The first square-planar copper(II) 1:2 complex with differently coordinated 2-hy­droxy­benzaldehyde 4-allyl­thio­semicarbazone ligands

The title compound, [(Z)-4-allyl-2-(2-hy­droxybenzyl­idene)thio­semicarbazide-κS][(E)-4-allyl-1-(2-oxidobenzyl­idene)thio­semicarbazidato-κ³O,N¹,S]copper(II) monohydrate, [Cu(C₁₁H₁₁N₃OS)(C₁₁H₁₃N₃OS)]·H₂O, crystallized as a rotational twin in the monoclinic crystal system (space group Cc) with two formula unit (Z′ = 2) in the asymmetric unit, one of which contains an allyl substituent disordered over two positions. The Cu^II atom exhibits a distorted square-planar geometry involving two differently coordinated thio­semicarbazone ligands. One ligand is bonded to the Cu^II atom in a tridentate manner via the phenolate O, azomethine N and thio­amide S atoms, while the other coordinates in a monodentate manner via the S atom only. The complex is stabilized by an intra­molecular hydrogen bond, which creates a six-membered pseudo-chelate metalla-ring. The structure analysis indicates the presence of the E isomer for the tridentate ligand and the Z isomer for the monodentate ligand. The crystal structure contains a three-dimensional network built from inter­molecular O—H...O, N—H...O, O—H...N and N—H...S hydrogen bonds.

S1. Comment

Thiosemicarbazones and their metal complexes attract constant scientific interest due to their antimicrobial, antifungal and antitumour activities (Garoufilis et al., 2009; Stanojkovic et al., 2010). Some thiosemicarbazones are also used as reagents for the determination of Co^II, Ni^II, Cu^II and Pd^II by solid-phase microextraction in high-performance liquid chromatography (Kaur et al., 2007).

The potentially tridentate salicylaldehyde thiosemicarbazone derivatives can give mono-, bi- or polynuclear complexes with transition metals, in each of which the multiple ligands usually all coordinate to the metal centre in the same manner (Soriano-García et al., 1985; Labisbal et al., 2003). However, the Cambridge Structural Database (Version?; Allen, 2002) records two structures of 1:2 square-planar Pd^II and Pt^II complexes, each containing two differently coordinated thiosemicarbazone ligands (Papathanasis et al., 2004). The present paper reports the structure of the title square-planar copper(II) complex, (I), containing two salicylaldehyde 4-N-allylthiosemicarbazone ligands which exhibit different coordination behaviours.

Compound (I) crystallizes in the noncentrosymmetric space group Cc as a inversion twin, with two molecules of the metal complex and two solvent water molecules in the asymmetric unit. The geometric parameters of the two independent complexes are very similar (Fig. 1); the only difference between them is the presence of a disordered allyl fragment (atoms C9 and C10) in one of them. The Cu^II centres exhibit a distorted square-planar coordination geometry, with mean deviations from the planes Cu1/O1/N2/S1/S2 and Cu2/O3/N8/S3/S4 of 0.1635 and 0.1498 Å, respectively.

The main interest in the structure lies in the different coordination modes of the two ligands around each Cu^II ion: one ligand is bonded in a tridentate manner via phenyl O, azomethine N and thioamide S atoms, while the other is coordinated in monodentate fashion via the thioamide S atom only (Fig. 1). The resulting six-membered Cu1/N2/C2/C3/C4/O1 (A) and Cu2/N8/C24/C25/C26/O3 (B) rings and five-membered Cu1/S1/C1/N1/N2 (C) and Cu2/S3/C23/N7/N8 (D) rings are nearly planar, with mean deviations from the planes of 0.0111, 0.0538, 0.0191 and 0.0658 Å, respectively. The dihedral angles between planes A/C and B/D are 9.78 (14) and 9.87 (14)°, respectively, which confirms the slight tetrahedral distortion of the coordination geometry at the Cu^II ion. The values of Cu—O and Cu—N bond lengths (Table 1) are in good agreement with those in related structures (Bon et al., 2010). The Cu1—S1 and Cu2—S3 bonds are shorter than Cu1—S2 and Cu2—S4 (Table 1), which can be explained by the strong influence of the chelate effect in the former case.

The C—S bond lengths (Table 1) do not permit a clear assignment of the dominant tautomeric form of the coordinated ligands, although the C—S bond lengths in the tridentate ligands are closer to the value expected for the thiolic tautomeric form, while the monodentate ligands have slightly shorter C—S bonds (Table 1). The values of adjacent angles around the Cu^II ions are in the range 84.48 (4)–98.83 (9)° (Table 1), which confirms the distorted square-planar geometry. The valence angles O1—Cu1—S2 and O3—Cu2—S4 deviate significantly from the ideal square-planar values (Table 1), which can be explained in terms of the six-membered pseudo-chelate metalla-rings Cu1/S2/C12/N4/H4N/O1 and Cu2/S4/C34/N10/H10N/O3, formed via intramolecular hydrogen bonds (Fig. 1, Table 2). The torsion angles N2—N1—C1—N3, N5—N4—C12—N6, N8—N7—C23—N9 and N11—N10—C34—N12 (Table 1) confirm the presence of the E isomer in the tridentate ligands and the Z isomer in the monodentate ligands. The intramolecular O2—H2O···N5 and O4—H4O···N11 hydrogen bonds (Table 2) are characteristic for structures containing noncoordinated azomethine fragments (Rubčić et al., 2008). The crystal structure of (I) contains an extended three-dimensional network of intermolecular O—H···O, N—H···O, O—H···N and N—H···S hydrogen bonds (Fig. 2, Table 2).

S2. Experimental

An aqueous solution of copper(II) acetate (20 ml, 5 mM) was stirred for 2 h with an ethanolic solution of salicylaldehyde 4-N-allylthiosemicarbazone (20 ml, 10 mM). The resulting solution was then set aside for 3 d in the dark, giving violet needle-like crystals of (I) suitable for single-crystal X-ray diffraction.

