 (18)
O1	0.0252 (8)	0.0342 (9)	0.0323 (9)	0.0163 (7)	−0.0021 (7)	−0.0039 (7)
O2	0.0665 (14)	0.0596 (13)	0.0337 (10)	0.0443 (11)	−0.0180 (9)	−0.0227 (9)
O3	0.0375 (11)	0.0532 (13)	0.1028 (18)	0.0046 (9)	0.0476 (12)	0.0035 (12)
O4	0.0644 (13)	0.0252 (9)	0.0538 (11)	0.0271 (9)	0.0276 (10)	0.0093 (8)
N2	0.0314 (10)	0.0336 (11)	0.0404 (11)	0.0152 (9)	0.0141 (9)	−0.0006 (9)
C12	0.0261 (11)	0.0257 (11)	0.0254 (10)	0.0103 (9)	0.0106 (9)	0.0036 (8)
C13	0.0544 (18)	0.0534 (18)	0.0444 (16)	0.0209 (14)	0.0167 (13)	−0.0118 (13)
C14	0.0354 (14)	0.0315 (14)	0.0718 (19)	0.0162 (11)	0.0248 (13)	0.0028 (13)
O5	0.0366 (9)	0.0426 (10)	0.0338 (9)	0.0231 (8)	0.0150 (7)	0.0032 (7)

Geometric parameters (Å, º)

Cu—N3B^i	1.9866 (16)	C4A—C5A	1.365 (3)
Cu—N3B	1.9867 (16)	C4A—H4A	0.9500
Cu—N3A	2.0009 (16)	C5A—C6A	1.463 (3)
Cu—N3A^i	2.0009 (16)	C6A—C11A	1.395 (3)
N1B—C2B	1.341 (3)	C6A—C7A	1.395 (3)
N1B—C5B	1.378 (3)	C7A—C8A	1.390 (3)
N1B—H1B	0.853 (10)	C7A—H7A	0.9500
C2B—N3B	1.323 (3)	C8A—C9A	1.382 (3)
C2B—H2B	0.9500	C8A—H8A	0.9500
N3B—C4B	1.380 (2)	C9A—C10A	1.389 (3)
C4B—C5B	1.363 (3)	C9A—H9A	0.9500
C4B—H4B	0.9500	C10A—C11A	1.389 (3)
C5B—C6B	1.468 (3)	C10A—H10A	0.9500
C6B—C7B	1.389 (3)	C11A—H11A	0.9500
C6B—C11B	1.395 (3)	Cl—O2	1.4242 (18)
C7B—C8B	1.393 (3)	Cl—O3	1.427 (2)
C7B—H7B	0.9500	Cl—O1	1.4288 (15)
C8B—C9B	1.378 (4)	Cl—O4	1.4307 (17)
C8B—H8B	0.9500	N2—C12	1.318 (3)
C9B—C10B	1.382 (4)	N2—C14	1.456 (3)
C9B—H9B	0.9500	N2—C13	1.464 (3)
C10B—C11B	1.387 (3)	C12—O5	1.227 (3)
C10B—H10B	0.9500	C12—H12	0.9500
C11B—H11B	0.9500	C13—H13A	0.9800
N1A—C2A	1.340 (3)	C13—H13B	0.9800
N1A—C5A	1.383 (2)	C13—H13C	0.9800
N1A—H1A	0.851 (10)	C14—H14A	0.9800
C2A—N3A	1.318 (3)	C14—H14B	0.9800
C2A—H2A	0.9500	C14—H14C	0.9800
N3A—C4A	1.378 (2)
N3B^i—Cu—N3B	180.0	C5A—C4A—N3A	109.92 (17)
N3B^i—Cu—N3A	88.25 (7)	C5A—C4A—H4A	125.0
N3B—Cu—N3A	91.75 (7)	N3A—C4A—H4A	125.0
N3B^i—Cu—N3A^i	91.74 (7)	C4A—C5A—N1A	104.74 (17)
N3B—Cu—N3A^i	88.26 (7)	C4A—C5A—C6A	131.54 (18)
N3A—Cu—N3A^i	180.0	N1A—C5A—C6A	123.70 (18)
C2B—N1B—C5B	108.22 (16)	C11A—C6A—C7A	118.71 (19)
C2B—N1B—H1B	125.7 (17)	C11A—C6A—C5A	119.43 (18)
C5B—N1B—H1B	126.0 (17)	C7A—C6A—C5A	121.86 (18)
N3B—C2B—N1B	110.77 (17)	C8A—C7A—C6A	120.2 (2)
N3B—C2B—H2B	124.6	C8A—C7A—H7A	119.9
N1B—C2B—H2B	124.6	C6A—C7A—H7A	119.9
C2B—N3B—C4B	106.01 (16)	C9A—C8A—C7A	120.8 (2)
C2B—N3B—Cu	130.49 (14)	C9A—C8A—H8A	119.6
C4B—N3B—Cu	123.44 (13)	C7A—C8A—H8A	119.6
C5B—C4B—N3B	109.64 (17)	C8A—C9A—C10A	119.4 (2)
C5B—C4B—H4B	125.2	C8A—C9A—H9A	120.3
N3B—C4B—H4B	125.2	C10A—C9A—H9A	120.3
C4B—C5B—N1B	105.37 (17)	C11A—C10A—C9A	120.2 (2)
C4B—C5B—C6B	129.71 (18)	C11A—C10A—H10A	119.9
N1B—C5B—C6B	124.91 (18)	C9A—C10A—H10A	119.9
C7B—C6B—C11B	119.02 (19)	C10A—C11A—C6A	120.7 (2)
C7B—C6B—C5B	121.69 (19)	C10A—C11A—H11A	119.6
C11B—C6B—C5B	119.27 (19)	C6A—C11A—H11A	119.6
C6B—C7B—C8B	119.9 (2)	O2—Cl—O3	110.28 (15)
C6B—C7B—H7B	120.1	O2—Cl—O1	108.93 (10)
C8B—C7B—H7B	120.1	O3—Cl—O1	108.75 (13)
C9B—C8B—C7B	120.9 (2)	O2—Cl—O4	109.46 (12)
C9B—C8B—H8B	119.6	O3—Cl—O4	109.25 (12)
C7B—C8B—H8B	119.6	O1—Cl—O4	110.16 (11)
C8B—C9B—C10B	119.4 (2)	C12—N2—C14	121.4 (2)
C8B—C9B—H9B	120.3	C12—N2—C13	120.4 (2)
C10B—C9B—H9B	120.3	C14—N2—C13	118.3 (2)
C9B—C10B—C11B	120.4 (2)	O5—C12—N2	125.3 (2)
C9B—C10B—H10B	119.8	O5—C12—H12	117.3
C11B—C10B—H10B	119.8	N2—C12—H12	117.3
C10B—C11B—C6B	120.4 (2)	N2—C13—H13A	109.5
C10B—C11B—H11B	119.8	N2—C13—H13B	109.5
C6B—C11B—H11B	119.8	H13A—C13—H13B	109.5
C2A—N1A—C5A	108.48 (16)	N2—C13—H13C	109.5
C2A—N1A—H1A	123.9 (17)	H13A—C13—H13C	109.5
C5A—N1A—H1A	127.6 (17)	H13B—C13—H13C	109.5
N3A—C2A—N1A	110.71 (17)	N2—C14—H14A	109.5
N3A—C2A—H2A	124.6	N2—C14—H14B	109.5
N1A—C2A—H2A	124.6	H14A—C14—H14B	109.5
C2A—N3A—C4A	106.15 (16)	N2—C14—H14C	109.5
C2A—N3A—Cu	124.59 (14)	H14A—C14—H14C	109.5
C4A—N3A—Cu	128.99 (13)	H14B—C14—H14C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

(8)

