Aqua-bis-[2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole-κ(2)N(2),N(3)](trifluoro-methane-sulfonato-κO)copper(II) trifluoro-methane-sulfonate.

2,5-Bis(pyridin-2-yl)-1,3,4-thia-diazole (denoted L) has been found to act as a bidentate ligand in the monomeric title complex, [Cu(CF(3)O(3)S)(C(12)H(8)N(4)S)(2)(H(2)O)](CF(3)O(3)S). The complex shows a distorted octahedrally coordinated copper(II) cation which is linked to two thia-diazole ligands, one water mol-ecule and one trifluoro-methane-sulfonate anion. The second trifluoro-methane-sulfonate anion does not coordinate the copper(II) cation. Each thia-diazole ligand uses one pyridyl and one thia-diazole N atom for the coordination of copper. The N atom of the second non-coordinating pyridyl substituent is found on the same side of the 1,3,4-thia-diazole ring as the S atom. The trifluoro-methane-sulfonate ions are involved in a three-dimensional network of O-H⋯O hydrogen bonds. C-H⋯N inter-actions also occur.

Related literature

For the synthesis of the ligand, see: Lebrini et al. (2005 ▶). For background to compounds with the same ligand but other metals and other counter-anions, see: Bentiss et al. (2002 ▶, 2004 ▶, 2011a ▶,b ▶); Keij et al. (1984 ▶); Zheng et al. (2006 ▶).

Experimental

Crystal data

[Cu(CF3O3S)(C12H8N4S)2(H2O)](CF3O3S)

M = 860.26

Triclinic,

a = 8.469 (3) Å

b = 11.116 (3) Å

c = 18.834 (6) Å

α = 92.111 (14)°

β = 90.823 (14)°

γ = 107.352 (14)°

V = 1690.6 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.98 mm−1

T = 100 K

0.39 × 0.30 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▶) T min = 0.879, T max = 1.000

12380 measured reflections

6517 independent reflections

5421 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.099

S = 1.03

6517 reflections

469 parameters

H-atom parameters constrained

Δρmax = 1.39 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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 ▶) and ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812008732/im2358sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008732/im2358Isup2.hkl

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

[Cu(CF3O3S)(C12H8N4S)2(H2O)](CF3O3S)	Z = 2
Mr = 860.26	F(000) = 866
Triclinic, P1	Dx = 1.690 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.469 (3) Å	Cell parameters from 4698 reflections
b = 11.116 (3) Å	θ = 2.5–28.2°
c = 18.834 (6) Å	µ = 0.98 mm−1
α = 92.111 (14)°	T = 100 K
β = 90.823 (14)°	Irregular parallelepiped, blue
γ = 107.352 (14)°	0.39 × 0.30 × 0.17 mm
V = 1690.6 (9) Å3

Bruker APEXII CCD diffractometer	6517 independent reflections
Radiation source: fine-focus sealed tube	5421 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	h = −10→10
Tmin = 0.879, Tmax = 1.000	k = −12→13
12380 measured reflections	l = −19→23