S3. Refinement

The structure refinement indicated disorder of one allyl group, atoms C10 and C11, over two sets of positions with occupancies of 0.669 (8) and 0.331 (8). C10 and C11 from both positions were refined with equal isotropic and anisotropic parameters. Due to disorder, the C9—C10 and C10—C11 distances were refined with restraints of 1.52 (2) and 1.33 (2) Å, respectively. The coordinates of H atoms bonded to N or O atoms were found from Fourier difference map and refined, with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O), using distance restraints 0.82 (4) Å for O5—H51O, O6—H61O, O6—H62O and O4—H4O, and 0.87 (4) Å for N6—H6N, N3—H3N, N4—H4N, N9—H9N and N10—H10N. All other H atoms were treated as riding, with C—H = 0.95 or 0.99 Å, and with U_iso(H) = 1.2U_eq(C). The structure was handled as an inversion twin, with twin fractions 0.535 (13) and 0.465 (13).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of the title compound, with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level. Dashed lines indicate intramolecular hydrogen bonds.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis. Dashed lines indicate hydrogen bonds.

[(E)-4-Allyl-1-(2-oxidobenzylidene)thiosemicarbazidato- κ³O,N¹,S][(Z)-4-allyl-2-(2- hydroxybenzylidene)thiosemicarbazide-κS]copper(II) monohydrate

Crystal data

[Cu(C11H11N3OS)(C11H13N3OS)]·H2O	F(000) = 2280
Mr = 550.15	Dx = 1.513 Mg m^−3
Monoclinic, Cc	Melting point: 231 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 25.763 (3) Å	Cell parameters from 5321 reflections
b = 8.5526 (9) Å	θ = 2.5–25.2°
c = 24.496 (3) Å	µ = 1.11 mm^−1
β = 116.458 (3)°	T = 173 K
V = 4832.1 (10) Å^3	Needle, violet
Z = 8	0.50 × 0.05 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer	8043 independent reflections
Radiation source: fine-focus sealed tube	6716 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ϕ and ω scans	θmax = 26.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −29→32
Tmin = 0.606, Tmax = 0.946	k = −10→10
25072 measured reflections	l = −30→28

