Bis(2,S-dimethyl-dithio-carbazate-κ(2)N(3),S)(nitrato-κO)copper(II) nitrate.

The title complex, [Cu(NO(3))(C(3)H(8)N(2)S(2))(2)]NO(3), represents a low-symmetry polymorph (P-1, Z = 4) of a previously reported form [P-1, Z = 2; Ali et al. (2011 ▶). Polyhedron, 30, 542-548]. The Cu(II) atom in each independent cation is found within a distorted square-pyramidal N(2)S(2)O coordination geometry defined by two N,S-bidentate ligands and an O atom derived from a monodentate nitrate. The primary difference between the cations is found in the relative orientations of the coordinated nitrate groups, which are directed to opposite sides of the mol-ecule. Supra-molecular layers along [110] and sustained by N-H⋯O inter-actions feature in the crystal packing. These are connected along the c axis by C-H⋯O inter-actions.

Related literature

For related dithio­carbazate compounds, see: Hazari et al. (2012 ▶). For the previously reported polymorph, see: Ali et al. (2011 ▶). For additional structural analysis, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu(NO3)(C3H8N2S2)2]NO3

M = 460.03

Triclinic,

a = 11.2716 (4) Å

b = 12.1741 (4) Å

c = 13.8970 (5) Å

α = 115.449 (3)°

β = 100.734 (3)°

γ = 97.258 (3)°

V = 1645.39 (10) Å3

Z = 4

Mo Kα radiation

μ = 1.87 mm−1

T = 100 K

0.40 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.634, T max = 1.000

25371 measured reflections

7555 independent reflections

5675 reflections with I > 2σ(I)

R int = 0.080

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.165

S = 1.09

7555 reflections

423 parameters

H-atom parameters constrained

Δρmax = 1.15 e Å−3

Δρmin = −0.95 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶), DIAMOND (Brandenburg, 2006 ▶) and QMol (Gans & Shalloway, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021423/hg5229sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021423/hg5229Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(NO3)(C3H8N2S2)2]NO3	Z = 4
Mr = 460.03	F(000) = 940
Triclinic, P1	Dx = 1.857 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.2716 (4) Å	Cell parameters from 9482 reflections
b = 12.1741 (4) Å	θ = 2.3–27.5°
c = 13.8970 (5) Å	µ = 1.87 mm−1
α = 115.449 (3)°	T = 100 K
β = 100.734 (3)°	Prism, dark-blue
γ = 97.258 (3)°	0.40 × 0.20 × 0.10 mm
V = 1645.39 (10) Å3