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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F2) = 0.099	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0306P)2 + 2.8618P] where P = (Fo2 + 2Fc2)/3
6517 reflections	(Δ/σ)max = 0.001
469 parameters	Δρmax = 1.39 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.7108 (3)	0.3893 (3)	0.21546 (15)	0.0167 (6)
C2	0.7265 (4)	0.3860 (3)	0.29290 (15)	0.0171 (6)
C3	0.8424 (4)	0.4766 (3)	0.33445 (16)	0.0215 (6)
H3	0.9241	0.5425	0.3132	0.026*
C4	0.8363 (4)	0.4688 (3)	0.40768 (16)	0.0244 (7)
H4	0.9141	0.5290	0.4378	0.029*
C5	0.7151 (4)	0.3720 (3)	0.43558 (16)	0.0227 (7)
H5	0.7062	0.3657	0.4856	0.027*
C6	0.6052 (4)	0.2830 (3)	0.39019 (15)	0.0214 (6)
H6	0.5235	0.2158	0.4104	0.026*
C7	0.6958 (4)	0.4195 (3)	0.09165 (15)	0.0177 (6)
C8	0.7178 (4)	0.4640 (3)	0.01825 (15)	0.0187 (6)
C9	0.6216 (4)	0.3978 (3)	−0.03813 (16)	0.0230 (7)
H9	0.5360	0.3219	−0.0309	0.028*
C10	0.6513 (4)	0.4437 (3)	−0.10520 (17)	0.0275 (7)
H10	0.5875	0.3995	−0.1452	0.033*
C11	0.7754 (4)	0.5548 (3)	−0.11309 (16)	0.0293 (7)
H11	0.7987	0.5887	−0.1587	0.035*
C12	0.8654 (5)	0.6161 (3)	−0.05375 (18)	0.0358 (9)
H12	0.9500	0.6931	−0.0600	0.043*
C13	0.2339 (3)	−0.0673 (3)	0.27519 (15)	0.0175 (6)
C14	0.2426 (3)	−0.0758 (3)	0.19841 (15)	0.0169 (6)
C15	0.1621 (4)	−0.1827 (3)	0.15729 (16)	0.0213 (6)
H15	0.1006	−0.2579	0.1786	0.026*
C16	0.1736 (4)	−0.1772 (3)	0.08417 (16)	0.0221 (6)
H16	0.1190	−0.2484	0.0541	0.026*
C17	0.2662 (4)	−0.0659 (3)	0.05565 (16)	0.0243 (7)
H17	0.2740	−0.0594	0.0056	0.029*
C18	0.3478 (4)	0.0364 (3)	0.10069 (16)	0.0225 (6)
H18	0.4131	0.1116	0.0805	0.027*
C19	0.1962 (4)	−0.0710 (3)	0.39831 (15)	0.0192 (6)
C20	0.1420 (4)	−0.0996 (3)	0.47119 (15)	0.0211 (6)
C21	0.2257 (4)	−0.0288 (3)	0.52982 (17)	0.0256 (7)
H21	0.3220	0.0405	0.5245	0.031*
C22	0.1648 (5)	−0.0620 (3)	0.59622 (17)	0.0303 (8)
H22	0.2179	−0.0160	0.6379	0.036*
C23	0.0248 (5)	−0.1638 (3)	0.60030 (17)	0.0324 (8)
H23	−0.0199	−0.1893	0.6452	0.039*
C24	−0.0505 (4)	−0.2287 (3)	0.53868 (18)	0.0295 (8)
H24	−0.1477	−0.2978	0.5428	0.035*
C25	0.7497 (4)	−0.0999 (3)	0.1475 (2)	0.0326 (8)
C26	0.5085 (5)	0.6738 (3)	0.3395 (2)	0.0406 (9)
Cu1	0.46280 (4)	0.16646 (3)	0.245633 (17)	0.01429 (10)
F1	0.8341 (3)	−0.1118 (2)	0.09071 (11)	0.0517 (6)
F2	0.5891 (3)	−0.1337 (2)	0.12690 (18)	0.0797 (10)
F3	0.7741 (3)	−0.18338 (19)	0.19345 (14)	0.0505 (6)
F4	0.5915 (3)	0.6734 (2)	0.40113 (16)	0.0634 (8)
F5	0.5912 (3)	0.6359 (3)	0.28793 (16)	0.0692 (8)
F6	0.5078 (3)	0.7939 (2)	0.32673 (17)	0.0646 (8)
N1	0.6097 (3)	0.2881 (2)	0.31953 (12)	0.0167 (5)
N2	0.5919 (3)	0.3016 (2)	0.18095 (12)	0.0169 (5)
N3	0.5828 (3)	0.3191 (2)	0.10989 (12)	0.0170 (5)
N4	0.8406 (4)	0.5733 (3)	0.01268 (14)	0.0305 (7)
N5	0.3375 (3)	0.0327 (2)	0.17125 (13)	0.0175 (5)
N6	0.3392 (3)	0.0282 (2)	0.31048 (12)	0.0183 (5)
N7	0.3180 (3)	0.0260 (2)	0.38209 (12)	0.0183 (5)
N8	0.0056 (3)	−0.1997 (3)	0.47406 (14)	0.0253 (6)
O1	0.2619 (2)	0.26218 (19)	0.24674 (11)	0.0229 (5)
H1W	0.2659	0.3116	0.2778	0.027*
H2W	0.1708	0.2137	0.2402	0.027*
O2	0.9771 (3)	0.0724 (2)	0.21448 (15)	0.0409 (7)
O3	0.8043 (3)	0.1395 (2)	0.12360 (13)	0.0413 (7)
O4	0.6920 (3)	0.0630 (2)	0.23593 (11)	0.0261 (5)
O5	0.2264 (3)	0.5841 (2)	0.27020 (11)	0.0337 (6)
O6	0.3212 (3)	0.4449 (2)	0.35242 (12)	0.0348 (6)
O7	0.2270 (3)	0.6206 (2)	0.39735 (11)	0.0320 (6)
S1	0.82436 (10)	0.50206 (7)	0.16166 (4)	0.02375 (18)
S2	0.09600 (9)	−0.16694 (7)	0.32694 (4)	0.02022 (17)
S3	0.81271 (9)	0.06319 (7)	0.18366 (4)	0.01879 (16)
S4	0.29722 (10)	0.56968 (7)	0.33972 (4)	0.02205 (17)