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 1.6385P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
8043 reflections	Δρmax = 0.48 e Å^−3
656 parameters	Δρmin = −0.36 e Å^−3
16 restraints	Absolute structure: Flack (1983), 3047 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.464 (13)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.40946 (2)	0.23917 (5)	0.11016 (2)	0.01915 (11)
S1	0.47493 (6)	0.36162 (13)	0.19397 (5)	0.0226 (3)
S2	0.34069 (5)	0.35102 (12)	0.13596 (5)	0.0242 (2)
O1	0.35948 (12)	0.1031 (3)	0.04694 (14)	0.0253 (7)
O2	0.09263 (13)	0.0620 (4)	−0.02904 (15)	0.0274 (8)
H2O	0.121 (2)	0.099 (6)	−0.009 (2)	0.041*
N1	0.52671 (19)	0.2851 (5)	0.1227 (2)	0.0223 (10)
N2	0.47390 (15)	0.2075 (4)	0.09008 (15)	0.0203 (8)
N3	0.5797 (2)	0.4281 (6)	0.2074 (2)	0.0355 (12)
H3N	0.581 (2)	0.475 (6)	0.2354 (19)	0.043*
N4	0.25815 (19)	0.2184 (5)	0.0390 (2)	0.0197 (10)
H4N	0.2821 (17)	0.170 (5)	0.032 (2)	0.024*
N5	0.20338 (15)	0.1575 (4)	0.00493 (15)	0.0196 (8)
N6	0.22710 (17)	0.3505 (4)	0.10128 (17)	0.0225 (9)
H6N	0.1949 (16)	0.325 (6)	0.079 (2)	0.027*
C1	0.52978 (19)	0.3554 (5)	0.17135 (18)	0.0224 (10)
C2	0.47400 (19)	0.1148 (4)	0.04825 (19)	0.0199 (9)
H2A	0.5089	0.1077	0.0442	0.024*
C3	0.42584 (19)	0.0218 (4)	0.00742 (18)	0.0207 (9)
C4	0.3718 (3)	0.0167 (5)	0.0087 (3)	0.0196 (12)
C5	0.3299 (2)	−0.0849 (5)	−0.0319 (2)	0.0248 (10)
H5A	0.2935	−0.0931	−0.0310	0.030*
C6	0.3399 (2)	−0.1725 (5)	−0.07291 (19)	0.0258 (10)
H6A	0.3103	−0.2400	−0.0999	0.031*
C7	0.3919 (2)	−0.1649 (5)	−0.0758 (2)	0.0283 (12)
H7A	0.3981	−0.2244	−0.1051	0.034*
C8	0.4347 (2)	−0.0693 (5)	−0.0353 (2)	0.0258 (10)
H8A	0.4711	−0.0649	−0.0363	0.031*
C9	0.6313 (2)	0.4200 (8)	0.1973 (2)	0.0569 (17)
H9A	0.6398	0.3087	0.1935	0.068*	0.67
H9B	0.6228	0.4718	0.1581	0.068*	0.67
H9C	0.6228	0.3516	0.1617	0.068*	0.33
H9D	0.6395	0.5259	0.1869	0.068*	0.33
C10A	0.6819 (3)	0.4904 (10)	0.2442 (3)	0.0441 (17)	0.67
H10A	0.6791	0.5986	0.2512	0.053*	0.67
C11A	0.7319 (8)	0.423 (3)	0.2788 (19)	0.064 (2)	0.67
H11A	0.7374	0.3153	0.2739	0.077*	0.67
H11B	0.7626	0.4829	0.3086	0.077*	0.67
C10B	0.6810 (6)	0.364 (2)	0.2467 (6)	0.0441 (17)	0.33
H10B	0.6789	0.2607	0.2598	0.053*	0.33
C11B	0.7307 (15)	0.439 (6)	0.277 (4)	0.064 (2)	0.33
H11C	0.7351	0.5428	0.2661	0.077*	0.33
H11D	0.7618	0.3891	0.3103	0.077*	0.33
Cu2	0.71165 (2)	0.00134 (5)	0.43649 (2)	0.01832 (11)
S3	0.64769 (5)	0.12090 (13)	0.35181 (5)	0.0222 (3)
S4	0.78095 (5)	0.11502 (13)	0.41212 (5)	0.0239 (2)
O3	0.76156 (12)	−0.1299 (3)	0.50184 (13)	0.0226 (7)
O4	1.02785 (14)	−0.1829 (4)	0.57227 (14)	0.0286 (7)
H4O	0.9978 (17)	−0.142 (6)	0.553 (2)	0.043*
N7	0.59260 (18)	0.0427 (5)	0.4206 (2)	0.0215 (10)
N8	0.64498 (15)	−0.0347 (4)	0.45353 (16)	0.0180 (8)
N9	0.54375 (18)	0.1984 (5)	0.3380 (2)	0.0230 (9)
H9N	0.5393 (19)	0.240 (5)	0.3066 (16)	0.028*
N10	0.8642 (2)	−0.0147 (4)	0.5090 (2)	0.0191 (10)
H10N	0.8382 (16)	−0.053 (5)	0.516 (2)	0.023*
N11	0.91835 (15)	−0.0831 (4)	0.54169 (15)	0.0196 (8)
N12	0.89361 (18)	0.1033 (4)	0.44378 (18)	0.0209 (9)
H12N	0.929 (2)	0.085 (5)	0.467 (2)	0.025*
C12	0.26968 (19)	0.3038 (5)	0.08882 (19)	0.0197 (10)
C13	0.19869 (18)	0.0857 (4)	−0.04314 (18)	0.0199 (9)
H13A	0.2303	0.0918	−0.0531	0.024*
C14	0.14868 (18)	−0.0034 (4)	−0.08293 (19)	0.0185 (9)
C15	0.0981 (3)	−0.0129 (5)	−0.0749 (3)	0.0230 (13)
C16	0.0518 (2)	−0.1037 (5)	−0.1141 (2)	0.0295 (11)
H16A	0.0178	−0.1114	−0.1082	0.035*
C17	0.0552 (2)	−0.1827 (6)	−0.1614 (3)	0.0327 (13)
H17A	0.0229	−0.2420	−0.1888	0.039*
C18	0.1052 (2)	−0.1768 (5)	−0.1697 (2)	0.0323 (11)
H18A	0.1076	−0.2338	−0.2018	0.039*
C19	0.1508 (2)	−0.0881 (5)	−0.1310 (2)	0.0263 (12)
H19A	0.1849	−0.0834	−0.1368	0.032*