Crystal data

C36H32Cl2CuN8O8·2(C3H6O)	Z = 1
Mr = 955.29	F(000) = 495
Triclinic, P1	Dx = 1.486 Mg m^−3
a = 9.4814 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7136 (5) Å	Cell parameters from 2736 reflections
c = 13.3146 (9) Å	θ = 5.0–29.3°
α = 69.117 (6)°	µ = 0.71 mm^−1
β = 80.660 (5)°	T = 100 K
γ = 68.833 (5)°	Prism, purple
V = 1067.61 (11) Å^3	0.16 × 0.11 × 0.10 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4579 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3483 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.045
ω scans	θmax = 27.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −12→11
Tmin = 0.586, Tmax = 1.000	k = −11→12
8762 measured reflections	l = −14→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: mixed
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.4849P] where P = (Fo^2 + 2Fc^2)/3
4579 reflections	(Δ/σ)max = 0.001
294 parameters	Δρmax = 0.86 e Å^−3
1 restraint	Δρmin = −0.86 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	0.0000	0.0000	0.5000	0.01941 (16)
N1A	−0.2753 (3)	0.4572 (3)	0.4290 (2)	0.0218 (5)
H1A	−0.288 (4)	0.545 (2)	0.436 (3)	0.033*
C2A	−0.1527 (3)	0.3337 (3)	0.4674 (2)	0.0217 (6)
H2A	−0.0705	0.3364	0.4982	0.026*
N3A	−0.1627 (2)	0.2082 (3)	0.4562 (2)	0.0202 (5)
C4A	−0.2989 (3)	0.2542 (3)	0.4088 (2)	0.0209 (6)
H4A	−0.3366	0.1879	0.3909	0.025*
C5A	−0.3707 (3)	0.4103 (3)	0.3917 (2)	0.0201 (6)
C6A	−0.5164 (3)	0.5148 (3)	0.3430 (2)	0.0212 (6)
C7A	−0.5507 (3)	0.6772 (3)	0.3044 (3)	0.0260 (7)
H7A	−0.4789	0.7221	0.3087	0.031*
C8A	−0.6894 (4)	0.7721 (4)	0.2599 (3)	0.0295 (7)
H8A	−0.7120	0.8821	0.2333	0.035*
C9A	−0.7953 (3)	0.7083 (4)	0.2537 (3)	0.0292 (7)
H9A	−0.8909	0.7743	0.2242	0.035*
C10A	−0.7617 (3)	0.5478 (4)	0.2906 (3)	0.0297 (7)
H10A	−0.8333	0.5034	0.2852	0.036*
C11A	−0.6230 (3)	0.4521 (4)	0.3357 (3)	0.0251 (7)
H11A	−0.6010	0.3421	0.3619	0.030*
N1B	0.3161 (3)	0.1490 (3)	0.2740 (2)	0.0225 (6)
H1B	0.410 (4)	0.145 (4)	0.259 (3)	0.034*
C2B	0.2715 (3)	0.0715 (3)	0.3720 (3)	0.0227 (6)
H2B	0.3354	0.0147	0.4316	0.027*
N3B	0.1281 (3)	0.0841 (3)	0.3752 (2)	0.0212 (5)
C4B	0.0791 (3)	0.1737 (3)	0.2724 (3)	0.0217 (6)
H4B	−0.0206	0.2024	0.2498	0.026*
C5B	0.1949 (3)	0.2149 (3)	0.2080 (3)	0.0212 (6)
C6B	0.2045 (3)	0.3041 (3)	0.0933 (3)	0.0239 (7)
C7B	0.2942 (4)	0.3995 (4)	0.0550 (3)	0.0341 (8)
H7B	0.3489	0.4110	0.1037	0.041*
C8B	0.3038 (4)	0.4782 (4)	−0.0549 (3)	0.0442 (10)
H8B	0.3666	0.5418	−0.0812	0.053*
C9B	0.2236 (4)	0.4643 (4)	−0.1251 (3)	0.0421 (10)
H9B	0.2317	0.5176	−0.1999	0.050*
C10B	0.1311 (4)	0.3740 (4)	−0.0884 (3)	0.0395 (9)
H10B	0.0735	0.3668	−0.1373	0.047*
C11B	0.1225 (4)	0.2931 (4)	0.0210 (3)	0.0304 (7)
H11B	0.0597	0.2295	0.0464	0.037*
Cl	0.22342 (8)	0.16061 (8)	0.62128 (6)	0.02379 (19)
O1	0.1220 (2)	0.0774 (2)	0.62806 (18)	0.0254 (5)
O2	0.3752 (2)	0.0722 (3)	0.5974 (2)	0.0327 (6)
O3	0.2175 (2)	0.1888 (3)	0.7209 (2)	0.0338 (6)
O4	0.1778 (2)	0.3086 (2)	0.5359 (2)	0.0329 (6)
C12	0.6675 (3)	0.1128 (4)	0.1203 (3)	0.0307 (8)
O5	0.6026 (2)	0.1788 (3)	0.18518 (19)	0.0294 (5)
C13	0.5917 (4)	0.0436 (4)	0.0704 (3)	0.0398 (9)
H13A	0.4950	0.0409	0.1089	0.060*
H13B	0.6569	−0.0628	0.0748	0.060*
H13C	0.5737	0.1072	−0.0052	0.060*
C14	0.8278 (4)	0.1021 (5)	0.0827 (4)	0.0506 (11)
H14A	0.8291	0.1760	0.0099	0.076*
H14B	0.8852	−0.0041	0.0820	0.076*
H14C	0.8740	0.1276	0.1315	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0183 (3)	0.0178 (3)	0.0185 (3)	−0.00400 (19)	−0.00156 (19)	−0.0032 (2)
N1A	0.0254 (12)	0.0162 (12)	0.0245 (15)	−0.0049 (10)	−0.0040 (10)	−0.0081 (11)
C2A	0.0210 (14)	0.0207 (15)	0.0201 (17)	−0.0058 (11)	−0.0041 (12)	−0.0026 (12)
N3A	0.0199 (12)	0.0195 (13)	0.0190 (14)	−0.0066 (10)	−0.0003 (10)	−0.0038 (10)
C4A	0.0220 (14)	0.0220 (15)	0.0180 (17)	−0.0080 (12)	−0.0016 (12)	−0.0046 (12)
C5A	0.0210 (14)	0.0223 (15)	0.0156 (16)	−0.0077 (11)	0.0006 (11)	−0.0046 (12)
C6A	0.0239 (14)	0.0209 (15)	0.0171 (16)	−0.0040 (11)	−0.0003 (12)	−0.0079 (12)
C7A	0.0256 (15)	0.0220 (16)	0.0297 (19)	−0.0069 (12)	−0.0028 (13)	−0.0078 (14)
C8A	0.0343 (17)	0.0186 (16)	0.028 (2)	−0.0008 (13)	−0.0046 (14)	−0.0057 (14)
C9A	0.0236 (15)	0.0325 (18)	0.0257 (19)	0.0026 (13)	−0.0058 (13)	−0.0126 (15)
C10A	0.0267 (16)	0.0354 (18)	0.030 (2)	−0.0106 (13)	−0.0044 (14)	−0.0117 (15)
C11A	0.0257 (15)	0.0222 (16)	0.0258 (18)	−0.0053 (12)	−0.0036 (13)	−0.0076 (13)
N1B	0.0194 (12)	0.0265 (14)	0.0224 (15)	−0.0094 (10)	0.0014 (10)	−0.0079 (11)
C2B	0.0250 (15)	0.0235 (16)	0.0195 (17)	−0.0071 (12)	−0.0023 (12)	−0.0072 (13)
N3B	0.0210 (12)	0.0192 (13)	0.0212 (15)	−0.0051 (10)	−0.0015 (10)	−0.0054 (11)
C4B	0.0225 (14)	0.0197 (15)	0.0198 (17)	−0.0050 (11)	−0.0025 (12)	−0.0040 (12)
C5B	0.0208 (14)	0.0178 (14)	0.0222 (17)	−0.0037 (11)	−0.0017 (12)	−0.0055 (12)
C6B	0.0233 (15)	0.0200 (15)	0.0215 (18)	−0.0012 (12)	0.0014 (12)	−0.0058 (13)
C7B	0.0292 (17)	0.0292 (18)	0.032 (2)	−0.0072 (13)	0.0014 (14)	−0.0002 (15)
C8B	0.0361 (19)	0.035 (2)	0.042 (3)	−0.0090 (16)	0.0075 (17)	0.0042 (17)
C9B	0.040 (2)	0.037 (2)	0.021 (2)	0.0046 (16)	0.0082 (16)	0.0008 (16)
C10B	0.044 (2)	0.038 (2)	0.023 (2)	0.0028 (16)	−0.0042 (16)	−0.0105 (16)
C11B	0.0333 (17)	0.0283 (17)	0.0246 (19)	−0.0059 (13)	−0.0003 (14)	−0.0074 (14)
Cl	0.0234 (4)	0.0229 (4)	0.0267 (4)	−0.0075 (3)	−0.0042 (3)	−0.0086 (3)
O1	0.0257 (11)	0.0217 (11)	0.0293 (13)	−0.0086 (9)	−0.0018 (9)	−0.0078 (9)
O2	0.0222 (11)	0.0412 (14)	0.0337 (15)	−0.0079 (10)	−0.0023 (10)	−0.0130 (11)
O3	0.0404 (13)	0.0366 (13)	0.0306 (14)	−0.0116 (10)	−0.0063 (10)	−0.0170 (11)
O4	0.0387 (13)	0.0238 (12)	0.0368 (15)	−0.0140 (10)	−0.0109 (11)	−0.0027 (10)
C12	0.0266 (16)	0.0357 (19)	0.027 (2)	−0.0086 (14)	−0.0030 (14)	−0.0082 (16)
O5	0.0256 (11)	0.0321 (12)	0.0306 (14)	−0.0110 (9)	−0.0005 (10)	−0.0089 (11)
C13	0.0361 (19)	0.045 (2)	0.043 (2)	−0.0065 (16)	−0.0079 (16)	−0.0230 (19)
C14	0.034 (2)	0.077 (3)	0.049 (3)	−0.0260 (19)	0.0093 (18)	−0.027 (2)

Geometric parameters (Å, º)

Cu—N3B^i	2.000 (2)	N3B—C4B	1.383 (4)
Cu—N3B	2.000 (2)	C4B—C5B	1.366 (4)
Cu—N3A	2.002 (2)	C4B—H4B	0.9500
Cu—N3A^i	2.002 (2)	C5B—C6B	1.470 (4)
N1A—C2A	1.341 (4)	C6B—C11B	1.385 (5)
N1A—C5A	1.371 (4)	C6B—C7B	1.391 (4)
N1A—H1A	0.851 (10)	C7B—C8B	1.395 (5)
C2A—N3A	1.318 (4)	C7B—H7B	0.9500
C2A—H2A	0.9500	C8B—C9B	1.365 (6)
N3A—C4A	1.384 (4)	C8B—H8B	0.9500
C4A—C5A	1.368 (4)	C9B—C10B	1.374 (5)
C4A—H4A	0.9500	C9B—H9B	0.9500
C5A—C6A	1.472 (4)	C10B—C11B	1.392 (5)
C6A—C11A	1.386 (4)	C10B—H10B	0.9500
C6A—C7A	1.401 (4)	C11B—H11B	0.9500
C7A—C8A	1.385 (4)	Cl—O3	1.436 (3)
C7A—H7A	0.9500	Cl—O2	1.436 (2)
C8A—C9A	1.383 (5)	Cl—O1	1.438 (2)
C8A—H8A	0.9500	Cl—O4	1.447 (2)
C9A—C10A	1.385 (5)	C12—O5	1.213 (4)
C9A—H9A	0.9500	C12—C13	1.494 (5)
C10A—C11A	1.389 (4)	C12—C14	1.500 (5)
C10A—H10A	0.9500	C13—H13A	0.9800
C11A—H11A	0.9500	C13—H13B	0.9800
N1B—C2B	1.341 (4)	C13—H13C	0.9800
N1B—C5B	1.378 (4)	C14—H14A	0.9800
N1B—H1B	0.87 (3)	C14—H14B	0.9800
C2B—N3B	1.316 (4)	C14—H14C	0.9800
C2B—H2B	0.9500
N3B^i—Cu—N3B	180.0	C4B—N3B—Cu	125.55 (18)
N3B^i—Cu—N3A	91.61 (9)	C5B—C4B—N3B	110.1 (3)
N3B—Cu—N3A	88.39 (9)	C5B—C4B—H4B	125.0
N3B^i—Cu—N3A^i	88.39 (9)	N3B—C4B—H4B	125.0
N3B—Cu—N3A^i	91.61 (9)	C4B—C5B—N1B	104.9 (3)
N3A—Cu—N3A^i	180.0	C4B—C5B—C6B	132.0 (3)
C2A—N1A—C5A	109.0 (2)	N1B—C5B—C6B	123.1 (3)
C2A—N1A—H1A	121 (2)	C11B—C6B—C7B	118.9 (3)
C5A—N1A—H1A	130 (2)	C11B—C6B—C5B	119.4 (3)
N3A—C2A—N1A	110.2 (3)	C7B—C6B—C5B	121.8 (3)
N3A—C2A—H2A	124.9	C6B—C7B—C8B	119.8 (4)
N1A—C2A—H2A	124.9	C6B—C7B—H7B	120.1
C2A—N3A—C4A	106.5 (2)	C8B—C7B—H7B	120.1
C2A—N3A—Cu	122.86 (19)	C9B—C8B—C7B	120.4 (3)
C4A—N3A—Cu	130.7 (2)	C9B—C8B—H8B	119.8
C5A—C4A—N3A	109.2 (3)	C7B—C8B—H8B	119.8
C5A—C4A—H4A	125.4	C8B—C9B—C10B	120.6 (3)
N3A—C4A—H4A	125.4	C8B—C9B—H9B	119.7
C4A—C5A—N1A	105.1 (2)	C10B—C9B—H9B	119.7
C4A—C5A—C6A	130.6 (3)	C9B—C10B—C11B	119.5 (4)
N1A—C5A—C6A	124.3 (3)	C9B—C10B—H10B	120.3
C11A—C6A—C7A	118.9 (3)	C11B—C10B—H10B	120.3
C11A—C6A—C5A	119.6 (3)	C6B—C11B—C10B	120.8 (3)
C7A—C6A—C5A	121.5 (3)	C6B—C11B—H11B	119.6
C8A—C7A—C6A	119.9 (3)	C10B—C11B—H11B	119.6
C8A—C7A—H7A	120.0	O3—Cl—O2	109.89 (14)
C6A—C7A—H7A	120.0	O3—Cl—O1	110.05 (13)
C9A—C8A—C7A	120.6 (3)	O2—Cl—O1	110.00 (13)
C9A—C8A—H8A	119.7	O3—Cl—O4	109.00 (14)
C7A—C8A—H8A	119.7	O2—Cl—O4	108.90 (14)
C8A—C9A—C10A	119.8 (3)	O1—Cl—O4	108.98 (13)
C8A—C9A—H9A	120.1	O5—C12—C13	122.5 (3)
C10A—C9A—H9A	120.1	O5—C12—C14	121.2 (3)
C9A—C10A—C11A	119.8 (3)	C13—C12—C14	116.3 (3)
C9A—C10A—H10A	120.1	C12—C13—H13A	109.5
C11A—C10A—H10A	120.1	C12—C13—H13B	109.5
C6A—C11A—C10A	120.9 (3)	H13A—C13—H13B	109.5
C6A—C11A—H11A	119.6	C12—C13—H13C	109.5
C10A—C11A—H11A	119.6	H13A—C13—H13C	109.5
C2B—N1B—C5B	108.2 (2)	H13B—C13—H13C	109.5
C2B—N1B—H1B	121 (2)	C12—C14—H14A	109.5
C5B—N1B—H1B	130 (2)	C12—C14—H14B	109.5
N3B—C2B—N1B	111.4 (3)	H14A—C14—H14B	109.5
N3B—C2B—H2B	124.3	C12—C14—H14C	109.5
N1B—C2B—H2B	124.3	H14A—C14—H14C	109.5
C2B—N3B—C4B	105.5 (2)	H14B—C14—H14C	109.5
C2B—N3B—Cu	128.9 (2)

Symmetry code: (i) −x, −y, −z+1.