	U11	U22	U33	U12	U13	U23
C1	0.0168 (14)	0.0142 (14)	0.0171 (14)	0.0016 (11)	0.0018 (11)	0.0011 (11)
C2	0.0179 (15)	0.0169 (14)	0.0171 (14)	0.0061 (12)	−0.0003 (11)	0.0011 (11)
C3	0.0207 (15)	0.0187 (15)	0.0212 (15)	0.0002 (12)	−0.0043 (12)	−0.0002 (12)
C4	0.0261 (17)	0.0230 (16)	0.0214 (16)	0.0041 (13)	−0.0088 (13)	−0.0055 (13)
C5	0.0234 (16)	0.0270 (16)	0.0164 (14)	0.0061 (13)	−0.0014 (12)	−0.0029 (12)
C6	0.0224 (16)	0.0238 (16)	0.0165 (14)	0.0048 (13)	0.0015 (12)	−0.0017 (12)
C7	0.0184 (15)	0.0182 (14)	0.0157 (14)	0.0044 (12)	−0.0003 (11)	−0.0016 (11)
C8	0.0232 (16)	0.0176 (14)	0.0168 (14)	0.0077 (12)	0.0061 (12)	0.0047 (11)
C9	0.0223 (16)	0.0213 (15)	0.0242 (16)	0.0052 (13)	0.0001 (13)	−0.0029 (12)
C10	0.0335 (19)	0.0321 (18)	0.0189 (15)	0.0133 (15)	−0.0022 (13)	−0.0009 (13)
C11	0.040 (2)	0.0361 (19)	0.0143 (15)	0.0137 (16)	0.0014 (14)	0.0096 (13)
C12	0.041 (2)	0.0284 (18)	0.0277 (18)	−0.0062 (16)	0.0045 (15)	0.0128 (15)
C13	0.0165 (14)	0.0157 (14)	0.0198 (15)	0.0033 (12)	0.0051 (12)	0.0044 (11)
C14	0.0137 (14)	0.0175 (14)	0.0190 (14)	0.0039 (11)	0.0025 (11)	−0.0010 (11)
C15	0.0187 (15)	0.0179 (15)	0.0243 (16)	0.0007 (12)	0.0020 (12)	−0.0002 (12)
C16	0.0199 (15)	0.0189 (15)	0.0230 (15)	0.0002 (12)	−0.0032 (12)	−0.0069 (12)
C17	0.0243 (16)	0.0276 (17)	0.0180 (15)	0.0037 (13)	−0.0024 (12)	−0.0014 (13)
C18	0.0228 (16)	0.0224 (16)	0.0187 (15)	0.0012 (13)	−0.0012 (12)	0.0034 (12)
C19	0.0218 (15)	0.0170 (14)	0.0192 (15)	0.0060 (12)	0.0035 (12)	0.0019 (11)
C20	0.0263 (16)	0.0243 (16)	0.0176 (15)	0.0142 (13)	0.0090 (12)	0.0075 (12)
C21	0.0258 (17)	0.0215 (16)	0.0285 (17)	0.0049 (13)	0.0047 (14)	0.0044 (13)
C22	0.044 (2)	0.0307 (18)	0.0189 (16)	0.0158 (16)	0.0018 (15)	−0.0017 (13)
C23	0.046 (2)	0.0355 (19)	0.0222 (17)	0.0198 (17)	0.0181 (15)	0.0139 (15)
C24	0.0293 (18)	0.0267 (17)	0.0341 (19)	0.0086 (15)	0.0164 (15)	0.0119 (14)
C25	0.0199 (17)	0.0327 (19)	0.045 (2)	0.0097 (14)	−0.0067 (15)	−0.0156 (16)
C26	0.030 (2)	0.030 (2)	0.065 (3)	0.0115 (16)	0.0039 (19)	0.0100 (18)