C20	0.23493 (19)	0.4489 (5)	0.15240 (19)	0.0244 (10)
H20A	0.1996	0.5128	0.1411	0.029*
H20B	0.2676	0.5213	0.1609	0.029*
C21	0.2467 (2)	0.3597 (6)	0.2091 (2)	0.0343 (11)
H21A	0.2707	0.2697	0.2179	0.041*
C22	0.2264 (2)	0.3972 (7)	0.2471 (2)	0.0495 (15)
H22A	0.2022	0.4865	0.2396	0.059*
H22B	0.2355	0.3353	0.2824	0.059*
C23	0.59128 (19)	0.1173 (5)	0.37296 (19)	0.0207 (9)
C24	0.64412 (18)	−0.1295 (5)	0.49362 (19)	0.0207 (9)
H24A	0.6083	−0.1413	0.4955	0.025*
C25	0.69211 (18)	−0.2196 (4)	0.53584 (19)	0.0187 (9)
C26	0.7479 (2)	−0.2177 (6)	0.5380 (2)	0.0194 (12)
C27	0.7900 (2)	−0.3162 (5)	0.5804 (2)	0.0233 (10)
H27A	0.8273	−0.3206	0.5815	0.028*
C28	0.7791 (2)	−0.4067 (5)	0.6205 (2)	0.0268 (10)
H28A	0.8090	−0.4704	0.6492	0.032*
C29	0.7249 (2)	−0.4060 (5)	0.6194 (2)	0.0258 (11)
H29A	0.7173	−0.4679	0.6473	0.031*
C30	0.6825 (2)	−0.3140 (5)	0.5773 (2)	0.0245 (10)
H30A	0.6451	−0.3142	0.5760	0.029*
C31	0.49110 (18)	0.2020 (5)	0.34599 (19)	0.0272 (10)
H31A	0.4669	0.2912	0.3226	0.033*
H31B	0.5017	0.2198	0.3896	0.033*
C32	0.45642 (18)	0.0564 (5)	0.32585 (19)	0.0284 (10)
H32A	0.4732	−0.0380	0.3467	0.034*
C33	0.4036 (2)	0.0507 (7)	0.2808 (2)	0.0497 (14)
H33A	0.3858	0.1433	0.2592	0.060*
H33B	0.3834	−0.0460	0.2698	0.060*
C34	0.85155 (18)	0.0637 (5)	0.45776 (19)	0.0168 (9)
C35	0.92363 (18)	−0.1547 (4)	0.59007 (18)	0.0197 (9)
H35A	0.8934	−0.1441	0.6020	0.024*
C36	0.97292 (19)	−0.2500 (5)	0.6271 (2)	0.0193 (9)
C37	1.0220 (3)	−0.2640 (5)	0.6178 (3)	0.0199 (12)
C38	1.0670 (2)	−0.3603 (5)	0.65349 (19)	0.0275 (10)
H38A	1.1004	−0.3682	0.6465	0.033*
C39	1.0635 (2)	−0.4452 (6)	0.6995 (2)	0.0280 (12)
H39A	1.0945	−0.5125	0.7241	0.034*
C40	1.0158 (2)	−0.4336 (5)	0.71008 (19)	0.0273 (10)
H40A	1.0137	−0.4929	0.7418	0.033*
C41	0.9711 (2)	−0.3366 (5)	0.6750 (2)	0.0235 (11)
H41A	0.9384	−0.3277	0.6831	0.028*
C42	0.88606 (19)	0.1936 (5)	0.39004 (19)	0.0237 (10)
H42A	0.9231	0.2453	0.3981	0.028*
H42B	0.8568	0.2763	0.3826	0.028*
C43	0.8672 (2)	0.0940 (6)	0.3343 (2)	0.0339 (11)
H43A	0.8360	0.0238	0.3259	0.041*
C44	0.8898 (2)	0.0953 (6)	0.2964 (2)	0.0431 (13)
H44A	0.9211	0.1637	0.3031	0.052*
H44B	0.8751	0.0278	0.2620	0.052*
O5	1.01768 (14)	0.1061 (4)	0.50618 (15)	0.0272 (7)
H51O	1.0408 (19)	0.052 (5)	0.506 (2)	0.041*
H52O	1.031 (2)	0.132 (5)	0.540 (2)	0.041*
O6	0.10257 (14)	0.3495 (4)	0.03666 (14)	0.0284 (7)
H61O	0.089 (2)	0.362 (5)	−0.0033 (14)	0.043*
H62O	0.0763 (18)	0.293 (5)	0.041 (2)	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0159 (3)	0.0212 (2)	0.0198 (2)	−0.0028 (2)	0.0075 (2)	−0.0014 (2)
S1	0.0187 (7)	0.0281 (6)	0.0194 (7)	−0.0037 (5)	0.0072 (5)	−0.0011 (5)
S2	0.0171 (6)	0.0299 (6)	0.0243 (6)	−0.0032 (5)	0.0080 (5)	−0.0077 (5)
O1	0.0177 (17)	0.0280 (17)	0.0321 (18)	−0.0031 (13)	0.0129 (15)	−0.0078 (14)
O2	0.0191 (18)	0.0341 (18)	0.0299 (19)	−0.0121 (14)	0.0117 (15)	−0.0102 (14)
N1	0.016 (3)	0.028 (2)	0.022 (3)	−0.0051 (19)	0.008 (2)	0.0017 (19)
N2	0.017 (2)	0.0248 (18)	0.0174 (19)	−0.0039 (16)	0.0059 (17)	0.0006 (15)
N3	0.023 (3)	0.060 (3)	0.023 (3)	−0.016 (2)	0.010 (2)	−0.009 (2)
N4	0.013 (2)	0.0208 (19)	0.025 (3)	−0.0004 (17)	0.008 (2)	−0.0037 (17)
N5	0.0156 (19)	0.0229 (18)	0.0179 (18)	−0.0030 (15)	0.0052 (16)	−0.0011 (14)
N6	0.014 (2)	0.030 (2)	0.023 (2)	−0.0038 (17)	0.0077 (19)	−0.0020 (17)
C1	0.020 (3)	0.028 (2)	0.016 (2)	−0.0040 (19)	0.004 (2)	0.0031 (18)
C2	0.023 (2)	0.018 (2)	0.022 (2)	0.0028 (18)	0.013 (2)	0.0042 (17)
C3	0.025 (3)	0.018 (2)	0.015 (2)	−0.0022 (18)	0.006 (2)	0.0007 (16)
C4	0.023 (3)	0.020 (2)	0.018 (3)	0.004 (2)	0.011 (2)	0.0010 (19)
C5	0.019 (3)	0.025 (2)	0.025 (3)	0.001 (2)	0.005 (2)	0.0006 (19)
C6	0.026 (3)	0.023 (2)	0.021 (2)	−0.001 (2)	0.005 (2)	0.0003 (18)