Agilent SuperNova Dual diffractometer with an Atlas detector	7555 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5675 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.080
Detector resolution: 10.4041 pixels mm-1	θmax = 27.7°, θmin = 2.7°
ω scan	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −15→15
Tmin = 0.634, Tmax = 1.000	l = −18→18
25371 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0751P)2 + 6.3265P] where P = (Fo2 + 2Fc2)/3
7555 reflections	(Δ/σ)max = 0.001
423 parameters	Δρmax = 1.15 e Å−3
0 restraints	Δρmin = −0.95 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Cu1	0.27022 (5)	0.71242 (5)	0.22467 (4)	0.01064 (15)
Cu2	0.20705 (5)	0.78519 (5)	0.77159 (4)	0.01078 (15)
S1	0.65195 (10)	0.59926 (12)	0.27050 (9)	0.0159 (2)
S2	0.40155 (10)	0.59825 (11)	0.14944 (9)	0.0155 (2)
S3	0.13598 (10)	0.65016 (11)	0.05685 (9)	0.0139 (2)
S4	−0.11634 (11)	0.70264 (12)	0.01711 (10)	0.0188 (3)
S5	0.60066 (11)	0.78742 (12)	0.95772 (10)	0.0190 (3)
S6	0.35150 (10)	0.85031 (11)	0.93451 (9)	0.0143 (2)
S7	0.06784 (10)	0.88609 (11)	0.84813 (9)	0.0139 (2)
S8	−0.16110 (10)	0.92279 (11)	0.72725 (9)	0.0133 (2)
O1	0.1587 (3)	0.5846 (3)	0.7551 (3)	0.0177 (7)
O2	−0.0076 (3)	0.4891 (3)	0.6179 (3)	0.0199 (7)
O3	0.0550 (3)	0.4046 (3)	0.7214 (3)	0.0202 (7)
O4	0.3519 (3)	0.9027 (3)	0.2425 (3)	0.0232 (8)
O5	0.5043 (3)	0.9861 (3)	0.3912 (3)	0.0235 (8)
O6	0.4745 (3)	1.0785 (3)	0.2888 (3)	0.0203 (7)
O7	0.3444 (3)	0.5699 (3)	0.4424 (3)	0.0263 (8)
O8	0.2260 (3)	0.3833 (3)	0.3526 (3)	0.0233 (8)
O9	0.2420 (4)	0.4953 (3)	0.5264 (3)	0.0245 (8)
O10	0.2186 (3)	0.8161 (3)	0.5108 (3)	0.0165 (7)
O11	0.2091 (4)	0.9896 (3)	0.5040 (3)	0.0255 (8)
O12	0.2295 (3)	0.9840 (3)	0.6602 (3)	0.0254 (8)
N1	0.4943 (3)	0.7112 (4)	0.3668 (3)	0.0106 (7)
N2	0.3831 (3)	0.7541 (4)	0.3726 (3)	0.0116 (7)
H21	0.4027	0.8358	0.4139	0.014*
H22	0.3421	0.7212	0.4056	0.014*
N3	0.1317 (3)	0.7749 (4)	0.2882 (3)	0.0127 (8)
H31	0.1039	0.7274	0.3160	0.015*