(9)

Crystal data

C36H32Cl2CuN8O8·2(C4H8O)	F(000) = 1022
Mr = 983.34	Dx = 1.501 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0943 (5) Å	Cell parameters from 3274 reflections
b = 25.0287 (17) Å	θ = 3.2–28.8°
c = 10.0253 (5) Å	µ = 0.69 mm^−1
β = 107.509 (6)°	T = 100 K
V = 2176.2 (2) Å^3	Block, pink
Z = 2	0.23 × 0.13 × 0.13 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	3808 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2800 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.089
ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→10
Tmin = 0.503, Tmax = 1.000	k = −28→29
8871 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: mixed
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 4.9457P] where P = (Fo^2 + 2Fc^2)/3
3808 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.87 e Å^−3
3 restraints	Δρmin = −0.58 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	1.0000	0.5000	1.0000	0.0174 (2)
N1A	0.7458 (5)	0.53575 (15)	0.5964 (4)	0.0186 (9)
H1A	0.740 (6)	0.539 (2)	0.5106 (17)	0.028*
C2A	0.8720 (5)	0.52004 (18)	0.6975 (4)	0.0179 (10)
H2A	0.9649	0.5081	0.6824	0.021*
N3A	0.8487 (4)	0.52353 (16)	0.8208 (4)	0.0195 (9)
C4A	0.7009 (5)	0.5419 (2)	0.7973 (4)	0.0207 (10)
H4A	0.6527	0.5483	0.8678	0.025*
C5A	0.6333 (5)	0.54968 (18)	0.6568 (4)	0.0171 (10)
C6A	0.4788 (5)	0.56786 (18)	0.5781 (4)	0.0185 (10)
C7A	0.4401 (6)	0.58266 (19)	0.4375 (5)	0.0229 (11)
H7A	0.5151	0.5802	0.3892	0.028*
C8A	0.2937 (6)	0.6009 (2)	0.3680 (5)	0.0273 (12)
H8A	0.2691	0.6105	0.2721	0.033*
C9A	0.1826 (6)	0.6055 (2)	0.4355 (5)	0.0293 (12)
H9A	0.0829	0.6188	0.3876	0.035*
C10A	0.2199 (6)	0.5900 (2)	0.5762 (5)	0.0284 (12)
H10A	0.1442	0.5923	0.6238	0.034*
C11A	0.3653 (6)	0.5716 (2)	0.6458 (5)	0.0244 (11)
H11A	0.3889	0.5612	0.7411	0.029*
N1B	1.3318 (5)	0.61396 (17)	1.0015 (4)	0.0253 (9)
H1B	1.412 (3)	0.6263 (19)	0.985 (4)	0.038*
C2B	1.2767 (6)	0.5640 (2)	0.9937 (5)	0.0248 (11)
H2B	1.3346	0.5327	0.9901	0.030*
N3B	1.1312 (4)	0.56417 (16)	0.9917 (4)	0.0195 (9)
C4B	1.0908 (6)	0.6171 (2)	0.9955 (5)	0.0253 (11)
H4B	0.9917	0.6297	0.9939	0.030*
C5B	1.2149 (6)	0.6485 (2)	1.0020 (4)	0.0229 (11)
C6B	1.2398 (6)	0.7066 (2)	1.0182 (5)	0.0282 (12)
C7B	1.3821 (7)	0.7275 (2)	1.0918 (5)	0.0351 (13)
H7B	1.4653	0.7041	1.1343	0.042*
C8B	1.4040 (9)	0.7825 (2)	1.1038 (6)	0.0477 (17)
H8B	1.5023	0.7965	1.1538	0.057*
C9B	1.2840 (10)	0.8168 (3)	1.0438 (7)	0.0534 (19)
H9B	1.2989	0.8544	1.0518	0.064*
C10B	1.1424 (9)	0.7961 (3)	0.9722 (7)	0.0528 (18)
H10B	1.0589	0.8195	0.9306	0.063*
C11B	1.1206 (8)	0.7412 (2)	0.9602 (6)	0.0405 (14)
H11B	1.0219	0.7274	0.9111	0.049*
Cl	0.75166 (13)	0.56940 (5)	1.20112 (10)	0.0192 (3)
O1	0.8659 (4)	0.56382 (14)	1.1289 (3)	0.0288 (8)
O2	0.6111 (4)	0.54488 (16)	1.1206 (4)	0.0381 (10)
O3	0.7245 (5)	0.62435 (15)	1.2222 (4)	0.0491 (11)
O4	0.8078 (4)	0.54341 (17)	1.3339 (3)	0.0403 (10)
O5	0.5364 (4)	0.66778 (15)	0.8771 (4)	0.0346 (9)
C12	0.6895 (7)	0.6889 (2)	0.9068 (6)	0.0423 (15)
H12A	0.7428	0.6734	0.8431	0.051*
H12B	0.7507	0.6811	1.0045	0.051*
C13	0.6683 (7)	0.7487 (2)	0.8836 (7)	0.0467 (16)
H13A	0.6803	0.7674	0.9732	0.056*
H13B	0.7448	0.7631	0.8407	0.056*
C14	0.5069 (7)	0.7555 (2)	0.7865 (6)	0.0394 (14)
H14A	0.5081	0.7726	0.6978	0.047*
H14B	0.4437	0.7774	0.8305	0.047*
C15	0.4450 (7)	0.6986 (2)	0.7611 (5)	0.0375 (14)
H15A	0.3349	0.6976	0.7570	0.045*
H15B	0.4552	0.6846	0.6720	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0132 (4)	0.0231 (5)	0.0141 (4)	−0.0010 (4)	0.0013 (3)	0.0014 (3)
N1A	0.023 (2)	0.020 (2)	0.0130 (18)	−0.0007 (18)	0.0055 (17)	−0.0003 (16)
C2A	0.018 (3)	0.017 (2)	0.018 (2)	0.000 (2)	0.0029 (19)	0.0013 (19)
N3A	0.015 (2)	0.026 (2)	0.0177 (19)	−0.0026 (18)	0.0050 (16)	−0.0007 (17)
C4A	0.019 (3)	0.027 (3)	0.017 (2)	0.001 (2)	0.0063 (19)	0.000 (2)
C5A	0.017 (2)	0.016 (2)	0.016 (2)	−0.002 (2)	0.0020 (19)	−0.0020 (19)
C6A	0.022 (3)	0.012 (2)	0.019 (2)	−0.006 (2)	0.003 (2)	−0.0048 (19)
C7A	0.026 (3)	0.021 (3)	0.019 (2)	−0.002 (2)	0.003 (2)	0.003 (2)
C8A	0.032 (3)	0.022 (3)	0.021 (2)	−0.001 (2)	−0.002 (2)	0.006 (2)
C9A	0.022 (3)	0.019 (3)	0.038 (3)	0.003 (2)	−0.006 (2)	0.004 (2)
C10A	0.020 (3)	0.028 (3)	0.036 (3)	−0.001 (2)	0.006 (2)	−0.005 (2)
C11A	0.024 (3)	0.027 (3)	0.021 (2)	−0.001 (2)	0.004 (2)	−0.001 (2)
N1B	0.022 (2)	0.025 (2)	0.032 (2)	−0.002 (2)	0.0117 (19)	0.0012 (19)
C2B	0.023 (3)	0.024 (3)	0.030 (3)	−0.004 (2)	0.011 (2)	−0.004 (2)
N3B	0.018 (2)	0.023 (2)	0.0150 (18)	−0.0040 (18)	0.0022 (16)	−0.0030 (16)
C4B	0.023 (3)	0.026 (3)	0.027 (2)	0.006 (2)	0.008 (2)	0.006 (2)
C5B	0.026 (3)	0.024 (3)	0.017 (2)	0.003 (2)	0.005 (2)	0.008 (2)
C6B	0.037 (3)	0.023 (3)	0.027 (3)	0.004 (3)	0.013 (2)	0.007 (2)
C7B	0.043 (4)	0.026 (3)	0.040 (3)	−0.004 (3)	0.017 (3)	0.000 (2)
C8B	0.069 (5)	0.032 (3)	0.049 (4)	−0.010 (3)	0.028 (3)	−0.004 (3)
C9B	0.088 (6)	0.022 (3)	0.060 (4)	0.002 (4)	0.038 (4)	0.002 (3)
C10B	0.070 (5)	0.035 (4)	0.060 (4)	0.018 (4)	0.029 (4)	0.013 (3)
C11B	0.048 (4)	0.031 (3)	0.046 (3)	0.011 (3)	0.020 (3)	0.012 (3)
Cl	0.0194 (6)	0.0216 (6)	0.0170 (5)	0.0012 (5)	0.0061 (4)	−0.0004 (5)
O1	0.028 (2)	0.040 (2)	0.0213 (17)	0.0006 (17)	0.0128 (15)	−0.0002 (15)
O2	0.019 (2)	0.049 (3)	0.042 (2)	−0.0015 (19)	0.0034 (17)	−0.0154 (19)
O3	0.064 (3)	0.025 (2)	0.068 (3)	0.002 (2)	0.036 (2)	−0.009 (2)
O4	0.031 (2)	0.068 (3)	0.0244 (18)	0.014 (2)	0.0124 (16)	0.0216 (19)
O5	0.030 (2)	0.033 (2)	0.042 (2)	−0.0030 (18)	0.0133 (18)	0.0058 (17)
C12	0.031 (3)	0.043 (4)	0.052 (3)	−0.006 (3)	0.012 (3)	0.003 (3)
C13	0.040 (4)	0.031 (3)	0.071 (4)	−0.005 (3)	0.020 (3)	0.002 (3)
C14	0.049 (4)	0.032 (3)	0.043 (3)	0.006 (3)	0.022 (3)	0.005 (3)
C15	0.041 (4)	0.038 (3)	0.035 (3)	0.003 (3)	0.014 (3)	0.008 (3)

Geometric parameters (Å, º)