C7	0.042 (3)	0.022 (2)	0.023 (3)	−0.002 (2)	0.016 (3)	−0.005 (2)
C8	0.031 (3)	0.024 (2)	0.030 (3)	0.001 (2)	0.020 (2)	−0.0001 (19)
C9	0.025 (3)	0.109 (5)	0.040 (3)	−0.032 (3)	0.018 (3)	−0.021 (3)
C10A	0.036 (4)	0.052 (4)	0.053 (4)	−0.012 (4)	0.029 (3)	−0.008 (4)
C11A	0.032 (3)	0.105 (6)	0.051 (4)	0.007 (4)	0.014 (3)	0.004 (6)
C10B	0.036 (4)	0.052 (4)	0.053 (4)	−0.012 (4)	0.029 (3)	−0.008 (4)
C11B	0.032 (3)	0.105 (6)	0.051 (4)	0.007 (4)	0.014 (3)	0.004 (6)
Cu2	0.0151 (2)	0.0204 (2)	0.0190 (2)	0.0023 (2)	0.0072 (2)	0.0017 (2)
S3	0.0172 (7)	0.0296 (6)	0.0195 (7)	0.0016 (5)	0.0079 (5)	0.0025 (5)
S4	0.0154 (6)	0.0302 (6)	0.0255 (6)	0.0036 (5)	0.0086 (5)	0.0088 (5)
O3	0.0162 (16)	0.0249 (15)	0.0280 (17)	0.0040 (13)	0.0110 (14)	0.0089 (13)
O4	0.0229 (18)	0.0383 (19)	0.0286 (18)	0.0076 (15)	0.0151 (16)	0.0112 (14)
N7	0.014 (2)	0.026 (2)	0.024 (2)	0.0082 (19)	0.007 (2)	0.0065 (19)
N8	0.020 (2)	0.0167 (17)	0.0195 (19)	0.0029 (15)	0.0104 (17)	−0.0003 (15)
N9	0.018 (2)	0.030 (2)	0.021 (2)	0.0081 (18)	0.0080 (19)	0.0063 (18)
N10	0.013 (2)	0.026 (2)	0.023 (2)	0.0018 (16)	0.012 (2)	0.0023 (17)
N11	0.0151 (19)	0.0182 (17)	0.0223 (19)	0.0020 (15)	0.0054 (16)	−0.0026 (15)
N12	0.014 (2)	0.025 (2)	0.021 (2)	−0.0017 (17)	0.0052 (18)	0.0037 (16)
C12	0.017 (3)	0.021 (2)	0.019 (2)	0.0015 (19)	0.007 (2)	0.0025 (18)
C13	0.020 (2)	0.022 (2)	0.019 (2)	0.0005 (18)	0.010 (2)	0.0007 (17)
C14	0.016 (2)	0.019 (2)	0.018 (2)	−0.0014 (17)	0.0051 (19)	0.0037 (16)
C15	0.028 (3)	0.020 (3)	0.022 (3)	−0.002 (2)	0.012 (3)	−0.002 (2)
C16	0.021 (3)	0.034 (3)	0.029 (3)	−0.005 (2)	0.008 (2)	−0.004 (2)
C17	0.027 (3)	0.037 (3)	0.025 (3)	−0.014 (2)	0.004 (2)	−0.008 (2)
C18	0.041 (3)	0.031 (2)	0.022 (2)	−0.007 (2)	0.012 (2)	−0.0069 (19)
C19	0.019 (3)	0.032 (3)	0.027 (3)	−0.002 (2)	0.010 (2)	0.000 (2)
C20	0.023 (3)	0.027 (2)	0.028 (3)	−0.0015 (19)	0.016 (2)	−0.008 (2)
C21	0.027 (3)	0.047 (3)	0.028 (3)	−0.005 (2)	0.012 (2)	−0.002 (2)
C22	0.044 (3)	0.068 (4)	0.038 (3)	−0.012 (3)	0.020 (3)	−0.007 (3)
C23	0.019 (2)	0.020 (2)	0.020 (2)	0.0000 (18)	0.006 (2)	−0.0060 (18)
C24	0.018 (2)	0.024 (2)	0.021 (2)	0.0023 (18)	0.0091 (19)	−0.0018 (18)
C25	0.014 (2)	0.019 (2)	0.023 (2)	−0.0003 (17)	0.0081 (19)	−0.0007 (17)
C26	0.021 (3)	0.016 (2)	0.019 (3)	−0.001 (2)	0.007 (2)	−0.0004 (19)
C27	0.018 (3)	0.024 (2)	0.025 (3)	−0.001 (2)	0.007 (2)	0.0016 (19)
C28	0.028 (3)	0.025 (2)	0.021 (2)	0.004 (2)	0.006 (2)	0.0027 (19)
C29	0.026 (3)	0.026 (2)	0.026 (3)	−0.001 (2)	0.012 (2)	0.000 (2)
C30	0.026 (3)	0.024 (2)	0.027 (2)	0.0007 (19)	0.015 (2)	0.0012 (19)
C31	0.017 (2)	0.040 (3)	0.021 (2)	0.008 (2)	0.005 (2)	0.0021 (19)
C32	0.023 (2)	0.039 (3)	0.026 (2)	0.004 (2)	0.013 (2)	0.0028 (19)
C33	0.036 (3)	0.057 (3)	0.047 (3)	−0.003 (3)	0.010 (3)	0.005 (3)
C34	0.016 (2)	0.016 (2)	0.017 (2)	0.0012 (18)	0.006 (2)	−0.0020 (17)
C35	0.017 (2)	0.021 (2)	0.022 (2)	−0.0040 (18)	0.0086 (19)	−0.0041 (17)
C36	0.018 (2)	0.020 (2)	0.016 (2)	0.0010 (17)	0.0044 (19)	−0.0031 (16)
C37	0.019 (3)	0.021 (2)	0.018 (3)	0.0021 (19)	0.006 (2)	−0.0021 (18)
C38	0.025 (3)	0.035 (3)	0.020 (2)	0.007 (2)	0.007 (2)	0.0028 (19)
C39	0.032 (3)	0.022 (2)	0.021 (3)	0.005 (2)	0.004 (2)	−0.0005 (19)
C40	0.038 (3)	0.025 (2)	0.016 (2)	0.001 (2)	0.009 (2)	0.0001 (18)
C41	0.028 (3)	0.023 (2)	0.018 (3)	−0.005 (2)	0.010 (2)	−0.0029 (19)
C42	0.018 (2)	0.028 (2)	0.025 (2)	−0.0015 (18)	0.009 (2)	0.0040 (19)
C43	0.035 (3)	0.038 (3)	0.023 (2)	−0.007 (2)	0.008 (2)	0.003 (2)
C44	0.042 (3)	0.058 (3)	0.028 (3)	0.002 (3)	0.015 (3)	0.000 (2)
O5	0.0170 (18)	0.0378 (19)	0.0267 (17)	0.0071 (14)	0.0097 (15)	−0.0018 (15)
O6	0.0219 (18)	0.0416 (19)	0.0244 (17)	−0.0075 (14)	0.0126 (15)	−0.0011 (14)