H32	0.1619	0.8512	0.3430	0.015*
N4	0.0302 (3)	0.7770 (4)	0.2120 (3)	0.0114 (7)
N5	0.4450 (3)	0.9892 (3)	0.3079 (3)	0.0119 (7)
N6	0.4480 (3)	0.7287 (4)	0.7694 (3)	0.0130 (8)
N7	0.3416 (3)	0.7342 (4)	0.6995 (3)	0.0124 (8)
H71	0.3115	0.6601	0.6416	0.015*
H72	0.3649	0.7874	0.6756	0.015*
N8	0.0826 (3)	0.7273 (4)	0.6262 (3)	0.0123 (8)
H81	0.1221	0.7324	0.5788	0.015*
H82	0.0468	0.6480	0.6008	0.015*
N9	−0.0108 (3)	0.7954 (3)	0.6308 (3)	0.0095 (7)
N10	0.0668 (3)	0.4928 (4)	0.6978 (3)	0.0133 (8)
N11	0.2703 (4)	0.4823 (4)	0.4388 (3)	0.0151 (8)
N12	0.2198 (4)	0.9315 (4)	0.5595 (3)	0.0169 (8)
C1	0.6459 (4)	0.5218 (5)	0.1266 (4)	0.0178 (10)
H1A	0.7211	0.4904	0.1176	0.027*
H1B	0.6405	0.5809	0.0963	0.027*
H1C	0.5728	0.4516	0.0871	0.027*
C2	0.5109 (4)	0.6429 (4)	0.2689 (4)	0.0110 (8)
C3	0.5857 (4)	0.7512 (5)	0.4715 (4)	0.0152 (9)
H3A	0.6280	0.6840	0.4663	0.023*
H3B	0.5440	0.7704	0.5307	0.023*
H3C	0.6468	0.8260	0.4879	0.023*
C4	−0.0671 (4)	0.8334 (5)	0.2569 (4)	0.0176 (10)
H4A	−0.1007	0.8761	0.2159	0.026*
H4B	−0.0321	0.8940	0.3352	0.026*
H4C	−0.1337	0.7680	0.2496	0.026*
C5	0.0214 (4)	0.7144 (4)	0.1053 (4)	0.0119 (9)
C6	−0.0918 (5)	0.6233 (5)	−0.1177 (4)	0.0203 (10)
H6A	−0.1655	0.6124	−0.1740	0.030*
H6B	−0.0769	0.5412	−0.1303	0.030*
H6C	−0.0196	0.6730	−0.1223	0.030*
C7	0.5800 (5)	0.8552 (5)	1.0945 (4)	0.0224 (11)
H7A	0.6548	0.8614	1.1473	0.034*
H7B	0.5086	0.8024	1.0969	0.034*
H7C	0.5653	0.9389	1.1141	0.034*
C8	0.4610 (4)	0.7851 (4)	0.8777 (4)	0.0133 (9)
C9	0.5417 (4)	0.6735 (5)	0.7175 (4)	0.0170 (10)
H9A	0.5769	0.6266	0.7534	0.025*
H9B	0.6078	0.7400	0.7257	0.025*
H9C	0.5032	0.6169	0.6388	0.025*
C10	−0.0875 (4)	0.7751 (4)	0.5256 (4)	0.0139 (9)
H10A	−0.1248	0.8467	0.5369	0.021*
H10B	−0.1533	0.6989	0.4947	0.021*
H10C	−0.0362	0.7660	0.4741	0.021*
C11	−0.0305 (4)	0.8604 (4)	0.7285 (4)	0.0113 (8)
C12	−0.1614 (4)	0.9903 (5)	0.8701 (4)	0.0174 (10)
H12A	−0.2341	1.0262	0.8793	0.026*
H12B	−0.0856	1.0562	0.9150	0.026*
H12C	−0.1646	0.9254	0.8941	0.026*