Cu—N3A	1.995 (4)	C4B—H4B	0.9500
Cu—N3A^i	1.995 (4)	C5B—C6B	1.473 (7)
Cu—N3B	2.018 (4)	C6B—C11B	1.372 (8)
Cu—N3B^i	2.018 (4)	C6B—C7B	1.385 (8)
N1A—C2A	1.341 (6)	C7B—C8B	1.390 (8)
N1A—C5A	1.381 (6)	C7B—H7B	0.9500
N1A—H1A	0.848 (10)	C8B—C9B	1.377 (9)
C2A—N3A	1.319 (5)	C8B—H8B	0.9500
C2A—H2A	0.9500	C9B—C10B	1.373 (10)
N3A—C4A	1.372 (6)	C9B—H9B	0.9500
C4A—C5A	1.371 (6)	C10B—C11B	1.389 (8)
C4A—H4A	0.9500	C10B—H10B	0.9500
C5A—C6A	1.461 (7)	C11B—H11B	0.9500
C6A—C7A	1.396 (6)	Cl—O3	1.424 (4)
C6A—C11A	1.398 (7)	Cl—O2	1.429 (4)
C7A—C8A	1.382 (7)	Cl—O4	1.430 (3)
C7A—H7A	0.9500	Cl—O1	1.440 (3)
C8A—C9A	1.379 (7)	O5—C12	1.435 (7)
C8A—H8A	0.9500	O5—C15	1.435 (6)
C9A—C10A	1.402 (7)	C12—C13	1.517 (8)
C9A—H9A	0.9500	C12—H12A	0.9900
C10A—C11A	1.376 (7)	C12—H12B	0.9900
C10A—H10A	0.9500	C13—C14	1.507 (8)
C11A—H11A	0.9500	C13—H13A	0.9900
N1B—C2B	1.341 (6)	C13—H13B	0.9900
N1B—C5B	1.372 (6)	C14—C15	1.523 (8)
N1B—H1B	0.858 (10)	C14—H14A	0.9900
C2B—N3B	1.317 (6)	C14—H14B	0.9900
C2B—H2B	0.9500	C15—H15A	0.9900
N3B—C4B	1.379 (6)	C15—H15B	0.9900
C4B—C5B	1.361 (7)
N3A—Cu—N3A^i	180.0 (2)	C4B—C5B—C6B	132.3 (5)
N3A—Cu—N3B	89.11 (15)	N1B—C5B—C6B	122.0 (4)
N3A^i—Cu—N3B	90.89 (15)	C11B—C6B—C7B	118.7 (5)
N3A—Cu—N3B^i	90.90 (15)	C11B—C6B—C5B	120.0 (5)
N3A^i—Cu—N3B^i	89.10 (15)	C7B—C6B—C5B	121.3 (5)
N3B—Cu—N3B^i	180.0	C6B—C7B—C8B	120.5 (6)
C2A—N1A—C5A	108.7 (4)	C6B—C7B—H7B	119.8
C2A—N1A—H1A	125 (4)	C8B—C7B—H7B	119.8
C5A—N1A—H1A	126 (4)	C9B—C8B—C7B	120.3 (7)
N3A—C2A—N1A	110.3 (4)	C9B—C8B—H8B	119.8
N3A—C2A—H2A	124.9	C7B—C8B—H8B	119.8
N1A—C2A—H2A	124.9	C10B—C9B—C8B	119.3 (6)
C2A—N3A—C4A	106.7 (4)	C10B—C9B—H9B	120.4
C2A—N3A—Cu	124.3 (3)	C8B—C9B—H9B	120.4
C4A—N3A—Cu	128.9 (3)	C9B—C10B—C11B	120.4 (6)
C5A—C4A—N3A	109.7 (4)	C9B—C10B—H10B	119.8
C5A—C4A—H4A	125.2	C11B—C10B—H10B	119.8
N3A—C4A—H4A	125.2	C6B—C11B—C10B	120.9 (6)
C4A—C5A—N1A	104.6 (4)	C6B—C11B—H11B	119.6
C4A—C5A—C6A	131.3 (4)	C10B—C11B—H11B	119.6
N1A—C5A—C6A	124.1 (4)	O3—Cl—O2	109.5 (3)
C7A—C6A—C11A	118.3 (5)	O3—Cl—O4	109.3 (3)
C7A—C6A—C5A	122.5 (4)	O2—Cl—O4	109.8 (2)
C11A—C6A—C5A	119.3 (4)	O3—Cl—O1	110.6 (2)
C8A—C7A—C6A	120.6 (5)	O2—Cl—O1	109.4 (2)
C8A—C7A—H7A	119.7	O4—Cl—O1	108.3 (2)
C6A—C7A—H7A	119.7	C12—O5—C15	105.0 (4)
C9A—C8A—C7A	121.1 (5)	O5—C12—C13	105.2 (5)
C9A—C8A—H8A	119.4	O5—C12—H12A	110.7
C7A—C8A—H8A	119.4	C13—C12—H12A	110.7
C8A—C9A—C10A	118.7 (5)	O5—C12—H12B	110.7
C8A—C9A—H9A	120.7	C13—C12—H12B	110.7
C10A—C9A—H9A	120.7	H12A—C12—H12B	108.8
C11A—C10A—C9A	120.4 (5)	C14—C13—C12	105.4 (5)
C11A—C10A—H10A	119.8	C14—C13—H13A	110.7
C9A—C10A—H10A	119.8	C12—C13—H13A	110.7
C10A—C11A—C6A	120.9 (4)	C14—C13—H13B	110.7
C10A—C11A—H11A	119.5	C12—C13—H13B	110.7
C6A—C11A—H11A	119.5	H13A—C13—H13B	108.8
C2B—N1B—C5B	108.2 (4)	C13—C14—C15	104.0 (5)
C2B—N1B—H1B	131 (4)	C13—C14—H14A	111.0
C5B—N1B—H1B	119 (3)	C15—C14—H14A	111.0
N3B—C2B—N1B	110.7 (4)	C13—C14—H14B	111.0
N3B—C2B—H2B	124.7	C15—C14—H14B	111.0
N1B—C2B—H2B	124.7	H14A—C14—H14B	109.0
C2B—N3B—C4B	106.2 (4)	O5—C15—C14	105.8 (5)
C2B—N3B—Cu	126.9 (3)	O5—C15—H15A	110.6
C4B—N3B—Cu	126.7 (3)	C14—C15—H15A	110.6
C5B—C4B—N3B	109.4 (4)	O5—C15—H15B	110.6
C5B—C4B—H4B	125.3	C14—C15—H15B	110.6
N3B—C4B—H4B	125.3	H15A—C15—H15B	108.7
C4B—C5B—N1B	105.6 (4)

Symmetry code: (i) −x+2, −y+1, −z+2.

(10)

Crystal data

C36H32Cl2CuN8O8·2(C4H8O2)	Z = 1
Mr = 1015.34	F(000) = 527
Triclinic, P1	Dx = 1.491 Mg m^−3
a = 9.3679 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2347 (8) Å	Cell parameters from 2153 reflections
c = 12.5311 (15) Å	θ = 4.0–27.8°
α = 79.661 (8)°	µ = 0.67 mm^−1
β = 84.578 (9)°	T = 100 K
γ = 73.249 (8)°	Prism, pink
V = 1130.6 (2) Å^3	0.22 × 0.10 × 0.10 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4867 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3144 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.083
ω scans	θmax = 27.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.489, Tmax = 1.000	k = −13→12
10186 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: mixed
wR(F^2) = 0.184	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0702P)^2 + 0.2104P] where P = (Fo^2 + 2Fc^2)/3
4867 reflections	(Δ/σ)max < 0.001
310 parameters	Δρmax = 0.99 e Å^−3
2 restraints	Δρmin = −0.59 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	0.0000	0.0000	0.0000	0.0228 (2)
N1A	−0.2415 (4)	0.3720 (3)	0.0907 (3)	0.0226 (8)
H1A	−0.250 (5)	0.4568 (16)	0.093 (4)	0.034*
C2A	−0.1179 (5)	0.2842 (4)	0.0555 (3)	0.0231 (9)
H2A	−0.0243	0.3037	0.0390	0.028*
N3A	−0.1446 (4)	0.1658 (3)	0.0469 (3)	0.0239 (8)
C4A	−0.2928 (5)	0.1820 (4)	0.0779 (3)	0.0233 (9)
H4A	−0.3443	0.1139	0.0804	0.028*
C5A	−0.3546 (5)	0.3102 (4)	0.1045 (3)	0.0226 (9)
C6A	−0.5088 (5)	0.3775 (4)	0.1388 (3)	0.0231 (9)
C7A	−0.5577 (5)	0.5199 (4)	0.1414 (3)	0.0282 (10)
H7A	−0.4897	0.5746	0.1239	0.034*
C8A	−0.7057 (5)	0.5806 (4)	0.1697 (4)	0.0340 (11)
H8A	−0.7382	0.6771	0.1715	0.041*
C9A	−0.8062 (5)	0.5038 (4)	0.1953 (3)	0.0331 (11)
H9A	−0.9071	0.5468	0.2149	0.040*
C10A	−0.7596 (5)	0.3645 (5)	0.1922 (4)	0.0349 (11)
H10A	−0.8287	0.3108	0.2087	0.042*
C11A	−0.6110 (5)	0.3017 (4)	0.1650 (4)	0.0348 (11)
H11A	−0.5795	0.2049	0.1644	0.042*
N1B	0.2299 (5)	−0.0630 (4)	0.2816 (3)	0.0327 (9)
H1B	0.304 (4)	−0.061 (5)	0.316 (4)	0.049*
C2B	0.2134 (5)	−0.0190 (4)	0.1747 (4)	0.0306 (10)
H2B	0.2795	0.0224	0.1277	0.037*
N3B	0.0923 (4)	−0.0414 (3)	0.1442 (3)	0.0244 (8)
C4B	0.0295 (5)	−0.1022 (4)	0.2366 (3)	0.0266 (10)
H4B	−0.0597	−0.1295	0.2394	0.032*
C5B	0.1135 (5)	−0.1177 (4)	0.3233 (3)	0.0261 (10)
C6B	0.0977 (5)	−0.1841 (4)	0.4363 (3)	0.0288 (10)
C7B	0.1703 (6)	−0.1587 (5)	0.5189 (4)	0.0389 (12)
H7B	0.2261	−0.0928	0.5036	0.047*
C8B	0.1616 (6)	−0.2292 (5)	0.6234 (4)	0.0407 (12)
H8B	0.2117	−0.2116	0.6795	0.049*
C9B	0.0801 (6)	−0.3252 (5)	0.6467 (4)	0.0400 (12)
H9B	0.0760	−0.3750	0.7180	0.048*
C10B	0.0047 (6)	−0.3479 (5)	0.5653 (4)	0.0463 (13)
H10B	−0.0536	−0.4117	0.5812	0.056*
C11B	0.0139 (6)	−0.2777 (5)	0.4602 (4)	0.0392 (12)
H11B	−0.0376	−0.2942	0.4044	0.047*
Cl	−0.26455 (12)	−0.23638 (10)	0.12344 (9)	0.0291 (3)
O1	−0.1892 (4)	−0.1389 (3)	0.0649 (3)	0.0352 (8)
O2	−0.2282 (6)	−0.2669 (5)	0.2349 (3)	0.0780 (14)
O3	−0.4184 (4)	−0.1889 (4)	0.1095 (4)	0.0800 (15)
O4	−0.2060 (5)	−0.3628 (3)	0.0814 (3)	0.0614 (12)
O5	0.4417 (4)	−0.0034 (3)	0.4005 (3)	0.0478 (9)
C12	0.4001 (6)	0.1176 (5)	0.4514 (4)	0.0479 (14)
H12A	0.2969	0.1714	0.4331	0.057*
H12B	0.4670	0.1763	0.4229	0.057*
C13	0.5909 (6)	−0.0807 (5)	0.4265 (4)	0.0479 (14)
H13A	0.6607	−0.0251	0.3971	0.057*
H13B	0.6197	−0.1660	0.3934	0.057*
O6	0.4680 (4)	0.3713 (3)	0.5179 (3)	0.0492 (10)
C14	0.4039 (7)	0.4775 (5)	0.4322 (4)	0.0463 (13)
H14A	0.3061	0.5337	0.4579	0.056*
H14B	0.3869	0.4356	0.3709	0.056*
C15	0.4936 (6)	0.4299 (5)	0.6064 (4)	0.0457 (13)
H15A	0.5402	0.3555	0.6651	0.055*
H15B	0.3975	0.4848	0.6357	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0215 (5)	0.0189 (4)	0.0295 (4)	−0.0064 (3)	0.0003 (3)	−0.0072 (3)
N1A	0.024 (2)	0.0173 (15)	0.0293 (19)	−0.0074 (15)	−0.0001 (15)	−0.0074 (14)
C2A	0.023 (2)	0.0214 (19)	0.028 (2)	−0.0089 (17)	0.0004 (17)	−0.0074 (16)
N3A	0.024 (2)	0.0198 (16)	0.031 (2)	−0.0084 (15)	−0.0063 (15)	−0.0062 (14)
C4A	0.023 (3)	0.0194 (19)	0.030 (2)	−0.0097 (17)	−0.0022 (18)	−0.0044 (16)
C5A	0.023 (2)	0.0226 (19)	0.023 (2)	−0.0075 (17)	−0.0037 (17)	−0.0049 (15)
C6A	0.028 (3)	0.0226 (19)	0.021 (2)	−0.0092 (18)	−0.0024 (17)	−0.0034 (16)
C7A	0.025 (3)	0.023 (2)	0.035 (2)	−0.0039 (18)	−0.0007 (19)	−0.0068 (17)
C8A	0.035 (3)	0.025 (2)	0.037 (3)	0.002 (2)	−0.004 (2)	−0.0082 (18)
C9A	0.025 (3)	0.039 (2)	0.028 (2)	0.000 (2)	0.0025 (19)	−0.0039 (19)
C10A	0.023 (3)	0.046 (3)	0.040 (3)	−0.016 (2)	0.004 (2)	−0.011 (2)
C11A	0.033 (3)	0.030 (2)	0.045 (3)	−0.013 (2)	0.002 (2)	−0.012 (2)
N1B	0.034 (3)	0.041 (2)	0.032 (2)	−0.0195 (18)	−0.0096 (17)	−0.0060 (16)
C2B	0.026 (3)	0.032 (2)	0.039 (3)	−0.017 (2)	0.002 (2)	−0.0076 (19)
N3B	0.022 (2)	0.0196 (16)	0.032 (2)	−0.0054 (15)	0.0007 (15)	−0.0069 (14)
C4B	0.022 (3)	0.024 (2)	0.036 (2)	−0.0043 (18)	−0.0007 (19)	−0.0115 (17)
C5B	0.020 (2)	0.025 (2)	0.036 (2)	−0.0060 (18)	−0.0001 (19)	−0.0127 (18)
C6B	0.022 (3)	0.033 (2)	0.030 (2)	−0.0016 (19)	−0.0020 (19)	−0.0116 (18)
C7B	0.036 (3)	0.047 (3)	0.038 (3)	−0.014 (2)	−0.010 (2)	−0.011 (2)
C8B	0.036 (3)	0.057 (3)	0.030 (3)	−0.011 (2)	−0.008 (2)	−0.010 (2)
C9B	0.033 (3)	0.061 (3)	0.027 (2)	−0.017 (2)	0.004 (2)	−0.006 (2)
C10B	0.044 (3)	0.070 (3)	0.032 (3)	−0.031 (3)	0.005 (2)	−0.007 (2)
C11B	0.035 (3)	0.056 (3)	0.034 (3)	−0.020 (2)	0.001 (2)	−0.014 (2)
Cl	0.0283 (7)	0.0276 (5)	0.0376 (6)	−0.0157 (5)	0.0053 (5)	−0.0122 (4)
O1	0.033 (2)	0.0248 (14)	0.052 (2)	−0.0167 (13)	0.0039 (15)	−0.0033 (13)
O2	0.106 (4)	0.123 (3)	0.039 (2)	−0.089 (3)	0.012 (2)	−0.014 (2)
O3	0.025 (2)	0.055 (2)	0.157 (5)	−0.0158 (19)	0.003 (3)	−0.004 (3)
O4	0.068 (3)	0.0314 (17)	0.094 (3)	−0.0252 (18)	0.023 (2)	−0.0282 (18)
O5	0.050 (3)	0.059 (2)	0.047 (2)	−0.0246 (19)	−0.0088 (18)	−0.0200 (17)
C12	0.039 (3)	0.052 (3)	0.057 (4)	−0.014 (3)	−0.004 (3)	−0.016 (3)
C13	0.048 (4)	0.052 (3)	0.053 (3)	−0.020 (3)	−0.004 (3)	−0.021 (2)
O6	0.069 (3)	0.0434 (19)	0.039 (2)	−0.0202 (18)	−0.0105 (18)	−0.0039 (15)
C14	0.052 (4)	0.046 (3)	0.043 (3)	−0.015 (3)	−0.015 (3)	−0.004 (2)
C15	0.055 (4)	0.041 (3)	0.044 (3)	−0.017 (3)	−0.011 (3)	−0.005 (2)