Geometric parameters (Å, º)

Cu1—O1	1.906 (3)	N11—C35	1.286 (5)
Cu1—N2	1.949 (4)	N12—C34	1.318 (6)
Cu1—S1	2.2519 (13)	N12—C42	1.463 (5)
Cu1—S2	2.3347 (12)	N12—H12N	0.84 (5)
S1—C1	1.733 (5)	C13—C14	1.439 (5)
S2—C12	1.721 (4)	C13—H13A	0.9500
O1—C4	1.337 (6)	C14—C19	1.404 (6)
O2—C15	1.354 (6)	C14—C15	1.405 (7)
O2—H2O	0.75 (5)	C15—C16	1.387 (7)
N1—C1	1.305 (6)	C16—C17	1.378 (7)
N1—N2	1.401 (5)	C16—H16A	0.9500
N2—C2	1.296 (5)	C17—C18	1.394 (7)
N3—C1	1.345 (6)	C17—H17A	0.9500
N3—C9	1.457 (6)	C18—C19	1.364 (6)
N3—H3N	0.78 (3)	C18—H18A	0.9500
N4—C12	1.338 (6)	C19—H19A	0.9500
N4—N5	1.382 (5)	C20—C21	1.493 (6)
N4—H4N	0.83 (3)	C20—H20A	0.9900
N5—C13	1.285 (5)	C20—H20B	0.9900
N6—C12	1.324 (6)	C21—C22	1.296 (7)
N6—C20	1.447 (5)	C21—H21A	0.9500
N6—H6N	0.79 (3)	C22—H22A	0.9500
C2—C3	1.437 (6)	C22—H22B	0.9500
C2—H2A	0.9500	C24—C25	1.432 (6)
C3—C8	1.403 (6)	C24—H24A	0.9500
C3—C4	1.407 (7)	C25—C30	1.404 (6)
C4—C5	1.398 (7)	C25—C26	1.414 (6)
C5—C6	1.366 (6)	C26—C27	1.401 (7)
C5—H5A	0.9500	C27—C28	1.374 (6)
C6—C7	1.375 (7)	C27—H27A	0.9500
C6—H6A	0.9500	C28—C29	1.386 (7)
C7—C8	1.376 (6)	C28—H28A	0.9500
C7—H7A	0.9500	C29—C30	1.368 (7)
C8—H8A	0.9500	C29—H29A	0.9500
C9—C10B	1.396 (14)	C30—H30A	0.9500
C9—C10A	1.431 (8)	C31—C32	1.483 (6)
C9—H9A	0.9900	C31—H31A	0.9900
C9—H9B	0.9900	C31—H31B	0.9900
C9—H9C	0.9900	C32—C33	1.316 (6)
C9—H9D	0.9900	C32—H32A	0.9500
C10A—C11A	1.317 (18)	C33—H33A	0.9500
C10A—H10A	0.9500	C33—H33B	0.9500
C11A—H11A	0.9500	C35—C36	1.440 (6)
C11A—H11B	0.9500	C35—H35A	0.9500
C10B—C11B	1.33 (2)	C36—C37	1.386 (7)
C10B—H10B	0.9500	C36—C41	1.405 (6)
C11B—H11C	0.9500	C37—C38	1.373 (6)
C11B—H11D	0.9500	C38—C39	1.378 (7)
Cu2—O3	1.908 (3)	C38—H38A	0.9500
Cu2—N8	1.964 (4)	C39—C40	1.368 (7)
Cu2—S3	2.2401 (13)	C39—H39A	0.9500
Cu2—S4	2.3320 (12)	C40—C41	1.367 (6)
S3—C23	1.747 (4)	C40—H40A	0.9500
S4—C34	1.714 (4)	C41—H41A	0.9500
O3—C26	1.323 (6)	C42—C43	1.495 (6)
O4—C37	1.377 (6)	C42—H42A	0.9900
O4—H4O	0.79 (3)	C42—H42B	0.9900
N7—C23	1.317 (6)	C43—C44	1.297 (7)
N7—N8	1.393 (5)	C43—H43A	0.9500
N8—C24	1.282 (5)	C44—H44A	0.9500
N9—C23	1.334 (6)	C44—H44B	0.9500
N9—C31	1.454 (6)	O5—H51O	0.75 (3)
N9—H9N	0.81 (3)	O5—H52O	0.78 (4)
N10—C34	1.330 (6)	O6—H61O	0.89 (3)
N10—N11	1.391 (5)	O6—H62O	0.87 (3)
N10—H10N	0.82 (3)
O1—Cu1—N2	93.03 (13)	N5—C13—C14	124.3 (4)
O1—Cu1—S1	170.07 (10)	N5—C13—H13A	117.8
N2—Cu1—S1	85.32 (11)	C14—C13—H13A	117.8
O1—Cu1—S2	98.68 (9)	C19—C14—C15	118.1 (4)
N2—Cu1—S2	163.67 (10)	C19—C14—C13	118.9 (4)
S1—Cu1—S2	85.02 (5)	C15—C14—C13	122.9 (4)
C1—S1—Cu1	94.62 (15)	O2—C15—C16	117.6 (5)
C12—S2—Cu1	115.49 (15)	O2—C15—C14	122.3 (5)
C4—O1—Cu1	128.4 (3)	C16—C15—C14	120.1 (5)
C15—O2—H2O	109 (4)	C17—C16—C15	119.9 (5)
C1—N1—N2	112.8 (4)	C17—C16—H16A	120.0
C2—N2—N1	113.4 (4)	C15—C16—H16A	120.0
C2—N2—Cu1	125.9 (3)	C16—C17—C18	121.0 (5)
N1—N2—Cu1	120.7 (3)	C16—C17—H17A	119.5
C1—N3—C9	122.9 (4)	C18—C17—H17A	119.5
C1—N3—H3N	118 (4)	C19—C18—C17	118.9 (5)
C9—N3—H3N	119 (4)	C19—C18—H18A	120.5
C12—N4—N5	120.6 (4)	C17—C18—H18A	120.5
C12—N4—H4N	126 (3)	C18—C19—C14	121.9 (5)
N5—N4—H4N	110 (3)	C18—C19—H19A	119.1
C13—N5—N4	112.8 (4)	C14—C19—H19A	119.1
C12—N6—C20	124.4 (4)	N6—C20—C21	113.6 (4)
C12—N6—H6N	118 (4)	N6—C20—H20A	108.8
C20—N6—H6N	117 (4)	C21—C20—H20A	108.8
N1—C1—N3	117.7 (4)	N6—C20—H20B	108.8
N1—C1—S1	125.4 (4)	C21—C20—H20B	108.8
N3—C1—S1	116.9 (3)	H20A—C20—H20B	107.7
N2—C2—C3	125.7 (4)	C22—C21—C20	124.2 (5)
N2—C2—H2A	117.2	C22—C21—H21A	117.9
C3—C2—H2A	117.2	C20—C21—H21A	117.9
C8—C3—C4	119.4 (4)	C21—C22—H22A	120.0