Cu1	0.01451 (18)	0.01443 (18)	0.01021 (17)	−0.00137 (13)	0.00210 (13)	0.00019 (13)
F1	0.0661 (16)	0.0668 (16)	0.0353 (12)	0.0430 (13)	−0.0024 (11)	−0.0231 (11)
F2	0.0279 (13)	0.0601 (17)	0.146 (3)	0.0165 (12)	−0.0325 (15)	−0.0682 (18)
F3	0.0520 (14)	0.0250 (11)	0.0757 (17)	0.0113 (10)	0.0231 (12)	0.0097 (11)
F4	0.0368 (14)	0.0513 (15)	0.097 (2)	0.0078 (12)	−0.0289 (14)	−0.0069 (14)
F5	0.0514 (16)	0.0765 (19)	0.096 (2)	0.0380 (14)	0.0465 (15)	0.0410 (16)
F6	0.0356 (13)	0.0272 (12)	0.128 (3)	0.0030 (10)	0.0041 (14)	0.0199 (14)
N1	0.0175 (12)	0.0163 (12)	0.0154 (12)	0.0039 (10)	0.0006 (10)	−0.0015 (9)
N2	0.0166 (12)	0.0171 (12)	0.0158 (12)	0.0033 (10)	0.0008 (10)	0.0013 (10)
N3	0.0162 (12)	0.0186 (12)	0.0154 (12)	0.0036 (10)	0.0035 (10)	0.0036 (10)
N4	0.0368 (17)	0.0254 (15)	0.0197 (14)	−0.0056 (12)	−0.0015 (12)	0.0033 (11)
N5	0.0138 (12)	0.0168 (12)	0.0204 (13)	0.0022 (10)	0.0020 (10)	0.0003 (10)
N6	0.0182 (13)	0.0205 (13)	0.0149 (12)	0.0034 (10)	0.0041 (10)	0.0016 (10)
N7	0.0195 (13)	0.0208 (13)	0.0144 (12)	0.0051 (10)	0.0056 (10)	0.0033 (10)
N8	0.0257 (14)	0.0264 (14)	0.0241 (14)	0.0078 (12)	0.0076 (11)	0.0039 (11)
O1	0.0169 (11)	0.0192 (11)	0.0298 (12)	0.0019 (9)	0.0015 (9)	−0.0042 (9)
O2	0.0171 (12)	0.0361 (14)	0.0670 (18)	0.0071 (11)	−0.0103 (12)	−0.0199 (13)
O3	0.0530 (17)	0.0461 (16)	0.0358 (14)	0.0286 (13)	0.0241 (12)	0.0165 (12)
O4	0.0288 (12)	0.0361 (13)	0.0177 (11)	0.0163 (10)	0.0043 (9)	0.0006 (9)
O5	0.0500 (16)	0.0384 (14)	0.0158 (11)	0.0187 (12)	−0.0012 (10)	−0.0026 (10)
O6	0.0509 (16)	0.0250 (12)	0.0297 (13)	0.0135 (11)	−0.0041 (11)	0.0005 (10)
O7	0.0366 (14)	0.0455 (15)	0.0162 (11)	0.0165 (12)	0.0027 (10)	−0.0048 (10)
S1	0.0251 (4)	0.0207 (4)	0.0170 (4)	−0.0060 (3)	0.0001 (3)	0.0026 (3)
S2	0.0211 (4)	0.0172 (4)	0.0192 (4)	0.0004 (3)	0.0049 (3)	0.0025 (3)
S3	0.0135 (3)	0.0188 (4)	0.0229 (4)	0.0035 (3)	0.0007 (3)	−0.0032 (3)
S4	0.0304 (4)	0.0206 (4)	0.0154 (4)	0.0085 (3)	−0.0008 (3)	−0.0021 (3)