Geometric parameters (Å, º)

Cu—N3A^i	1.986 (3)	C5B—C6B	1.471 (6)
Cu—N3A	1.986 (3)	C6B—C11B	1.382 (7)
Cu—N3B	2.000 (3)	C6B—C7B	1.389 (6)
Cu—N3B^i	2.000 (3)	C7B—C8B	1.385 (7)
N1A—C2A	1.338 (5)	C7B—H7B	0.9500
N1A—C5A	1.365 (5)	C8B—C9B	1.386 (7)
N1A—H1A	0.854 (10)	C8B—H8B	0.9500
C2A—N3A	1.330 (5)	C9B—C10B	1.381 (7)
C2A—H2A	0.9500	C9B—H9B	0.9500
N3A—C4A	1.377 (5)	C10B—C11B	1.390 (7)
C4A—C5A	1.360 (5)	C10B—H10B	0.9500
C4A—H4A	0.9500	C11B—H11B	0.9500
C5A—C6A	1.470 (6)	Cl—O3	1.399 (4)
C6A—C11A	1.379 (6)	Cl—O2	1.426 (4)
C6A—C7A	1.402 (5)	Cl—O4	1.426 (3)
C7A—C8A	1.387 (6)	Cl—O1	1.442 (3)
C7A—H7A	0.9500	O5—C13	1.429 (6)
C8A—C9A	1.373 (7)	O5—C12	1.432 (5)
C8A—H8A	0.9500	C12—C13^ii	1.514 (7)
C9A—C10A	1.372 (6)	C12—H12A	0.9900
C9A—H9A	0.9500	C12—H12B	0.9900
C10A—C11A	1.393 (6)	C13—C12^ii	1.514 (7)
C10A—H10A	0.9500	C13—H13A	0.9900
C11A—H11A	0.9500	C13—H13B	0.9900
N1B—C2B	1.342 (6)	O6—C14	1.421 (6)
N1B—C5B	1.383 (6)	O6—C15	1.422 (5)
N1B—H1B	0.859 (10)	C14—C15^iii	1.526 (8)
C2B—N3B	1.323 (5)	C14—H14A	0.9900
C2B—H2B	0.9500	C14—H14B	0.9900
N3B—C4B	1.377 (5)	C15—C14^iii	1.526 (8)
C4B—C5B	1.362 (6)	C15—H15A	0.9900
C4B—H4B	0.9500	C15—H15B	0.9900
N3A^i—Cu—N3A	180.0	C4B—C5B—C6B	130.5 (4)
N3A^i—Cu—N3B	91.19 (13)	N1B—C5B—C6B	124.8 (4)
N3A—Cu—N3B	88.81 (13)	C11B—C6B—C7B	119.3 (4)
N3A^i—Cu—N3B^i	88.81 (13)	C11B—C6B—C5B	119.3 (4)
N3A—Cu—N3B^i	91.19 (13)	C7B—C6B—C5B	121.3 (4)
N3B—Cu—N3B^i	180.0	C8B—C7B—C6B	120.2 (5)
C2A—N1A—C5A	108.8 (3)	C8B—C7B—H7B	119.9
C2A—N1A—H1A	124 (3)	C6B—C7B—H7B	119.9
C5A—N1A—H1A	126 (3)	C7B—C8B—C9B	120.3 (4)
N3A—C2A—N1A	110.3 (4)	C7B—C8B—H8B	119.9
N3A—C2A—H2A	124.8	C9B—C8B—H8B	119.9
N1A—C2A—H2A	124.8	C10B—C9B—C8B	119.5 (5)
C2A—N3A—C4A	105.7 (3)	C10B—C9B—H9B	120.2
C2A—N3A—Cu	127.0 (3)	C8B—C9B—H9B	120.2
C4A—N3A—Cu	127.3 (2)	C9B—C10B—C11B	120.2 (5)
C5A—C4A—N3A	109.8 (4)	C9B—C10B—H10B	119.9
C5A—C4A—H4A	125.1	C11B—C10B—H10B	119.9
N3A—C4A—H4A	125.1	C6B—C11B—C10B	120.3 (4)
C4A—C5A—N1A	105.4 (4)	C6B—C11B—H11B	119.8
C4A—C5A—C6A	130.4 (4)	C10B—C11B—H11B	119.8
N1A—C5A—C6A	124.2 (3)	O3—Cl—O2	112.8 (3)
C11A—C6A—C7A	118.3 (4)	O3—Cl—O4	109.2 (3)
C11A—C6A—C5A	120.2 (3)	O2—Cl—O4	106.0 (3)
C7A—C6A—C5A	121.4 (4)	O3—Cl—O1	111.1 (2)
C8A—C7A—C6A	119.7 (4)	O2—Cl—O1	109.9 (2)
C8A—C7A—H7A	120.2	O4—Cl—O1	107.5 (2)
C6A—C7A—H7A	120.2	C13—O5—C12	109.3 (4)
C9A—C8A—C7A	121.3 (4)	O5—C12—C13^ii	111.5 (4)
C9A—C8A—H8A	119.4	O5—C12—H12A	109.3
C7A—C8A—H8A	119.4	C13^ii—C12—H12A	109.3
C10A—C9A—C8A	119.4 (4)	O5—C12—H12B	109.3
C10A—C9A—H9A	120.3	C13^ii—C12—H12B	109.3
C8A—C9A—H9A	120.3	H12A—C12—H12B	108.0
C9A—C10A—C11A	120.0 (5)	O5—C13—C12^ii	109.2 (4)
C9A—C10A—H10A	120.0	O5—C13—H13A	109.8
C11A—C10A—H10A	120.0	C12^ii—C13—H13A	109.8
C6A—C11A—C10A	121.3 (4)	O5—C13—H13B	109.8
C6A—C11A—H11A	119.4	C12^ii—C13—H13B	109.8
C10A—C11A—H11A	119.4	H13A—C13—H13B	108.3
C2B—N1B—C5B	108.6 (4)	C14—O6—C15	110.2 (4)
C2B—N1B—H1B	124 (4)	O6—C14—C15^iii	110.6 (4)
C5B—N1B—H1B	127 (4)	O6—C14—H14A	109.5
N3B—C2B—N1B	110.5 (4)	C15^iii—C14—H14A	109.5
N3B—C2B—H2B	124.8	O6—C14—H14B	109.5
N1B—C2B—H2B	124.8	C15^iii—C14—H14B	109.5
C2B—N3B—C4B	106.0 (4)	H14A—C14—H14B	108.1
C2B—N3B—Cu	131.8 (3)	O6—C15—C14^iii	109.4 (4)
C4B—N3B—Cu	122.2 (3)	O6—C15—H15A	109.8
C5B—C4B—N3B	110.3 (4)	C14^iii—C15—H15A	109.8
C5B—C4B—H4B	124.9	O6—C15—H15B	109.8
N3B—C4B—H4B	124.9	C14^iii—C15—H15B	109.8
C4B—C5B—N1B	104.6 (4)	H15A—C15—H15B	108.3

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

(11)