C8—C3—C2	116.7 (4)	C21—C22—H22B	120.0
C4—C3—C2	123.8 (4)	H22A—C22—H22B	120.0
O1—C4—C5	119.5 (5)	N7—C23—N9	118.3 (4)
O1—C4—C3	123.1 (5)	N7—C23—S3	125.1 (3)
C5—C4—C3	117.5 (4)	N9—C23—S3	116.6 (3)
C6—C5—C4	121.7 (5)	N8—C24—C25	126.1 (4)
C6—C5—H5A	119.1	N8—C24—H24A	116.9
C4—C5—H5A	119.1	C25—C24—H24A	116.9
C5—C6—C7	121.2 (4)	C30—C25—C26	118.9 (4)
C5—C6—H6A	119.4	C30—C25—C24	117.2 (4)
C7—C6—H6A	119.4	C26—C25—C24	123.8 (4)
C8—C7—C6	118.5 (5)	O3—C26—C27	119.2 (5)
C8—C7—H7A	120.7	O3—C26—C25	123.4 (4)
C6—C7—H7A	120.7	C27—C26—C25	117.4 (4)
C7—C8—C3	121.6 (5)	C28—C27—C26	122.1 (5)
C7—C8—H8A	119.2	C28—C27—H27A	119.0
C3—C8—H8A	119.2	C26—C27—H27A	119.0
C10B—C9—C10A	45.0 (7)	C27—C28—C29	120.6 (4)
C10B—C9—N3	115.1 (7)	C27—C28—H28A	119.7
C10A—C9—N3	114.7 (5)	C29—C28—H28A	119.7
C10B—C9—H9A	66.2	C30—C29—C28	118.4 (5)
C10A—C9—H9A	108.6	C30—C29—H29A	120.8
N3—C9—H9A	108.6	C28—C29—H29A	120.8
C10B—C9—H9B	135.6	C29—C30—C25	122.5 (4)
C10A—C9—H9B	108.6	C29—C30—H30A	118.7
N3—C9—H9B	108.6	C25—C30—H30A	118.7
H9A—C9—H9B	107.6	N9—C31—C32	113.4 (4)
C10B—C9—H9C	108.5	N9—C31—H31A	108.9
C10A—C9—H9C	136.0	C32—C31—H31A	108.9
N3—C9—H9C	108.5	N9—C31—H31B	108.9
H9A—C9—H9C	47.2	C32—C31—H31B	108.9
H9B—C9—H9C	62.8	H31A—C31—H31B	107.7
C10B—C9—H9D	108.5	C33—C32—C31	123.7 (5)
C10A—C9—H9D	66.3	C33—C32—H32A	118.2
N3—C9—H9D	108.5	C31—C32—H32A	118.2
H9A—C9—H9D	140.6	C32—C33—H33A	120.0
H9B—C9—H9D	47.1	C32—C33—H33B	120.0
H9C—C9—H9D	107.5	H33A—C33—H33B	120.0
C11A—C10A—C9	127.9 (14)	N12—C34—N10	119.4 (4)
C11A—C10A—H10A	116.1	N12—C34—S4	121.4 (3)
C9—C10A—H10A	116.1	N10—C34—S4	119.2 (3)
C10A—C11A—H11A	120.0	N11—C35—C36	123.5 (4)
C10A—C11A—H11B	120.0	N11—C35—H35A	118.3
H11A—C11A—H11B	120.0	C36—C35—H35A	118.3
C11B—C10B—C9	127 (3)	C37—C36—C41	117.6 (4)
C11B—C10B—H10B	116.4	C37—C36—C35	123.9 (4)
C9—C10B—H10B	116.4	C41—C36—C35	118.5 (4)
C10B—C11B—H11C	120.0	C38—C37—O4	116.8 (5)
C10B—C11B—H11D	120.0	C38—C37—C36	121.3 (5)
H11C—C11B—H11D	120.0	O4—C37—C36	121.8 (4)
O3—Cu2—N8	93.19 (13)	C37—C38—C39	119.5 (5)
O3—Cu2—S3	171.12 (9)	C37—C38—H38A	120.2
N8—Cu2—S3	85.19 (11)	C39—C38—H38A	120.2
O3—Cu2—S4	98.83 (9)	C40—C39—C38	120.6 (5)
N8—Cu2—S4	164.03 (10)	C40—C39—H39A	119.7
S3—Cu2—S4	84.48 (4)	C38—C39—H39A	119.7
C23—S3—Cu2	94.78 (15)	C39—C40—C41	120.1 (4)
C34—S4—Cu2	115.93 (15)	C39—C40—H40A	120.0
C26—O3—Cu2	127.9 (3)	C41—C40—H40A	120.0
C37—O4—H4O	105 (4)	C40—C41—C36	120.9 (5)
C23—N7—N8	112.3 (4)	C40—C41—H41A	119.6
C24—N8—N7	113.7 (4)	C36—C41—H41A	119.6
C24—N8—Cu2	125.3 (3)	N12—C42—C43	112.3 (4)
N7—N8—Cu2	121.0 (3)	N12—C42—H42A	109.1
C23—N9—C31	124.7 (4)	C43—C42—H42A	109.1
C23—N9—H9N	123 (3)	N12—C42—H42B	109.1
C31—N9—H9N	112 (3)	C43—C42—H42B	109.1
C34—N10—N11	121.1 (4)	H42A—C42—H42B	107.9
C34—N10—H10N	121 (3)	C44—C43—C42	125.6 (5)
N11—N10—H10N	115 (3)	C44—C43—H43A	117.2
C35—N11—N10	113.4 (4)	C42—C43—H43A	117.2
C34—N12—C42	125.0 (4)	C43—C44—H44A	120.0
C34—N12—H12N	122 (4)	C43—C44—H44B	120.0
C42—N12—H12N	113 (4)	H44A—C44—H44B	120.0
N6—C12—N4	120.3 (4)	H51O—O5—H52O	102 (5)
N6—C12—S2	121.1 (3)	H61O—O6—H62O	105 (4)
N4—C12—S2	118.5 (3)
O1—Cu1—S1—C1	88.0 (6)	N5—N4—C12—N6	−10.0 (7)
N2—Cu1—S1—C1	7.14 (17)	N5—N4—C12—S2	170.0 (3)
S2—Cu1—S1—C1	−159.67 (14)	Cu1—S2—C12—N6	174.9 (3)
O1—Cu1—S2—C12	−7.56 (19)	Cu1—S2—C12—N4	−5.0 (4)
N2—Cu1—S2—C12	127.8 (4)	N4—N5—C13—C14	172.7 (4)
S1—Cu1—S2—C12	−178.27 (17)	N5—C13—C14—C19	−174.4 (4)
N2—Cu1—O1—C4	3.7 (4)	N5—C13—C14—C15	3.9 (6)
S1—Cu1—O1—C4	−76.5 (7)	C19—C14—C15—O2	178.6 (4)
S2—Cu1—O1—C4	172.3 (3)	C13—C14—C15—O2	0.3 (7)