C1—N2	1.317 (4)	C18—H18	0.9500
C1—C2	1.465 (4)	C19—N7	1.300 (4)
C1—S1	1.711 (3)	C19—C20	1.469 (4)
C2—N1	1.352 (4)	C19—S2	1.728 (3)
C2—C3	1.386 (4)	C20—N8	1.348 (4)
C3—C4	1.386 (4)	C20—C21	1.386 (4)
C3—H3	0.9500	C21—C22	1.380 (4)
C4—C5	1.374 (4)	C21—H21	0.9500
C4—H4	0.9500	C22—C23	1.379 (5)
C5—C6	1.393 (4)	C22—H22	0.9500
C5—H5	0.9500	C23—C24	1.384 (5)
C6—N1	1.335 (4)	C23—H23	0.9500
C6—H6	0.9500	C24—N8	1.328 (4)
C7—N3	1.296 (4)	C24—H24	0.9500
C7—C8	1.481 (4)	C25—F1	1.319 (4)
C7—S1	1.743 (3)	C25—F2	1.346 (4)
C8—N4	1.352 (4)	C25—F3	1.350 (4)
C8—C9	1.376 (4)	C25—S3	1.832 (3)
C9—C10	1.378 (4)	C26—F5	1.333 (5)
C9—H9	0.9500	C26—F4	1.349 (5)
C10—C11	1.377 (5)	C26—F6	1.367 (4)
C10—H10	0.9500	C26—S4	1.818 (4)
C11—C12	1.380 (5)	Cu1—N1	2.030 (2)
C11—H11	0.9500	Cu1—N2	2.032 (2)
C12—N4	1.352 (4)	Cu1—N5	2.040 (2)
C12—H12	0.9500	Cu1—N6	2.041 (2)
C13—N6	1.315 (4)	Cu1—O1	2.259 (2)
C13—C14	1.450 (4)	N2—N3	1.364 (3)
C13—S2	1.698 (3)	N6—N7	1.363 (3)
C14—N5	1.357 (4)	O1—H1W	0.7805
C14—C15	1.382 (4)	O1—H2W	0.8032
C15—C16	1.385 (4)	O2—S3	1.474 (2)
C15—H15	0.9500	O3—S3	1.452 (3)
C16—C17	1.384 (4)	O4—S3	1.429 (2)
C16—H16	0.9500	O5—S4	1.466 (2)
C17—C18	1.390 (4)	O6—S4	1.487 (2)
C17—H17	0.9500	O7—S4	1.424 (2)
C18—N5	1.334 (4)
N2—C1—C2	119.3 (3)	C23—C22—H22	121.0
N2—C1—S1	113.2 (2)	C21—C22—H22	121.0
C2—C1—S1	127.4 (2)	C22—C23—C24	119.7 (3)
N1—C2—C3	123.8 (3)	C22—C23—H23	120.1
N1—C2—C1	112.3 (2)	C24—C23—H23	120.1
C3—C2—C1	123.9 (3)	N8—C24—C23	123.7 (3)
C2—C3—C4	118.5 (3)	N8—C24—H24	118.2
C2—C3—H3	120.8	C23—C24—H24	118.2
C4—C3—H3	120.8	F1—C25—F2	106.9 (3)
C5—C4—C3	118.4 (3)	F1—C25—F3	105.8 (3)
C5—C4—H4	120.8	F2—C25—F3	109.4 (3)
C3—C4—H4	120.8	F1—C25—S3	111.3 (3)
C4—C5—C6	119.7 (3)	F2—C25—S3	109.5 (2)