	U11	U22	U33	U12	U13	U23
Cu1	0.0092 (3)	0.0148 (3)	0.0094 (3)	0.0038 (2)	0.0040 (2)	0.0061 (2)
Cu2	0.0107 (3)	0.0145 (3)	0.0087 (3)	0.0045 (2)	0.0051 (2)	0.0053 (2)
S1	0.0118 (5)	0.0270 (6)	0.0099 (5)	0.0089 (5)	0.0055 (4)	0.0072 (5)
S2	0.0147 (5)	0.0221 (6)	0.0080 (5)	0.0077 (5)	0.0028 (4)	0.0047 (5)
S3	0.0117 (5)	0.0191 (6)	0.0109 (5)	0.0048 (4)	0.0040 (4)	0.0062 (4)
S4	0.0141 (5)	0.0261 (7)	0.0169 (6)	0.0074 (5)	0.0027 (4)	0.0105 (5)
S5	0.0137 (5)	0.0261 (7)	0.0180 (6)	0.0077 (5)	0.0043 (5)	0.0101 (5)
S6	0.0119 (5)	0.0195 (6)	0.0100 (5)	0.0049 (4)	0.0045 (4)	0.0046 (4)
S7	0.0154 (5)	0.0204 (6)	0.0079 (5)	0.0079 (4)	0.0055 (4)	0.0063 (4)
S8	0.0124 (5)	0.0191 (6)	0.0102 (5)	0.0066 (4)	0.0055 (4)	0.0066 (4)
O1	0.0163 (16)	0.0150 (17)	0.0197 (17)	−0.0026 (13)	0.0004 (13)	0.0095 (14)
O2	0.0180 (17)	0.0208 (18)	0.0191 (18)	0.0047 (14)	0.0013 (14)	0.0089 (15)
O3	0.0219 (17)	0.0162 (17)	0.0255 (19)	0.0010 (14)	0.0068 (15)	0.0131 (15)
O4	0.0195 (17)	0.0203 (18)	0.0231 (19)	−0.0062 (14)	−0.0062 (15)	0.0119 (16)
O5	0.0216 (18)	0.026 (2)	0.0210 (19)	−0.0025 (15)	−0.0026 (15)	0.0142 (16)
O6	0.0257 (18)	0.0164 (17)	0.0232 (19)	0.0010 (14)	0.0095 (15)	0.0130 (15)
O7	0.029 (2)	0.023 (2)	0.031 (2)	−0.0001 (16)	0.0144 (17)	0.0157 (17)
O8	0.0241 (18)	0.0227 (19)	0.0165 (18)	0.0043 (15)	0.0075 (15)	0.0026 (15)
O9	0.034 (2)	0.0234 (19)	0.0134 (17)	−0.0020 (16)	0.0096 (15)	0.0076 (15)
O10	0.0196 (17)	0.0166 (17)	0.0159 (16)	0.0060 (13)	0.0114 (14)	0.0067 (14)
O11	0.032 (2)	0.0192 (19)	0.0225 (19)	0.0047 (16)	−0.0014 (16)	0.0106 (16)
O12	0.028 (2)	0.027 (2)	0.0144 (18)	0.0047 (16)	0.0112 (15)	0.0020 (15)
N1	0.0094 (17)	0.0160 (19)	0.0099 (18)	0.0053 (14)	0.0047 (14)	0.0076 (15)
N2	0.0140 (18)	0.0132 (19)	0.0108 (18)	0.0082 (15)	0.0069 (15)	0.0056 (15)
N3	0.0112 (17)	0.018 (2)	0.0090 (18)	0.0026 (15)	0.0010 (14)	0.0073 (16)
N4	0.0088 (17)	0.0159 (19)	0.0117 (18)	0.0047 (14)	0.0042 (14)	0.0073 (16)
N5	0.0113 (17)	0.0116 (18)	0.0150 (19)	0.0051 (14)	0.0087 (15)	0.0053 (15)
N6	0.0101 (17)	0.016 (2)	0.0129 (19)	0.0040 (15)	0.0057 (15)	0.0056 (16)
N7	0.0132 (18)	0.0137 (19)	0.0103 (18)	0.0019 (15)	0.0042 (15)	0.0055 (15)
N8	0.0140 (18)	0.0161 (19)	0.0113 (18)	0.0089 (15)	0.0067 (15)	0.0077 (16)
N9	0.0089 (16)	0.0122 (18)	0.0098 (17)	0.0034 (14)	0.0051 (14)	0.0061 (15)
N10	0.0101 (17)	0.0131 (19)	0.017 (2)	0.0048 (15)	0.0083 (15)	0.0047 (16)
N11	0.0132 (18)	0.018 (2)	0.018 (2)	0.0046 (15)	0.0061 (16)	0.0099 (17)
N12	0.0109 (18)	0.021 (2)	0.018 (2)	0.0034 (16)	0.0054 (15)	0.0072 (17)
C1	0.016 (2)	0.025 (3)	0.012 (2)	0.0083 (19)	0.0065 (18)	0.006 (2)
C2	0.013 (2)	0.009 (2)	0.010 (2)	0.0026 (16)	0.0056 (16)	0.0036 (17)
C3	0.012 (2)	0.025 (3)	0.008 (2)	0.0068 (18)	0.0028 (17)	0.0054 (19)
C4	0.015 (2)	0.019 (2)	0.019 (2)	0.0091 (19)	0.0097 (19)	0.006 (2)
C5	0.010 (2)	0.013 (2)	0.014 (2)	0.0021 (16)	0.0036 (17)	0.0075 (18)
C6	0.024 (2)	0.025 (3)	0.017 (2)	0.005 (2)	0.006 (2)	0.014 (2)
C7	0.022 (2)	0.030 (3)	0.015 (2)	0.007 (2)	0.004 (2)	0.011 (2)
C8	0.015 (2)	0.014 (2)	0.009 (2)	0.0033 (17)	0.0047 (17)	0.0039 (18)
C9	0.015 (2)	0.021 (2)	0.016 (2)	0.0094 (19)	0.0099 (18)	0.0060 (19)
C10	0.014 (2)	0.019 (2)	0.010 (2)	0.0056 (18)	0.0025 (17)	0.0072 (18)
C11	0.011 (2)	0.014 (2)	0.011 (2)	0.0032 (17)	0.0059 (16)	0.0063 (18)
C12	0.017 (2)	0.025 (3)	0.010 (2)	0.010 (2)	0.0076 (18)	0.0050 (19)