Crystal data

C36H32Cl2CuN8O8·2(C4H8O2)	Z = 1
Mr = 1015.34	F(000) = 527
Triclinic, P1	Dx = 1.482 Mg m^−3
a = 10.0363 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1867 (6) Å	Cell parameters from 3986 reflections
c = 11.9902 (6) Å	θ = 3.9–28.9°
α = 83.078 (5)°	µ = 0.67 mm^−1
β = 82.032 (4)°	T = 100 K
γ = 70.015 (5)°	Prism, orange
V = 1137.37 (11) Å^3	0.16 × 0.13 × 0.10 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4877 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4265 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.033
ω scans	θmax = 27.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→12
Tmin = 0.703, Tmax = 1.000	k = −12→12
9285 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: mixed
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 0.8435P] where P = (Fo^2 + 2Fc^2)/3
4877 reflections	(Δ/σ)max < 0.001
312 parameters	Δρmax = 0.66 e Å^−3
2 restraints	Δρmin = −0.51 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Cu	1.0000	0.5000	1.0000	0.01548 (12)
N1A	0.60749 (19)	0.7687 (2)	0.92316 (15)	0.0180 (4)
H1A	0.5210 (13)	0.785 (3)	0.913 (2)	0.027*
C2A	0.6982 (2)	0.6449 (2)	0.95736 (18)	0.0183 (4)
H2A	0.6755	0.5609	0.9733	0.022*
N3A	0.82432 (19)	0.65544 (19)	0.96611 (15)	0.0170 (4)
C4A	0.8111 (2)	0.7942 (2)	0.93622 (18)	0.0169 (4)
H4A	0.8847	0.8333	0.9350	0.020*
C5A	0.6764 (2)	0.8670 (2)	0.90860 (17)	0.0166 (4)
C6A	0.6084 (2)	1.0129 (2)	0.86708 (17)	0.0169 (4)
C7A	0.4766 (2)	1.0548 (3)	0.8247 (2)	0.0231 (5)
H7A	0.4300	0.9883	0.8229	0.028*
C8A	0.4128 (3)	1.1928 (3)	0.7853 (2)	0.0269 (5)
H8A	0.3225	1.2203	0.7571	0.032*
C9A	0.4799 (3)	1.2909 (3)	0.7865 (2)	0.0261 (5)
H9A	0.4359	1.3855	0.7595	0.031*
C10A	0.6115 (3)	1.2498 (3)	0.8277 (2)	0.0251 (5)
H10A	0.6583	1.3165	0.8282	0.030*
C11A	0.6758 (2)	1.1119 (2)	0.86818 (19)	0.0208 (5)
H11A	0.7658	1.0849	0.8967	0.025*
N1B	0.9876 (2)	0.6772 (2)	1.29786 (16)	0.0198 (4)
H1B	1.016 (3)	0.726 (3)	1.337 (2)	0.030*
N3B	0.98404 (19)	0.56610 (19)	1.15271 (15)	0.0166 (4)
C2B	1.0324 (2)	0.6575 (2)	1.18829 (19)	0.0209 (5)
H2B	1.0910	0.7032	1.1425	0.025*
C4B	0.9050 (2)	0.5250 (2)	1.24494 (18)	0.0163 (4)
H4B	0.8573	0.4588	1.2451	0.020*
C5B	0.9052 (2)	0.5935 (2)	1.33614 (18)	0.0159 (4)
C6B	0.8283 (2)	0.5926 (2)	1.44915 (18)	0.0166 (4)
C7B	0.8361 (2)	0.6741 (3)	1.53131 (19)	0.0224 (5)
H7B	0.8962	0.7301	1.5158	0.027*
C8B	0.7567 (3)	0.6743 (3)	1.6363 (2)	0.0253 (5)
H8B	0.7638	0.7296	1.6922	0.030*
C9B	0.6678 (3)	0.5947 (3)	1.6594 (2)	0.0252 (5)
H9B	0.6122	0.5965	1.7305	0.030*
C10B	0.6600 (3)	0.5123 (3)	1.5785 (2)	0.0316 (6)
H10B	0.6001	0.4561	1.5946	0.038*
C11B	0.7393 (3)	0.5113 (3)	1.4741 (2)	0.0289 (6)
H11B	0.7330	0.4546	1.4190	0.035*
Cl	0.72729 (6)	0.29022 (6)	1.13303 (5)	0.02421 (15)
O1	0.84558 (17)	0.32499 (18)	1.06948 (14)	0.0255 (4)
O2	0.71998 (19)	0.31419 (19)	1.24939 (14)	0.0290 (4)
O3	0.7446 (3)	0.1466 (2)	1.12386 (18)	0.0590 (7)
O4	0.5982 (2)	0.3768 (3)	1.08721 (17)	0.0452 (6)
C12	0.9753 (3)	−0.0701 (3)	0.6799 (2)	0.0310 (6)
H12A	1.0431	−0.1357	0.6286	0.046*
H12B	0.9179	−0.1184	0.7299	0.046*
H12C	1.0276	−0.0346	0.7254	0.046*
C13	0.8799 (3)	0.0494 (3)	0.61274 (19)	0.0237 (5)
C14	0.6787 (3)	0.1169 (3)	0.5061 (2)	0.0280 (5)
H14A	0.7165	0.1920	0.4715	0.034*
H14B	0.5908	0.1594	0.5561	0.034*
C15	0.6465 (3)	0.0450 (3)	0.4156 (2)	0.0314 (6)
H15A	0.7310	0.0137	0.3611	0.047*
H15B	0.5672	0.1106	0.3768	0.047*
H15C	0.6203	−0.0362	0.4501	0.047*
O5	0.8893 (2)	0.1657 (2)	0.59590 (15)	0.0315 (4)
O6	0.78386 (18)	0.01200 (18)	0.57048 (15)	0.0275 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0173 (2)	0.0191 (2)	0.00949 (19)	−0.00581 (15)	0.00155 (14)	−0.00302 (14)
N1A	0.0153 (9)	0.0252 (10)	0.0151 (9)	−0.0092 (8)	0.0016 (7)	−0.0041 (8)
C2A	0.0211 (11)	0.0208 (11)	0.0144 (10)	−0.0097 (9)	0.0019 (9)	−0.0032 (9)
N3A	0.0194 (9)	0.0218 (9)	0.0108 (9)	−0.0090 (8)	0.0017 (7)	−0.0020 (7)
C4A	0.0169 (10)	0.0211 (11)	0.0139 (10)	−0.0083 (9)	0.0010 (8)	−0.0025 (8)
C5A	0.0172 (10)	0.0227 (11)	0.0110 (10)	−0.0087 (9)	0.0035 (8)	−0.0051 (8)
C6A	0.0170 (10)	0.0216 (11)	0.0102 (10)	−0.0057 (9)	0.0049 (8)	−0.0037 (8)
C7A	0.0234 (11)	0.0256 (12)	0.0196 (11)	−0.0071 (10)	−0.0019 (9)	−0.0029 (9)
C8A	0.0224 (12)	0.0312 (13)	0.0218 (12)	−0.0016 (10)	−0.0033 (10)	−0.0020 (10)
C9A	0.0284 (12)	0.0215 (11)	0.0197 (12)	−0.0007 (10)	0.0058 (10)	−0.0004 (9)
C10A	0.0281 (12)	0.0228 (11)	0.0235 (12)	−0.0099 (10)	0.0058 (10)	−0.0035 (10)
C11A	0.0174 (10)	0.0257 (11)	0.0185 (11)	−0.0077 (9)	0.0034 (9)	−0.0033 (9)
N1B	0.0237 (10)	0.0250 (10)	0.0149 (9)	−0.0133 (8)	0.0017 (8)	−0.0062 (8)
N3B	0.0159 (8)	0.0204 (9)	0.0127 (9)	−0.0053 (7)	0.0009 (7)	−0.0025 (7)
C2B	0.0237 (11)	0.0254 (12)	0.0159 (11)	−0.0123 (10)	0.0026 (9)	−0.0033 (9)
C4B	0.0175 (10)	0.0187 (10)	0.0132 (10)	−0.0073 (8)	0.0004 (8)	−0.0014 (8)
C5B	0.0166 (10)	0.0163 (10)	0.0140 (10)	−0.0052 (8)	0.0002 (8)	−0.0012 (8)
C6B	0.0170 (10)	0.0187 (10)	0.0126 (10)	−0.0045 (8)	−0.0008 (8)	−0.0009 (8)
C7B	0.0239 (11)	0.0286 (12)	0.0178 (11)	−0.0129 (10)	0.0031 (9)	−0.0078 (10)
C8B	0.0289 (12)	0.0314 (13)	0.0167 (11)	−0.0112 (11)	0.0042 (10)	−0.0105 (10)
C9B	0.0274 (12)	0.0329 (13)	0.0136 (11)	−0.0104 (10)	0.0064 (9)	−0.0033 (10)
C10B	0.0421 (15)	0.0391 (15)	0.0217 (12)	−0.0270 (13)	0.0066 (11)	−0.0046 (11)
C11B	0.0422 (15)	0.0348 (14)	0.0183 (12)	−0.0254 (12)	0.0058 (11)	−0.0082 (10)
Cl	0.0354 (3)	0.0313 (3)	0.0150 (3)	−0.0237 (3)	−0.0007 (2)	−0.0008 (2)
O1	0.0230 (8)	0.0319 (9)	0.0218 (9)	−0.0123 (7)	0.0060 (7)	−0.0027 (7)
O2	0.0403 (10)	0.0394 (10)	0.0152 (8)	−0.0244 (9)	0.0017 (7)	−0.0046 (7)
O3	0.128 (2)	0.0410 (12)	0.0282 (11)	−0.0560 (14)	−0.0021 (13)	−0.0047 (9)
O4	0.0302 (10)	0.0832 (16)	0.0330 (11)	−0.0353 (11)	−0.0089 (9)	0.0107 (11)
C12	0.0309 (13)	0.0466 (16)	0.0203 (12)	−0.0203 (12)	0.0010 (10)	−0.0030 (11)
C13	0.0263 (12)	0.0353 (13)	0.0141 (11)	−0.0171 (11)	0.0073 (9)	−0.0088 (10)
C14	0.0281 (13)	0.0293 (13)	0.0287 (13)	−0.0120 (11)	−0.0007 (10)	−0.0058 (11)
C15	0.0306 (13)	0.0415 (15)	0.0265 (13)	−0.0175 (12)	−0.0034 (11)	−0.0019 (11)
O5	0.0399 (10)	0.0379 (10)	0.0273 (10)	−0.0260 (9)	−0.0009 (8)	−0.0060 (8)
O6	0.0308 (9)	0.0298 (9)	0.0279 (9)	−0.0167 (8)	−0.0060 (7)	−0.0022 (7)

Geometric parameters (Å, º)

Cu—N3A^i	1.9790 (18)	C4B—H4B	0.9500
Cu—N3A	1.9790 (18)	C5B—C6B	1.464 (3)
Cu—N3B	1.9934 (17)	C6B—C7B	1.389 (3)
Cu—N3B^i	1.9934 (17)	C6B—C11B	1.395 (3)
N1A—C2A	1.334 (3)	C7B—C8B	1.393 (3)
N1A—C5A	1.382 (3)	C7B—H7B	0.9500
N1A—H1A	0.848 (10)	C8B—C9B	1.379 (3)
C2A—N3A	1.325 (3)	C8B—H8B	0.9500
C2A—H2A	0.9500	C9B—C10B	1.384 (3)
N3A—C4A	1.381 (3)	C9B—H9B	0.9500
C4A—C5A	1.366 (3)	C10B—C11B	1.386 (3)
C4A—H4A	0.9500	C10B—H10B	0.9500
C5A—C6A	1.464 (3)	C11B—H11B	0.9500
C6A—C7A	1.392 (3)	Cl—O3	1.429 (2)
C6A—C11A	1.395 (3)	Cl—O2	1.4329 (17)
C7A—C8A	1.385 (3)	Cl—O4	1.434 (2)
C7A—H7A	0.9500	Cl—O1	1.4446 (16)
C8A—C9A	1.385 (4)	C12—C13	1.493 (4)
C8A—H8A	0.9500	C12—H12A	0.9800
C9A—C10A	1.384 (4)	C12—H12B	0.9800
C9A—H9A	0.9500	C12—H12C	0.9800
C10A—C11A	1.389 (3)	C13—O5	1.211 (3)
C10A—H10A	0.9500	C13—O6	1.328 (3)
C11A—H11A	0.9500	C14—O6	1.452 (3)
N1B—C2B	1.344 (3)	C14—C15	1.506 (3)
N1B—C5B	1.380 (3)	C14—H14A	0.9900
N1B—H1B	0.857 (10)	C14—H14B	0.9900
N3B—C2B	1.321 (3)	C15—H15A	0.9800
N3B—C4B	1.378 (3)	C15—H15B	0.9800
C2B—H2B	0.9500	C15—H15C	0.9800
C4B—C5B	1.367 (3)
N3A^i—Cu—N3A	180.0	N3B—C4B—H4B	125.0
N3A^i—Cu—N3B	89.86 (7)	C4B—C5B—N1B	105.11 (18)
N3A—Cu—N3B	90.14 (7)	C4B—C5B—C6B	130.0 (2)
N3A^i—Cu—N3B^i	90.14 (7)	N1B—C5B—C6B	124.73 (19)
N3A—Cu—N3B^i	89.86 (7)	C7B—C6B—C11B	118.5 (2)
N3B—Cu—N3B^i	180.0	C7B—C6B—C5B	122.5 (2)
C2A—N1A—C5A	108.90 (18)	C11B—C6B—C5B	118.96 (19)
C2A—N1A—H1A	125.9 (19)	C6B—C7B—C8B	120.6 (2)
C5A—N1A—H1A	125.2 (19)	C6B—C7B—H7B	119.7
N3A—C2A—N1A	110.64 (19)	C8B—C7B—H7B	119.7
N3A—C2A—H2A	124.7	C9B—C8B—C7B	120.3 (2)
N1A—C2A—H2A	124.7	C9B—C8B—H8B	119.9
C2A—N3A—C4A	105.86 (18)	C7B—C8B—H8B	119.9
C2A—N3A—Cu	126.68 (15)	C8B—C9B—C10B	119.6 (2)
C4A—N3A—Cu	127.20 (14)	C8B—C9B—H9B	120.2
C5A—C4A—N3A	109.99 (19)	C10B—C9B—H9B	120.2
C5A—C4A—H4A	125.0	C9B—C10B—C11B	120.3 (2)
N3A—C4A—H4A	125.0	C9B—C10B—H10B	119.9
C4A—C5A—N1A	104.61 (19)	C11B—C10B—H10B	119.9
C4A—C5A—C6A	132.5 (2)	C10B—C11B—C6B	120.7 (2)
N1A—C5A—C6A	122.88 (19)	C10B—C11B—H11B	119.6
C7A—C6A—C11A	118.9 (2)	C6B—C11B—H11B	119.6
C7A—C6A—C5A	120.7 (2)	O3—Cl—O2	109.59 (11)
C11A—C6A—C5A	120.4 (2)	O3—Cl—O4	108.88 (15)
C8A—C7A—C6A	120.6 (2)	O2—Cl—O4	109.89 (12)
C8A—C7A—H7A	119.7	O3—Cl—O1	110.03 (13)
C6A—C7A—H7A	119.7	O2—Cl—O1	109.74 (10)
C7A—C8A—C9A	120.4 (2)	O4—Cl—O1	108.70 (11)
C7A—C8A—H8A	119.8	C13—C12—H12A	109.5
C9A—C8A—H8A	119.8	C13—C12—H12B	109.5
C10A—C9A—C8A	119.4 (2)	H12A—C12—H12B	109.5
C10A—C9A—H9A	120.3	C13—C12—H12C	109.5
C8A—C9A—H9A	120.3	H12A—C12—H12C	109.5
C9A—C10A—C11A	120.6 (2)	H12B—C12—H12C	109.5
C9A—C10A—H10A	119.7	O5—C13—O6	123.4 (2)
C11A—C10A—H10A	119.7	O5—C13—C12	125.0 (2)
C10A—C11A—C6A	120.2 (2)	O6—C13—C12	111.6 (2)
C10A—C11A—H11A	119.9	O6—C14—C15	107.7 (2)
C6A—C11A—H11A	119.9	O6—C14—H14A	110.2
C2B—N1B—C5B	108.05 (18)	C15—C14—H14A	110.2
C2B—N1B—H1B	124 (2)	O6—C14—H14B	110.2
C5B—N1B—H1B	128 (2)	C15—C14—H14B	110.2
C2B—N3B—C4B	105.76 (18)	H14A—C14—H14B	108.5
C2B—N3B—Cu	131.48 (15)	C14—C15—H15A	109.5
C4B—N3B—Cu	122.63 (14)	C14—C15—H15B	109.5
N3B—C2B—N1B	111.1 (2)	H15A—C15—H15B	109.5
N3B—C2B—H2B	124.5	C14—C15—H15C	109.5
N1B—C2B—H2B	124.5	H15A—C15—H15C	109.5
C5B—C4B—N3B	109.98 (19)	H15B—C15—H15C	109.5
C5B—C4B—H4B	125.0	C13—O6—C14	118.99 (19)