C4—C5—H5	120.1	F3—C25—S3	113.6 (2)
C6—C5—H5	120.1	F5—C26—F4	107.1 (3)
N1—C6—C5	122.9 (3)	F5—C26—F6	108.1 (3)
N1—C6—H6	118.6	F4—C26—F6	109.7 (3)
C5—C6—H6	118.6	F5—C26—S4	109.7 (3)
N3—C7—C8	124.4 (3)	F4—C26—S4	112.2 (3)
N3—C7—S1	114.4 (2)	F6—C26—S4	109.8 (2)
C8—C7—S1	121.2 (2)	N1—Cu1—N2	80.50 (10)
N4—C8—C9	124.2 (3)	N1—Cu1—N5	172.75 (10)
N4—C8—C7	113.7 (3)	N2—Cu1—N5	99.89 (10)
C9—C8—C7	122.1 (3)	N1—Cu1—N6	99.32 (10)
C8—C9—C10	118.9 (3)	N2—Cu1—N6	178.16 (10)
C8—C9—H9	120.6	N5—Cu1—N6	80.05 (10)
C10—C9—H9	120.6	N1—Cu1—O1	94.74 (9)
C11—C10—C9	118.6 (3)	N2—Cu1—O1	88.18 (9)
C11—C10—H10	120.7	N5—Cu1—O1	92.51 (9)
C9—C10—H10	120.7	N6—Cu1—O1	93.66 (9)
C10—C11—C12	119.0 (3)	C6—N1—C2	116.7 (2)
C10—C11—H11	120.5	C6—N1—Cu1	128.3 (2)
C12—C11—H11	120.5	C2—N1—Cu1	115.00 (18)
N4—C12—C11	123.9 (3)	C1—N2—N3	114.0 (2)
N4—C12—H12	118.0	C1—N2—Cu1	112.38 (19)
C11—C12—H12	118.0	N3—N2—Cu1	133.64 (18)
N6—C13—C14	118.8 (2)	C7—N3—N2	111.5 (2)
N6—C13—S2	114.3 (2)	C8—N4—C12	115.3 (3)
C14—C13—S2	126.9 (2)	C18—N5—C14	117.4 (2)
N5—C14—C15	123.6 (3)	C18—N5—Cu1	127.9 (2)
N5—C14—C13	112.7 (2)	C14—N5—Cu1	114.52 (19)
C15—C14—C13	123.6 (3)	C13—N6—N7	113.2 (2)
C14—C15—C16	118.2 (3)	C13—N6—Cu1	112.52 (19)
C14—C15—H15	120.9	N7—N6—Cu1	132.57 (19)
C16—C15—H15	120.9	C19—N7—N6	110.9 (2)
C17—C16—C15	118.8 (3)	C24—N8—C20	115.7 (3)
C17—C16—H16	120.6	Cu1—O1—H1W	116.9
C15—C16—H16	120.6	Cu1—O1—H2W	113.1
C16—C17—C18	119.6 (3)	H1W—O1—H2W	112.6
C16—C17—H17	120.2	C1—S1—C7	86.88 (14)
C18—C17—H17	120.2	C13—S2—C19	86.41 (14)
N5—C18—C17	122.3 (3)	O4—S3—O3	113.60 (14)
N5—C18—H18	118.8	O4—S3—O2	113.34 (15)
C17—C18—H18	118.8	O3—S3—O2	118.12 (17)
N7—C19—C20	124.1 (3)	O4—S3—C25	103.53 (15)
N7—C19—S2	115.2 (2)	O3—S3—C25	105.14 (17)
C20—C19—S2	120.7 (2)	O2—S3—C25	100.60 (15)