C1—N1—N2—C2	−168.4 (4)	C19—C14—C15—C16	−0.2 (7)
C1—N1—N2—Cu1	10.2 (5)	C13—C14—C15—C16	−178.5 (4)
O1—Cu1—N2—C2	−2.7 (3)	O2—C15—C16—C17	−179.8 (4)
S1—Cu1—N2—C2	167.5 (3)	C14—C15—C16—C17	−1.0 (7)
S2—Cu1—N2—C2	−138.6 (3)	C15—C16—C17—C18	1.9 (8)
O1—Cu1—N2—N1	178.9 (3)	C16—C17—C18—C19	−1.6 (8)
S1—Cu1—N2—N1	−10.9 (3)	C17—C18—C19—C14	0.4 (7)
S2—Cu1—N2—N1	43.1 (6)	C15—C14—C19—C18	0.5 (7)
C12—N4—N5—C13	176.5 (4)	C13—C14—C19—C18	178.9 (4)
N2—N1—C1—N3	177.3 (4)	C12—N6—C20—C21	−89.1 (5)
N2—N1—C1—S1	−2.1 (6)	N6—C20—C21—C22	−141.8 (5)
C9—N3—C1—N1	−5.4 (8)	N8—N7—C23—N9	−178.9 (4)
C9—N3—C1—S1	174.0 (4)	N8—N7—C23—S3	0.3 (6)
Cu1—S1—C1—N1	−5.0 (4)	C31—N9—C23—N7	−4.6 (7)
Cu1—S1—C1—N3	175.7 (4)	C31—N9—C23—S3	176.1 (3)
N1—N2—C2—C3	−179.3 (4)	Cu2—S3—C23—N7	−8.1 (4)
Cu1—N2—C2—C3	2.2 (6)	Cu2—S3—C23—N9	171.2 (3)
N2—C2—C3—C8	179.1 (4)	N7—N8—C24—C25	−177.1 (4)
N2—C2—C3—C4	−1.7 (7)	Cu2—N8—C24—C25	4.1 (6)
Cu1—O1—C4—C5	175.4 (3)	N8—C24—C25—C30	178.4 (4)
Cu1—O1—C4—C3	−4.2 (6)	N8—C24—C25—C26	−1.3 (7)
C8—C3—C4—O1	−178.2 (4)	Cu2—O3—C26—C27	174.8 (3)
C2—C3—C4—O1	2.6 (7)	Cu2—O3—C26—C25	−4.3 (6)
C8—C3—C4—C5	2.3 (6)	C30—C25—C26—O3	−178.4 (4)
C2—C3—C4—C5	−177.0 (4)	C24—C25—C26—O3	1.3 (7)
O1—C4—C5—C6	178.3 (4)	C30—C25—C26—C27	2.5 (6)
C3—C4—C5—C6	−2.1 (7)	C24—C25—C26—C27	−177.8 (4)
C4—C5—C6—C7	0.2 (7)	O3—C26—C27—C28	178.0 (4)
C5—C6—C7—C8	1.5 (7)	C25—C26—C27—C28	−2.8 (7)
C6—C7—C8—C3	−1.4 (7)	C26—C27—C28—C29	1.4 (7)
C4—C3—C8—C7	−0.6 (7)	C27—C28—C29—C30	0.5 (7)
C2—C3—C8—C7	178.8 (4)	C28—C29—C30—C25	−0.8 (7)
C1—N3—C9—C10B	−123.5 (9)	C26—C25—C30—C29	−0.7 (7)
C1—N3—C9—C10A	−173.4 (6)	C24—C25—C30—C29	179.5 (4)
C10B—C9—C10A—C11A	19 (3)	C23—N9—C31—C32	−74.2 (6)
N3—C9—C10A—C11A	120 (3)	N9—C31—C32—C33	−116.7 (5)
C10A—C9—C10B—C11B	−18 (5)	C42—N12—C34—N10	−177.9 (4)
N3—C9—C10B—C11B	−119 (5)	C42—N12—C34—S4	0.6 (6)
O3—Cu2—S3—C23	89.0 (6)	N11—N10—C34—N12	−13.1 (6)
N8—Cu2—S3—C23	9.12 (16)	N11—N10—C34—S4	168.3 (3)
S4—Cu2—S3—C23	−158.68 (14)	Cu2—S4—C34—N12	170.7 (3)
O3—Cu2—S4—C34	−3.31 (18)	Cu2—S4—C34—N10	−10.7 (4)
N8—Cu2—S4—C34	135.1 (4)	N10—N11—C35—C36	172.2 (4)
S3—Cu2—S4—C34	−175.00 (17)	N11—C35—C36—C37	5.8 (7)
N8—Cu2—O3—C26	5.2 (4)	N11—C35—C36—C41	−173.0 (4)
S3—Cu2—O3—C26	−74.0 (8)	C41—C36—C37—C38	0.7 (7)
S4—Cu2—O3—C26	174.7 (3)	C35—C36—C37—C38	−178.1 (4)
C23—N7—N8—C24	−168.7 (4)	C41—C36—C37—O4	−179.6 (4)
C23—N7—N8—Cu2	10.2 (5)	C35—C36—C37—O4	1.7 (7)
O3—Cu2—N8—C24	−5.0 (3)	O4—C37—C38—C39	−179.6 (4)
S3—Cu2—N8—C24	166.2 (3)	C36—C37—C38—C39	0.2 (7)
S4—Cu2—N8—C24	−143.9 (3)	C37—C38—C39—C40	−0.5 (7)
O3—Cu2—N8—N7	176.2 (3)	C38—C39—C40—C41	−0.2 (7)
S3—Cu2—N8—N7	−12.6 (3)	C39—C40—C41—C36	1.1 (7)
S4—Cu2—N8—N7	37.3 (6)	C37—C36—C41—C40	−1.4 (6)
C34—N10—N11—C35	−179.9 (4)	C35—C36—C41—C40	177.5 (4)
C20—N6—C12—N4	−177.0 (4)	C34—N12—C42—C43	−82.6 (5)
C20—N6—C12—S2	3.0 (6)	N12—C42—C43—C44	−132.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N5	0.75 (5)	2.05 (5)	2.718 (5)	148 (6)
N4—H4N···O1	0.83 (3)	1.94 (3)	2.715 (5)	155 (4)
N6—H6N···O6	0.79 (3)	2.14 (4)	2.876 (5)	154 (5)
O4—H4O···N11	0.79 (3)	2.00 (4)	2.714 (5)	151 (6)
N9—H9N···S1	0.81 (3)	2.71 (3)	3.460 (4)	154 (4)
N10—H10N···O3	0.82 (3)	1.96 (3)	2.753 (5)	160 (4)
N12—H12N···O5	0.84 (5)	2.06 (5)	2.864 (5)	159 (5)
O5—H51O···O2^i	0.75 (3)	2.13 (4)	2.833 (4)	157 (5)
O5—H52O···N1^ii	0.78 (4)	2.19 (5)	2.912 (6)	155 (5)
O6—H61O···N7^iii	0.89 (3)	2.07 (3)	2.890 (5)	153 (4)
O6—H62O···O4^iv	0.87 (3)	1.97 (3)	2.827 (4)	165 (4)

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