Cu1—S2	2.2502 (12)	N3—N4	1.417 (5)
Cu1—S3	2.2759 (12)	N3—H31	0.8800
Cu1—O4	2.271 (3)	N3—H32	0.8800
Cu1—N2	2.017 (4)	N4—C5	1.321 (6)
Cu1—N3	2.008 (4)	N4—C4	1.463 (6)
Cu2—S6	2.2724 (12)	N6—C8	1.328 (6)
Cu2—S7	2.2557 (12)	N6—N7	1.424 (5)
Cu2—O1	2.334 (3)	N6—C9	1.459 (6)
Cu2—N7	1.990 (4)	N7—H71	0.8800
Cu2—N8	2.004 (4)	N7—H72	0.8800
S1—C2	1.738 (4)	N8—N9	1.414 (5)
S1—C1	1.790 (5)	N8—H81	0.8800
S2—C2	1.692 (5)	N8—H82	0.8800
S3—C5	1.691 (4)	N9—C11	1.324 (6)
S4—C5	1.737 (4)	N9—C10	1.454 (6)
S4—C6	1.795 (5)	C1—H1A	0.9800
S5—C8	1.739 (5)	C1—H1B	0.9800
S5—C7	1.793 (5)	C1—H1C	0.9800
S6—C8	1.688 (5)	C3—H3A	0.9800
S7—C11	1.694 (5)	C3—H3B	0.9800
S8—C11	1.740 (4)	C3—H3C	0.9800
S8—C12	1.794 (5)	C4—H4A	0.9800
O1—N10	1.262 (5)	C4—H4B	0.9800
O2—N10	1.241 (5)	C4—H4C	0.9800
O3—N10	1.250 (5)	C6—H6A	0.9800
O4—N5	1.257 (5)	C6—H6B	0.9800
O5—N5	1.242 (5)	C6—H6C	0.9800
O6—N5	1.246 (5)	C7—H7A	0.9800
O7—N11	1.246 (5)	C7—H7B	0.9800
O8—N11	1.234 (5)	C7—H7C	0.9800
O9—N11	1.264 (5)	C9—H9A	0.9800
O10—N12	1.268 (5)	C9—H9B	0.9800
O11—N12	1.252 (5)	C9—H9C	0.9800
O12—N12	1.239 (5)	C10—H10A	0.9800
N1—C2	1.318 (6)	C10—H10B	0.9800
N1—N2	1.420 (5)	C10—H10C	0.9800
N1—C3	1.457 (6)	C12—H12A	0.9800
N2—H21	0.8800	C12—H12B	0.9800
N2—H22	0.8800	C12—H12C	0.9800
N3—Cu1—N2	94.04 (14)	O2—N10—O3	121.1 (4)
N3—Cu1—S2	166.11 (12)	O2—N10—O1	120.4 (4)
N2—Cu1—S2	86.27 (11)	O3—N10—O1	118.4 (4)
N3—Cu1—O4	91.59 (15)	O8—N11—O7	121.4 (4)
N2—Cu1—O4	91.09 (14)	O8—N11—O9	119.8 (4)
S2—Cu1—O4	102.29 (11)	O7—N11—O9	118.8 (4)
N3—Cu1—S3	85.68 (11)	O12—N12—O11	121.4 (4)
N2—Cu1—S3	175.33 (12)	O12—N12—O10	119.7 (4)
S2—Cu1—S3	92.88 (4)	O11—N12—O10	118.9 (4)
O4—Cu1—S3	93.58 (9)	S1—C1—H1A	109.5
N7—Cu2—N8	92.53 (15)	S1—C1—H1B	109.5
N7—Cu2—S7	165.60 (12)	H1A—C1—H1B	109.5
N8—Cu2—S7	85.68 (11)	S1—C1—H1C	109.5
N7—Cu2—S6	86.25 (11)	H1A—C1—H1C	109.5
N8—Cu2—S6	178.76 (11)	H1B—C1—H1C	109.5
S7—Cu2—S6	95.44 (4)	N1—C2—S2	122.5 (3)
N7—Cu2—O1	87.60 (14)	N1—C2—S1	115.5 (3)
N8—Cu2—O1	89.83 (14)	S2—C2—S1	122.0 (3)
S7—Cu2—O1	106.66 (9)	N1—C3—H3A	109.5
S6—Cu2—O1	90.35 (9)	N1—C3—H3B	109.5
C2—S1—C1	102.6 (2)	H3A—C3—H3B	109.5
C2—S2—Cu1	97.03 (15)	N1—C3—H3C	109.5
C5—S3—Cu1	96.68 (16)	H3A—C3—H3C	109.5
C5—S4—C6	103.3 (2)	H3B—C3—H3C	109.5
C8—S5—C7	102.6 (2)	N4—C4—H4A	109.5
C8—S6—Cu2	95.88 (16)	N4—C4—H4B	109.5