Symmetry code: (i) −x+2, −y+1, −z+2.

(12)

Crystal data

C36H32Cl2CuN8O8·C4H10O	Z = 1
Mr = 913.25	F(000) = 473
Triclinic, P1	Dx = 1.482 Mg m^−3
a = 8.6577 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8396 (4) Å	Cell parameters from 4469 reflections
c = 12.8200 (6) Å	θ = 4.3–28.8°
α = 97.084 (4)°	µ = 0.73 mm^−1
β = 93.897 (4)°	T = 100 K
γ = 108.096 (4)°	Prism, blue
V = 1023.61 (8) Å^3	0.18 × 0.11 × 0.09 mm

Data collection

Oxford Diffraction SuperNova with Atlas CCD detector diffractometer	4386 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4098 reflections with I > 2σ(I)
Detector resolution: 10.4223 pixels mm^-1	Rint = 0.023
ω scans	θmax = 27.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.812, Tmax = 1.000	k = −11→12
7915 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: mixed
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.676P] where P = (Fo^2 + 2Fc^2)/3
4386 reflections	(Δ/σ)max < 0.001
330 parameters	Δρmax = 0.37 e Å^−3
10 restraints	Δρmin = −0.46 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu	0.5000	0.5000	0.0000	0.01443 (9)
N1A	0.23606 (17)	0.10513 (15)	0.07610 (11)	0.0159 (3)
H1A	0.232 (3)	0.0184 (12)	0.0797 (17)	0.024*
C2A	0.3595 (2)	0.19666 (18)	0.03637 (13)	0.0170 (3)
H2A	0.4490	0.1729	0.0095	0.020*
N3A	0.33873 (16)	0.32474 (14)	0.03994 (10)	0.0151 (3)
C4A	0.19500 (19)	0.31291 (17)	0.08347 (12)	0.0149 (3)
H4A	0.1490	0.3886	0.0958	0.018*
C5A	0.12830 (19)	0.17613 (17)	0.10639 (12)	0.0137 (3)
C6A	−0.02134 (19)	0.10991 (17)	0.15313 (12)	0.0138 (3)
C7A	−0.0473 (2)	−0.01865 (18)	0.19543 (14)	0.0195 (3)
H7A	0.0332	−0.0658	0.1938	0.023*
C8A	−0.1905 (2)	−0.07763 (19)	0.23985 (15)	0.0238 (4)
H8A	−0.2077	−0.1656	0.2678	0.029*
C9A	−0.3084 (2)	−0.00990 (19)	0.24389 (14)	0.0220 (4)
H9A	−0.4058	−0.0505	0.2749	0.026*
C10A	−0.2833 (2)	0.11789 (19)	0.20227 (14)	0.0207 (3)
H10A	−0.3638	0.1651	0.2050	0.025*
C11A	−0.1419 (2)	0.17721 (18)	0.15683 (13)	0.0173 (3)
H11A	−0.1266	0.2642	0.1279	0.021*
N1B	0.13121 (17)	0.42449 (15)	−0.24305 (11)	0.0171 (3)
H1B	0.0292 (13)	0.391 (2)	−0.2641 (16)	0.026*
C2B	0.1915 (2)	0.43359 (17)	−0.14255 (13)	0.0169 (3)
H2B	0.1269	0.4040	−0.0873	0.020*
N3B	0.35165 (16)	0.48879 (15)	−0.13034 (10)	0.0156 (3)
C4B	0.3952 (2)	0.5160 (2)	−0.22964 (14)	0.0255 (4)
H4B	0.5040	0.5567	−0.2457	0.031*
C5B	0.2589 (2)	0.4756 (2)	−0.30072 (13)	0.0214 (4)
C6B	0.2275 (5)	0.4518 (4)	−0.4167 (2)	0.0176 (12)	0.5
C7B	0.0841 (5)	0.3549 (4)	−0.4720 (3)	0.0222 (12)	0.5
H7B	0.0042	0.2957	−0.4352	0.027*	0.5
C8B	0.0575 (4)	0.3445 (4)	−0.5813 (3)	0.0289 (13)	0.5
H8B	−0.0405	0.2783	−0.6191	0.035*	0.5
C9B	0.1744 (4)	0.4311 (4)	−0.6352 (2)	0.0242 (11)	0.5
H9B	0.1562	0.4241	−0.7099	0.029*	0.5
C10B	0.3178 (3)	0.5280 (4)	−0.5799 (2)	0.0259 (8)	0.5
H10B	0.3976	0.5872	−0.6167	0.031*	0.5
C11B	0.3443 (3)	0.5383 (3)	−0.4706 (2)	0.0218 (8)	0.5
H11B	0.4424	0.6046	−0.4328	0.026*	0.5
C6C	0.2419 (5)	0.4922 (4)	−0.4147 (2)	0.0164 (11)	0.5
C7C	0.1351 (6)	0.3726 (4)	−0.4809 (3)	0.0265 (12)	0.5
H7C	0.0735	0.2909	−0.4519	0.032*	0.5
C8C	0.1184 (5)	0.3724 (3)	−0.5896 (3)	0.0319 (14)	0.5
H8C	0.0454	0.2906	−0.6348	0.038*	0.5
C9C	0.2084 (5)	0.4919 (4)	−0.6320 (2)	0.0258 (12)	0.5
H9C	0.1970	0.4917	−0.7062	0.031*	0.5
C10C	0.3152 (4)	0.6115 (3)	−0.56579 (19)	0.0264 (8)	0.5
H10C	0.3768	0.6932	−0.5948	0.032*	0.5
C11C	0.3319 (4)	0.6117 (3)	−0.45717 (18)	0.0217 (7)	0.5
H11C	0.4049	0.6935	−0.4119	0.026*	0.5
Cl	0.26988 (5)	0.72337 (4)	0.12601 (3)	0.01654 (10)
O1	0.39920 (15)	0.66131 (13)	0.13604 (10)	0.0214 (3)
O2	0.21253 (17)	0.74779 (16)	0.22694 (11)	0.0319 (3)
O3	0.13731 (15)	0.62726 (13)	0.05218 (10)	0.0228 (3)
O4	0.33199 (16)	0.85956 (13)	0.08722 (12)	0.0271 (3)
O5	0.5000	0.0000	0.5000	0.0568 (7)
C12A	0.6054 (6)	−0.0650 (5)	0.5269 (4)	0.0401 (10)	0.5
H12A	0.5910	−0.1481	0.4708	0.048*	0.5
H12B	0.5746	−0.1051	0.5924	0.048*	0.5
C13A	0.7838 (6)	0.0207 (7)	0.5451 (5)	0.0426 (13)	0.5
H13A	0.8470	−0.0425	0.5617	0.064*	0.5
H13B	0.8031	0.0993	0.6043	0.064*	0.5
H13C	0.8180	0.0615	0.4812	0.064*	0.5
C12B	0.6568 (5)	0.0530 (5)	0.5237 (4)	0.0401 (11)	0.5
H12C	0.6807	0.1339	0.5829	0.048*	0.5
H12D	0.7055	0.0937	0.4621	0.048*	0.5
C13B	0.7390 (9)	−0.0509 (8)	0.5543 (7)	0.069 (2)	0.5
H13D	0.8576	−0.0027	0.5660	0.104*	0.5
H13E	0.7134	−0.1335	0.4975	0.104*	0.5
H13F	0.7001	−0.0849	0.6194	0.104*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01181 (14)	0.01697 (15)	0.01191 (14)	−0.00014 (11)	0.00048 (10)	0.00545 (10)
N1A	0.0163 (7)	0.0130 (6)	0.0196 (7)	0.0051 (5)	0.0047 (5)	0.0043 (5)
C2A	0.0147 (8)	0.0191 (8)	0.0163 (7)	0.0040 (6)	0.0022 (6)	0.0028 (6)
N3A	0.0135 (6)	0.0164 (7)	0.0133 (6)	0.0014 (5)	0.0002 (5)	0.0042 (5)
C4A	0.0158 (7)	0.0147 (7)	0.0141 (7)	0.0042 (6)	0.0016 (6)	0.0038 (6)
C5A	0.0151 (7)	0.0137 (7)	0.0121 (7)	0.0045 (6)	0.0001 (6)	0.0025 (6)
C6A	0.0145 (7)	0.0133 (7)	0.0122 (7)	0.0025 (6)	0.0016 (6)	0.0021 (6)
C7A	0.0218 (8)	0.0156 (8)	0.0239 (8)	0.0078 (7)	0.0067 (7)	0.0063 (6)
C8A	0.0285 (9)	0.0161 (8)	0.0279 (9)	0.0048 (7)	0.0103 (8)	0.0095 (7)
C9A	0.0181 (8)	0.0225 (9)	0.0215 (8)	0.0005 (7)	0.0074 (7)	0.0023 (7)
C10A	0.0158 (8)	0.0229 (9)	0.0232 (8)	0.0064 (7)	0.0019 (7)	0.0024 (7)
C11A	0.0180 (8)	0.0160 (8)	0.0180 (8)	0.0053 (6)	0.0004 (6)	0.0044 (6)
N1B	0.0118 (6)	0.0198 (7)	0.0191 (7)	0.0051 (5)	−0.0005 (5)	0.0022 (5)
C2B	0.0166 (8)	0.0175 (8)	0.0178 (8)	0.0063 (6)	0.0035 (6)	0.0047 (6)
N3B	0.0143 (6)	0.0183 (7)	0.0133 (6)	0.0036 (5)	0.0024 (5)	0.0039 (5)
C4B	0.0150 (8)	0.0441 (11)	0.0161 (8)	0.0045 (8)	0.0033 (7)	0.0119 (8)
C5B	0.0180 (8)	0.0317 (10)	0.0163 (8)	0.0103 (7)	0.0018 (6)	0.0045 (7)
C6B	0.020 (2)	0.019 (2)	0.018 (2)	0.0108 (19)	0.0028 (19)	0.0056 (16)
C7B	0.022 (3)	0.025 (2)	0.016 (2)	0.0053 (17)	−0.0021 (17)	−0.0009 (17)
C8B	0.030 (3)	0.033 (3)	0.021 (2)	0.011 (2)	−0.005 (2)	−0.0018 (18)
C9B	0.039 (3)	0.025 (3)	0.013 (2)	0.017 (2)	0.0000 (18)	0.0026 (18)
C10B	0.031 (2)	0.031 (2)	0.0186 (18)	0.0124 (18)	0.0045 (17)	0.0052 (16)
C11B	0.0220 (19)	0.024 (2)	0.0201 (18)	0.0081 (16)	0.0010 (14)	0.0034 (16)
C6C	0.018 (2)	0.020 (3)	0.013 (2)	0.0096 (16)	−0.0037 (16)	−0.0001 (13)
C7C	0.029 (3)	0.026 (2)	0.023 (2)	0.006 (2)	0.001 (2)	0.0058 (19)
C8C	0.040 (4)	0.033 (3)	0.017 (2)	0.010 (3)	−0.009 (2)	−0.005 (2)
C9C	0.038 (3)	0.029 (3)	0.018 (2)	0.019 (2)	0.0049 (19)	0.0063 (19)
C10C	0.030 (2)	0.034 (2)	0.0197 (18)	0.0137 (18)	0.0051 (15)	0.0092 (17)
C11C	0.0245 (19)	0.024 (2)	0.0175 (17)	0.0084 (16)	0.0019 (14)	0.0047 (15)
Cl	0.01331 (18)	0.01325 (18)	0.0218 (2)	0.00314 (14)	0.00448 (15)	−0.00059 (14)
O1	0.0178 (6)	0.0201 (6)	0.0281 (6)	0.0087 (5)	0.0030 (5)	0.0037 (5)
O2	0.0281 (7)	0.0382 (8)	0.0252 (7)	0.0066 (6)	0.0114 (6)	−0.0053 (6)
O3	0.0163 (6)	0.0192 (6)	0.0289 (7)	0.0034 (5)	−0.0008 (5)	−0.0034 (5)
O4	0.0217 (6)	0.0154 (6)	0.0463 (8)	0.0066 (5)	0.0090 (6)	0.0084 (5)
O5	0.0474 (15)	0.088 (2)	0.0395 (13)	0.0344 (15)	0.0006 (11)	−0.0021 (13)
C12A	0.055 (3)	0.031 (2)	0.035 (2)	0.015 (2)	0.008 (2)	0.0031 (18)
C13A	0.040 (3)	0.050 (4)	0.033 (2)	0.015 (3)	−0.003 (2)	−0.010 (3)
C12B	0.034 (2)	0.043 (3)	0.031 (2)	0.000 (2)	0.0016 (18)	−0.0044 (19)
C13B	0.033 (4)	0.065 (5)	0.096 (6)	0.006 (3)	−0.012 (3)	−0.009 (4)