N8—C20—C21	124.8 (3)	O7—S4—O5	113.30 (14)
N8—C20—C19	113.1 (3)	O7—S4—O6	114.47 (15)
C21—C20—C19	122.1 (3)	O5—S4—O6	116.62 (14)
C22—C21—C20	118.0 (3)	O7—S4—C26	103.02 (17)
C22—C21—H21	121.0	O5—S4—C26	104.58 (18)
C20—C21—H21	121.0	O6—S4—C26	102.59 (16)
C23—C22—C21	118.1 (3)
N2—C1—C2—N1	−0.2 (4)	C1—N2—N3—C7	0.4 (3)
S1—C1—C2—N1	175.6 (2)	Cu1—N2—N3—C7	−178.3 (2)
N2—C1—C2—C3	−177.1 (3)	C9—C8—N4—C12	−0.1 (5)
S1—C1—C2—C3	−1.2 (4)	C7—C8—N4—C12	179.3 (3)
N1—C2—C3—C4	−1.7 (5)	C11—C12—N4—C8	−0.6 (6)
C1—C2—C3—C4	174.8 (3)	C17—C18—N5—C14	−0.3 (4)
C2—C3—C4—C5	−0.3 (5)	C17—C18—N5—Cu1	174.3 (2)
C3—C4—C5—C6	1.7 (5)	C15—C14—N5—C18	2.4 (4)
C4—C5—C6—N1	−1.2 (5)	C13—C14—N5—C18	−177.2 (3)
N3—C7—C8—N4	177.9 (3)	C15—C14—N5—Cu1	−172.9 (2)
S1—C7—C8—N4	−1.8 (4)	C13—C14—N5—Cu1	7.5 (3)
N3—C7—C8—C9	−2.6 (5)	N2—Cu1—N5—C18	2.3 (3)
S1—C7—C8—C9	177.6 (2)	N6—Cu1—N5—C18	−175.8 (3)
N4—C8—C9—C10	0.7 (5)	O1—Cu1—N5—C18	90.9 (3)
C7—C8—C9—C10	−178.7 (3)	N2—Cu1—N5—C14	177.03 (19)
C8—C9—C10—C11	−0.6 (5)	N6—Cu1—N5—C14	−1.1 (2)
C9—C10—C11—C12	0.0 (5)	O1—Cu1—N5—C14	−94.4 (2)
C10—C11—C12—N4	0.6 (6)	C14—C13—N6—N7	179.7 (2)
N6—C13—C14—N5	−13.6 (4)	S2—C13—N6—N7	1.2 (3)
S2—C13—C14—N5	164.6 (2)	C14—C13—N6—Cu1	12.6 (3)
N6—C13—C14—C15	166.7 (3)	S2—C13—N6—Cu1	−165.88 (14)
S2—C13—C14—C15	−15.0 (4)	N1—Cu1—N6—C13	−178.8 (2)
N5—C14—C15—C16	−2.7 (5)	N5—Cu1—N6—C13	−6.2 (2)
C13—C14—C15—C16	176.9 (3)	O1—Cu1—N6—C13	85.7 (2)
C14—C15—C16—C17	0.7 (4)	N1—Cu1—N6—N7	17.3 (3)
C15—C16—C17—C18	1.3 (5)	N5—Cu1—N6—N7	−170.0 (3)
C16—C17—C18—N5	−1.5 (5)	O1—Cu1—N6—N7	−78.1 (3)
N7—C19—C20—N8	175.3 (3)	C20—C19—N7—N6	−179.8 (3)
S2—C19—C20—N8	−3.7 (4)	S2—C19—N7—N6	−0.7 (3)
N7—C19—C20—C21	−4.8 (5)	C13—N6—N7—C19	−0.4 (3)
S2—C19—C20—C21	176.1 (2)	Cu1—N6—N7—C19	163.4 (2)