C11—S7—Cu2	96.78 (15)	H4A—C4—H4B	109.5
C11—S8—C12	102.0 (2)	N4—C4—H4C	109.5
N10—O1—Cu2	133.0 (3)	H4A—C4—H4C	109.5
N5—O4—Cu1	133.9 (3)	H4B—C4—H4C	109.5
C2—N1—N2	119.0 (4)	N4—C5—S3	122.7 (3)
C2—N1—C3	124.2 (4)	N4—C5—S4	115.4 (3)
N2—N1—C3	116.7 (3)	S3—C5—S4	121.8 (3)
N1—N2—Cu1	114.4 (3)	S4—C6—H6A	109.5
N1—N2—H21	108.6	S4—C6—H6B	109.5
Cu1—N2—H21	108.6	H6A—C6—H6B	109.5
N1—N2—H22	108.6	S4—C6—H6C	109.5
Cu1—N2—H22	108.6	H6A—C6—H6C	109.5
H21—N2—H22	107.6	H6B—C6—H6C	109.5
N4—N3—Cu1	115.0 (3)	S5—C7—H7A	109.5
N4—N3—H31	108.5	S5—C7—H7B	109.5
Cu1—N3—H31	108.5	H7A—C7—H7B	109.5
N4—N3—H32	108.5	S5—C7—H7C	109.5
Cu1—N3—H32	108.5	H7A—C7—H7C	109.5
H31—N3—H32	107.5	H7B—C7—H7C	109.5
C5—N4—N3	118.3 (4)	N6—C8—S6	123.1 (3)
C5—N4—C4	124.2 (4)	N6—C8—S5	114.8 (3)
N3—N4—C4	116.9 (4)	S6—C8—S5	122.1 (3)
O5—N5—O6	121.1 (4)	N6—C9—H9A	109.5
O5—N5—O4	120.0 (4)	N6—C9—H9B	109.5
O6—N5—O4	118.9 (4)	H9A—C9—H9B	109.5
C8—N6—N7	117.8 (4)	N6—C9—H9C	109.5
C8—N6—C9	124.5 (4)	H9A—C9—H9C	109.5
N7—N6—C9	117.3 (4)	H9B—C9—H9C	109.5
N6—N7—Cu2	114.5 (3)	N9—C10—H10A	109.5
N6—N7—H71	108.6	N9—C10—H10B	109.5
Cu2—N7—H71	108.6	H10A—C10—H10B	109.5
N6—N7—H72	108.6	N9—C10—H10C	109.5
Cu2—N7—H72	108.6	H10A—C10—H10C	109.5
H71—N7—H72	107.6	H10B—C10—H10C	109.5
N9—N8—Cu2	114.5 (3)	N9—C11—S7	122.3 (3)
N9—N8—H81	108.6	N9—C11—S8	115.9 (3)
Cu2—N8—H81	108.6	S7—C11—S8	121.8 (3)
N9—N8—H82	108.6	S8—C12—H12A	109.5
Cu2—N8—H82	108.6	S8—C12—H12B	109.5
H81—N8—H82	107.6	H12A—C12—H12B	109.5
C11—N9—N8	117.6 (4)	S8—C12—H12C	109.5
C11—N9—C10	125.2 (4)	H12A—C12—H12C	109.5
N8—N9—C10	116.6 (3)	H12B—C12—H12C	109.5
N3—Cu1—S2—C2	−98.7 (5)	S6—Cu2—N7—N6	15.0 (3)
N2—Cu1—S2—C2	−6.90 (19)	O1—Cu2—N7—N6	−75.5 (3)
O4—Cu1—S2—C2	83.40 (18)	N7—Cu2—N8—N9	−149.6 (3)
S3—Cu1—S2—C2	177.70 (16)	S7—Cu2—N8—N9	16.1 (3)
N3—Cu1—S3—C5	5.78 (19)	S6—Cu2—N8—N9	−139 (5)
N2—Cu1—S3—C5	92.5 (13)	O1—Cu2—N8—N9	122.8 (3)
S2—Cu1—S3—C5	171.94 (16)	Cu2—N8—N9—C11	−20.0 (5)
O4—Cu1—S3—C5	−85.54 (18)	Cu2—N8—N9—C10	167.7 (3)
N7—Cu2—S6—C8	−9.96 (19)	Cu2—O1—N10—O2	15.7 (6)
N8—Cu2—S6—C8	−21 (5)	Cu2—O1—N10—O3	−166.4 (3)
S7—Cu2—S6—C8	−175.62 (16)	N2—N1—C2—S2	−3.0 (6)
O1—Cu2—S6—C8	77.61 (18)	C3—N1—C2—S2	179.8 (3)
N7—Cu2—S7—C11	74.6 (5)	N2—N1—C2—S1	178.0 (3)
N8—Cu2—S7—C11	−8.69 (19)	C3—N1—C2—S1	0.7 (6)
S6—Cu2—S7—C11	170.78 (16)	Cu1—S2—C2—N1	7.4 (4)
O1—Cu2—S7—C11	−97.22 (18)	Cu1—S2—C2—S1	−173.6 (2)