Geometric parameters (Å, º)

Cu—N3A	2.0012 (13)	C8B—C9B	1.3900
Cu—N3A^i	2.0012 (13)	C8B—H8B	0.9500
Cu—N3B^i	2.0072 (13)	C9B—C10B	1.3900
Cu—N3B	2.0072 (13)	C9B—H9B	0.9500
N1A—C2A	1.342 (2)	C10B—C11B	1.3900
N1A—C5A	1.377 (2)	C10B—H10B	0.9500
N1A—H1A	0.851 (9)	C11B—H11B	0.9500
C2A—N3A	1.323 (2)	C6C—C7C	1.3900
C2A—H2A	0.9500	C6C—C11C	1.3900
N3A—C4A	1.376 (2)	C7C—C8C	1.3900
C4A—C5A	1.367 (2)	C7C—H7C	0.9500
C4A—H4A	0.9500	C8C—C9C	1.3900
C5A—C6A	1.463 (2)	C8C—H8C	0.9500
C6A—C7A	1.398 (2)	C9C—C10C	1.3900
C6A—C11A	1.400 (2)	C9C—H9C	0.9500
C7A—C8A	1.389 (2)	C10C—C11C	1.3900
C7A—H7A	0.9500	C10C—H10C	0.9500
C8A—C9A	1.382 (3)	C11C—H11C	0.9500
C8A—H8A	0.9500	Cl—O2	1.4364 (13)
C9A—C10A	1.387 (2)	Cl—O3	1.4370 (12)
C9A—H9A	0.9500	Cl—O1	1.4379 (12)
C10A—C11A	1.384 (2)	Cl—O4	1.4441 (13)
C10A—H10A	0.9500	O5—C12B^ii	1.293 (4)
C11A—H11A	0.9500	O5—C12B	1.293 (4)
N1B—C2B	1.339 (2)	O5—C12A^ii	1.317 (4)
N1B—C5B	1.371 (2)	O5—C12A	1.317 (4)
N1B—H1B	0.852 (9)	C12A—C13A	1.499 (6)
C2B—N3B	1.313 (2)	C12A—H12A	0.9900
C2B—H2B	0.9500	C12A—H12B	0.9900
N3B—C4B	1.386 (2)	C13A—H13A	0.9800
C4B—C5B	1.361 (2)	C13A—H13B	0.9800
C4B—H4B	0.9500	C13A—H13C	0.9800
C5B—C6B	1.469 (3)	C12B—C13B	1.489 (7)
C5B—C6C	1.493 (3)	C12B—H12C	0.9900
C6B—C7B	1.3900	C12B—H12D	0.9900
C6B—C11B	1.3900	C13B—H13D	0.9800
C7B—C8B	1.3900	C13B—H13E	0.9800
C7B—H7B	0.9500	C13B—H13F	0.9800
N3A—Cu—N3A^i	180.0	C7B—C8B—C9B	120.0
N3A—Cu—N3B^i	89.00 (5)	C7B—C8B—H8B	120.0
N3A^i—Cu—N3B^i	91.00 (5)	C9B—C8B—H8B	120.0
N3A—Cu—N3B	91.00 (5)	C8B—C9B—C10B	120.0
N3A^i—Cu—N3B	89.00 (5)	C8B—C9B—H9B	120.0
N3B^i—Cu—N3B	180.0	C10B—C9B—H9B	120.0
C2A—N1A—C5A	108.81 (13)	C11B—C10B—C9B	120.0
C2A—N1A—H1A	121.5 (15)	C11B—C10B—H10B	120.0
C5A—N1A—H1A	129.7 (15)	C9B—C10B—H10B	120.0
N3A—C2A—N1A	110.30 (14)	C10B—C11B—C6B	120.0
N3A—C2A—H2A	124.8	C10B—C11B—H11B	120.0
N1A—C2A—H2A	124.8	C6B—C11B—H11B	120.0
C2A—N3A—C4A	106.19 (13)	C7C—C6C—C11C	120.0
C2A—N3A—Cu	124.72 (11)	C7C—C6C—C5B	115.1 (2)
C4A—N3A—Cu	128.89 (11)	C11C—C6C—C5B	124.7 (2)
C5A—C4A—N3A	109.94 (14)	C6C—C7C—C8C	120.0
C5A—C4A—H4A	125.0	C6C—C7C—H7C	120.0
N3A—C4A—H4A	125.0	C8C—C7C—H7C	120.0
C4A—C5A—N1A	104.74 (14)	C9C—C8C—C7C	120.0
C4A—C5A—C6A	131.12 (15)	C9C—C8C—H8C	120.0
N1A—C5A—C6A	124.13 (14)	C7C—C8C—H8C	120.0
C7A—C6A—C11A	118.68 (15)	C10C—C9C—C8C	120.0
C7A—C6A—C5A	121.88 (15)	C10C—C9C—H9C	120.0
C11A—C6A—C5A	119.44 (14)	C8C—C9C—H9C	120.0
C8A—C7A—C6A	120.18 (16)	C9C—C10C—C11C	120.0
C8A—C7A—H7A	119.9	C9C—C10C—H10C	120.0
C6A—C7A—H7A	119.9	C11C—C10C—H10C	120.0
C9A—C8A—C7A	120.77 (16)	C10C—C11C—C6C	120.0
C9A—C8A—H8A	119.6	C10C—C11C—H11C	120.0
C7A—C8A—H8A	119.6	C6C—C11C—H11C	120.0
C8A—C9A—C10A	119.35 (16)	O2—Cl—O3	109.66 (8)
C8A—C9A—H9A	120.3	O2—Cl—O1	110.24 (8)
C10A—C9A—H9A	120.3	O3—Cl—O1	109.57 (7)
C11A—C10A—C9A	120.54 (16)	O2—Cl—O4	109.28 (8)
C11A—C10A—H10A	119.7	O3—Cl—O4	109.24 (8)
C9A—C10A—H10A	119.7	O1—Cl—O4	108.82 (7)
C10A—C11A—C6A	120.48 (15)	C12B^ii—O5—C12B	180.0
C10A—C11A—H11A	119.8	C12A^ii—O5—C12A	180.0
C6A—C11A—H11A	119.8	O5—C12A—C13A	118.8 (4)
C2B—N1B—C5B	108.59 (14)	O5—C12A—H12A	107.6
C2B—N1B—H1B	122.8 (15)	C13A—C12A—H12A	107.6
C5B—N1B—H1B	128.6 (15)	O5—C12A—H12B	107.6
N3B—C2B—N1B	111.10 (14)	C13A—C12A—H12B	107.6
N3B—C2B—H2B	124.5	H12A—C12A—H12B	107.1
N1B—C2B—H2B	124.5	C12A—C13A—H13A	109.5
C2B—N3B—C4B	105.49 (14)	C12A—C13A—H13B	109.5
C2B—N3B—Cu	126.11 (11)	H13A—C13A—H13B	109.5
C4B—N3B—Cu	127.74 (11)	C12A—C13A—H13C	109.5
C5B—C4B—N3B	109.91 (15)	H13A—C13A—H13C	109.5
C5B—C4B—H4B	125.0	H13B—C13A—H13C	109.5
N3B—C4B—H4B	125.0	O5—C12B—C13B	115.5 (4)
C4B—C5B—N1B	104.91 (15)	O5—C12B—H12C	108.4
C4B—C5B—C6B	135.0 (2)	C13B—C12B—H12C	108.4
N1B—C5B—C6B	118.9 (2)	O5—C12B—H12D	108.4
C4B—C5B—C6C	129.9 (2)	C13B—C12B—H12D	108.4
N1B—C5B—C6C	125.0 (2)	H12C—C12B—H12D	107.5
C7B—C6B—C11B	120.0	C12B—C13B—H13D	109.5
C7B—C6B—C5B	123.0 (2)	C12B—C13B—H13E	109.5
C11B—C6B—C5B	116.9 (2)	H13D—C13B—H13E	109.5
C8B—C7B—C6B	120.0	C12B—C13B—H13F	109.5
C8B—C7B—H7B	120.0	H13D—C13B—H13F	109.5
C6B—C7B—H7B	120.0	H13E—C13B—H13F	109.5

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

 

Footnotes

‡Current address: School of Chemistry, National University of Ireland Galway, H91 TK33, Galway, Ireland