N8—C20—C21—C22	−0.6 (5)	C23—C24—N8—C20	−1.2 (5)
C19—C20—C21—C22	179.5 (3)	C21—C20—N8—C24	1.1 (5)
C20—C21—C22—C23	0.2 (5)	C19—C20—N8—C24	−179.0 (3)
C21—C22—C23—C24	−0.3 (5)	N2—C1—S1—C7	0.4 (2)
C22—C23—C24—N8	0.9 (5)	C2—C1—S1—C7	−175.7 (3)
C5—C6—N1—C2	−0.8 (4)	N3—C7—S1—C1	−0.1 (2)
C5—C6—N1—Cu1	179.1 (2)	C8—C7—S1—C1	179.6 (3)
C3—C2—N1—C6	2.3 (4)	N6—C13—S2—C19	−1.3 (2)
C1—C2—N1—C6	−174.6 (3)	C14—C13—S2—C19	−179.6 (3)
C3—C2—N1—Cu1	−177.6 (2)	N7—C19—S2—C13	1.1 (2)
C1—C2—N1—Cu1	5.5 (3)	C20—C19—S2—C13	−179.8 (3)
N2—Cu1—N1—C6	173.7 (3)	F1—C25—S3—O4	170.5 (2)
N6—Cu1—N1—C6	−8.2 (3)	F2—C25—S3—O4	52.5 (3)
O1—Cu1—N1—C6	86.3 (3)	F3—C25—S3—O4	−70.1 (3)
N2—Cu1—N1—C2	−6.5 (2)	F1—C25—S3—O3	51.1 (3)
N6—Cu1—N1—C2	171.7 (2)	F2—C25—S3—O3	−66.9 (3)
O1—Cu1—N1—C2	−93.8 (2)	F3—C25—S3—O3	170.4 (2)
C2—C1—N2—N3	175.9 (2)	F1—C25—S3—O2	−72.1 (3)
S1—C1—N2—N3	−0.5 (3)	F2—C25—S3—O2	169.9 (3)
C2—C1—N2—Cu1	−5.1 (3)	F3—C25—S3—O2	47.2 (3)
S1—C1—N2—Cu1	178.51 (13)	F5—C26—S4—O7	179.2 (3)
N1—Cu1—N2—C1	6.1 (2)	F4—C26—S4—O7	60.3 (3)
N5—Cu1—N2—C1	−166.6 (2)	F6—C26—S4—O7	−62.1 (3)
O1—Cu1—N2—C1	101.2 (2)	F5—C26—S4—O5	−62.1 (3)
N1—Cu1—N2—N3	−175.2 (3)	F4—C26—S4—O5	178.9 (3)
N5—Cu1—N2—N3	12.2 (3)	F6—C26—S4—O5	56.5 (3)
O1—Cu1—N2—N3	−80.0 (3)	F5—C26—S4—O6	60.0 (3)
C8—C7—N3—N2	−179.9 (3)	F4—C26—S4—O6	−58.9 (3)
S1—C7—N3—N2	−0.1 (3)	F6—C26—S4—O6	178.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O6	0.78	1.95	2.721 (3)	169
O1—H2W···O2i	0.80	1.94	2.732 (3)	167
C6—H6···N7	0.95	2.33	3.146 (4)	143
C18—H18···N3	0.95	2.36	3.174 (4)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯O6	0.78	1.95	2.721 (3)	169
O1—H2W⋯O2i	0.80	1.94	2.732 (3)	167
C6—H6⋯N7	0.95	2.33	3.146 (4)	143
C18—H18⋯N3	0.95	2.36	3.174 (4)	143

Symmetry code: (i) .