N7—Cu2—O1—N10	−111.8 (4)	C1—S1—C2—N1	−175.2 (4)
N8—Cu2—O1—N10	−19.2 (4)	C1—S1—C2—S2	5.8 (3)
S7—Cu2—O1—N10	66.2 (4)	N3—N4—C5—S3	−9.1 (6)
S6—Cu2—O1—N10	162.0 (4)	C4—N4—C5—S3	−179.8 (3)
N3—Cu1—O4—N5	105.5 (4)	N3—N4—C5—S4	171.0 (3)
N2—Cu1—O4—N5	11.4 (4)	C4—N4—C5—S4	0.4 (6)
S2—Cu1—O4—N5	−75.0 (4)	Cu1—S3—C5—N4	−0.1 (4)
S3—Cu1—O4—N5	−168.7 (4)	Cu1—S3—C5—S4	179.7 (2)
C2—N1—N2—Cu1	−4.4 (5)	C6—S4—C5—N4	176.2 (3)
C3—N1—N2—Cu1	173.1 (3)	C6—S4—C5—S3	−3.7 (4)
N3—Cu1—N2—N1	173.2 (3)	N7—N6—C8—S6	5.9 (6)
S2—Cu1—N2—N1	7.1 (3)	C9—N6—C8—S6	178.8 (4)
O4—Cu1—N2—N1	−95.2 (3)	N7—N6—C8—S5	−173.9 (3)
S3—Cu1—N2—N1	86.8 (14)	C9—N6—C8—S5	−1.0 (6)
N2—Cu1—N3—N4	173.4 (3)	Cu2—S6—C8—N6	5.2 (4)
S2—Cu1—N3—N4	−95.8 (5)	Cu2—S6—C8—S5	−175.0 (3)
O4—Cu1—N3—N4	82.2 (3)	C7—S5—C8—N6	−174.7 (4)
S3—Cu1—N3—N4	−11.3 (3)	C7—S5—C8—S6	5.5 (4)
Cu1—N3—N4—C5	14.6 (5)	N8—N9—C11—S7	11.7 (6)
Cu1—N3—N4—C4	−174.1 (3)	C10—N9—C11—S7	−176.7 (3)
Cu1—O4—N5—O5	−9.9 (6)	N8—N9—C11—S8	−170.5 (3)
Cu1—O4—N5—O6	171.7 (3)	C10—N9—C11—S8	1.1 (6)
C8—N6—N7—Cu2	−15.9 (5)	Cu2—S7—C11—N9	1.2 (4)
C9—N6—N7—Cu2	170.7 (3)	Cu2—S7—C11—S8	−176.6 (2)
N8—Cu2—N7—N6	−165.2 (3)	C12—S8—C11—N9	175.4 (3)
S7—Cu2—N7—N6	112.3 (5)	C12—S8—C11—S7	−6.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O5	0.88	2.21	2.860 (5)	131
N2—H22···O7	0.88	2.11	2.817 (5)	136
N3—H31···O3i	0.88	2.07	2.776 (5)	137
N3—H32···O11	0.88	2.05	2.881 (5)	156
N7—H71···O9	0.88	1.89	2.768 (5)	174
N7—H72···O6ii	0.88	2.10	2.807 (5)	137
N8—H81···O10	0.88	2.01	2.842 (5)	157
N8—H82···O2	0.88	2.08	2.894 (5)	154
C6—H6A···O8iii	0.98	2.47	3.295 (6)	141
C7—H7A···O12iv	0.98	2.48	3.247 (6)	135

Table 1

Selected bond lengths (Å)

Cu1—S2	2.2502 (12)
Cu1—S3	2.2759 (12)
Cu1—O4	2.271 (3)
Cu1—N2	2.017 (4)
Cu1—N3	2.008 (4)
Cu2—S6	2.2724 (12)
Cu2—S7	2.2557 (12)
Cu2—O1	2.334 (3)
Cu2—N7	1.990 (4)
Cu2—N8	2.004 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O5	0.88	2.21	2.860 (5)	131
N2—H22⋯O7	0.88	2.11	2.817 (5)	136
N3—H31⋯O3i	0.88	2.07	2.776 (5)	137
N3—H32⋯O11	0.88	2.05	2.881 (5)	156
N7—H71⋯O9	0.88	1.89	2.768 (5)	174
N7—H72⋯O6ii	0.88	2.10	2.807 (5)	137
N8—H81⋯O10	0.88	2.01	2.842 (5)	157
N8—H82⋯O2	0.88	2.08	2.894 (5)	154
C6—H6A⋯O8iii	0.98	2.47	3.295 (6)	141
C7—H7A⋯O12iv	0.98	2.48	3.247 (6)	135

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .