catena-Poly[[[bis­[2,2′-(propane-1,3-diyl­dithio)bis­(1,3,4-thia­diazole)-κN4]copper(II)]-bis­[μ-2,2′-(propane-1,3-diyldithio)bis­(1,3,4-thia­diazole)-κ2N4:N4′]] bis­(perchlorate)]

Qin, J.-H.; Wang, J.-G.; Hu, P.-Z.

doi:10.1107/S1600536809006722

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages m349-m350

doi:10.1107/S1600536809006722

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catena-Poly[[[bis[2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole)-κN⁴]copper(II)]-bis[μ-2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole)-κ²N⁴:N^4′]] bis(perchlorate)]

Jian-Hua Qin,^a ^* Jian-Ge Wang ^a and Pu-Zhou Hu ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: jh_q128105@126.com

(Received 15 February 2009; accepted 24 February 2009; online 28 February 2009)

In the title compound, {[Cu(C₇H₈N₄S₄)₄](ClO₄)₂}_n, the Cu^II atom, occupying a crystallographic inversion centre, is six-coordinated by six N atoms of three symmetry-related 2,2′-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole) (L) ligands in a slightly distorted octahedral geometry. The ligand L adopts two kinds of coordination modes in the crystal structure; one is a monodentate coordination mode and serves to complete the octahedral coordination of the Cu atom and the other is an N:N′-bidentate bridging mode in a trans configuration, bridging Cu atoms via translation symmetry along the b axis into a chain structure. The perchlorate ions serve as acceptors for intermolecular C—H⋯O hydrogen bonds, which link the chains into a three-dimensional network.

Related literature

For Cu—N bonds see, for example: Huang et al. (2009 ); Wang et al. (2008 ).

Experimental

Crystal data

[Cu(C₇H₈N₄S₄)₄](ClO₄)₂
M_r = 1368.10
Triclinic, $[P \overline 1]$
a = 10.321 (3) Å
b = 11.122 (3) Å
c = 12.908 (4) Å
α = 67.213 (3)°
β = 76.602 (3)°
γ = 76.675 (3)°
V = 1312.3 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 294 K
0.39 × 0.28 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.646, T_max = 0.756
9833 measured reflections
4857 independent reflections
4081 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.03
4857 reflections
322 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.021 (2)
Cu1—N5	2.053 (2)
Cu1—N4ⁱ	2.445 (3)
Symmetry code: (i) x, y-1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O3ⁱⁱ	0.97	2.47	3.357 (6)	153
C7—H7⋯O3ⁱⁱⁱ	0.93	2.51	3.172 (6)	128
C8—H8⋯O4ⁱ	0.93	2.47	3.010 (6)	117
C10—H10A⋯O2^iv	0.97	2.50	3.423 (7)	159
C14—H14⋯O1^v	0.93	2.51	3.419 (7)	167
Symmetry codes: (i) x, y-1, z; (ii) x-1, y, z; (iii) x-1, y+1, z; (iv) -x+1, -y, -z+2; (v) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006722/si2158sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006722/si2158Isup2.hkl

checkCIF report

Comment top

The asymmetric structure unit of the title compound consists of a half Cu(II) atom, two [1,3-propanediylbis(thio)]bis[1,3,4-thiadiazole] ligands L, and one perchlorate ion. As depicted in Fig. 1,the Cu(II) atom is coordinated by six N atoms from six ligands L in a slightly distorted octahedral geometry of the central atom. All six Cu—N bond distances are within the range expected for such coordination bonds (Tab. 1) (Huang et al., 2009; Wang et al., 2008). The ligand L adopts two kinds of coordination modes in the crystal structure. One N,N-bidentate bridging mode in trans configuration for bridging the copper atom into a one-dimensional chain, with the bridged Cu-Cu distance of 11.122 (3) Å (Fig. 2). The centroid separation and dihedral angle of thiadiazole rings are 9.131 (2) Å and 74.09 (8) °, respectively. The other thiadiazole ligands adopt monodentate coordination mode and serve to complete the octahedral coordination sphere of the copper atom. The corresponding centroid separation and dihedral angle are 8.1499 (16) Å and 65.04 (12) °, respectively. The region between the chains is taken up by uncoordinated perchlorate ions. The perchlorate ions serve as acceptor for C—H···O hydrogen-bonds, which link the chains into a three-dimensional network (Tab. 2. & Fig. 3).

Related literature top

For Cu—N bonds see, for example: Huang et al. (2009); Wang et al. (2008). [Please revise scheme to show the correct proportions within square brackets, i.e. 4 thiadiazole ligands per Cu atom]

Experimental top

The reaction of [1,3-propanediylbis(thio)]bis[1,3,4-thiadiazole] (0.4 mmol) with Cu(ClO₄)₂ (0.1 mmol) in MeOH(10 ml) for a few minutes afforded a light blue solid, which was filtered, washed with acetone, and dried on air. The single crystals suitable for X-ray analysis were obtained by slow diffusion of Et₂O into the acetonitrile solution of the solid.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the local coordination of the Cu(II) cation in the title compound. Displacement ellipsoids are drawn at the 30% probability level. The H atoms and perchlorate ion were omitted for clarity. Symmetry codes: (A) -x + 1, -y, -z + 1; (B) x, y - 1, z; (C) -x + 1, -y + 1, -z + 1.
	Fig. 2. A view of the polymeric chain in the title compound.
	Fig. 3. A view of the compound packing down the b axis.

catena-Poly[[[bis[2,2'-(propane-1,3-diyldithio)bis(1,3,4-thiadiazole)- κN⁴]copper(II)]-bis[µ-2,2'-(propane-1,3-diyldithio)bis(1,3,4- thiadiazole)-κ²N⁴:N^4']] bis(perchlorate)] top

Crystal data top

[Cu(C₇H₈N₄S₄)₄](ClO₄)₂	Z = 1
M_r = 1368.10	F(000) = 695
Triclinic, P1	D_x = 1.731 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.321 (3) Å	Cell parameters from 4352 reflections
b = 11.122 (3) Å	θ = 2.5–28.1°
c = 12.908 (4) Å	µ = 1.22 mm⁻¹
α = 67.213 (3)°	T = 294 K
β = 76.602 (3)°	Block, blue
γ = 76.675 (3)°	0.39 × 0.28 × 0.24 mm
V = 1312.3 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4857 independent reflections
Radiation source: fine-focus sealed tube	4081 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→12
T_min = 0.646, T_max = 0.756	k = −13→13
9833 measured reflections	l = −15→15

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0533P)² + 1.507P] where P = (F_o² + 2F_c²)/3
4857 reflections	(Δ/σ)_max < 0.001
322 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Cu(C₇H₈N₄S₄)₄](ClO₄)₂	γ = 76.675 (3)°
M_r = 1368.10	V = 1312.3 (6) Å³
Triclinic, P1	Z = 1
a = 10.321 (3) Å	Mo Kα radiation
b = 11.122 (3) Å	µ = 1.22 mm⁻¹
c = 12.908 (4) Å	T = 294 K
α = 67.213 (3)°	0.39 × 0.28 × 0.24 mm
β = 76.602 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4857 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	4081 reflections with I > 2σ(I)
T_min = 0.646, T_max = 0.756	R_int = 0.017
9833 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	Δρ_max = 1.05 e Å⁻³
4857 reflections	Δρ_min = −0.50 e Å⁻³
322 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.0000	0.5000	0.02910 (14)
Cl1	0.89564 (9)	0.39343 (8)	0.71273 (7)	0.0469 (2)
S1	0.60750 (10)	0.13642 (9)	0.74944 (8)	0.0494 (2)
S2	0.42947 (13)	0.39702 (10)	0.69426 (11)	0.0728 (4)
S3	−0.00185 (9)	0.78315 (9)	0.62689 (9)	0.0516 (2)
S4	0.02700 (10)	1.01392 (10)	0.68458 (9)	0.0569 (3)
S5	0.58105 (10)	−0.40131 (8)	0.77434 (7)	0.0458 (2)
S6	0.33608 (12)	−0.34525 (10)	0.94441 (8)	0.0615 (3)
S7	0.15521 (18)	0.11517 (12)	0.90859 (13)	0.0951 (5)
S8	0.11321 (15)	0.35074 (11)	0.97930 (11)	0.0777 (4)
O1	0.8989 (5)	0.4074 (5)	0.8153 (4)	0.1235 (17)
O2	0.8069 (6)	0.3095 (6)	0.7325 (4)	0.156 (2)
O3	1.0235 (4)	0.3459 (4)	0.6637 (4)	0.1009 (12)
O4	0.8505 (4)	0.5164 (4)	0.6350 (4)	0.1255 (17)
N1	0.5187 (2)	0.0858 (2)	0.6070 (2)	0.0307 (5)
N2	0.4504 (3)	0.2109 (2)	0.6008 (2)	0.0347 (6)
N3	0.2075 (2)	0.9204 (2)	0.5508 (2)	0.0371 (6)
N4	0.2550 (3)	1.0248 (2)	0.5561 (2)	0.0376 (6)
N5	0.5102 (3)	−0.1771 (2)	0.6333 (2)	0.0336 (5)
N6	0.4134 (3)	−0.1871 (2)	0.7283 (2)	0.0399 (6)
N7	0.2510 (4)	0.1319 (3)	1.0804 (3)	0.0609 (9)
N8	0.2522 (4)	0.2173 (4)	1.1350 (3)	0.0696 (10)
C1	0.6013 (3)	0.0364 (3)	0.6800 (3)	0.0366 (7)
H1	0.6529	−0.0470	0.6933	0.044*
C2	0.4879 (3)	0.2496 (3)	0.6710 (3)	0.0402 (7)
C3	0.3046 (4)	0.4799 (3)	0.6013 (3)	0.0510 (9)
H3A	0.3478	0.5122	0.5226	0.061*
H3B	0.2451	0.4200	0.6088	0.061*
C4	0.2261 (4)	0.5940 (3)	0.6378 (4)	0.0560 (10)
H4A	0.2884	0.6480	0.6366	0.067*
H4B	0.1801	0.5594	0.7154	0.067*
C5	0.1235 (4)	0.6790 (3)	0.5613 (3)	0.0466 (8)
H5A	0.0789	0.6227	0.5442	0.056*
H5B	0.1696	0.7341	0.4901	0.056*
C6	0.0906 (3)	0.9029 (3)	0.6139 (3)	0.0376 (7)
C7	0.1716 (3)	1.0817 (3)	0.6212 (3)	0.0462 (8)
H7	0.1887	1.1538	0.6326	0.055*
C8	0.6026 (3)	−0.2808 (3)	0.6447 (3)	0.0381 (7)
H8	0.6739	−0.2882	0.5873	0.046*
C9	0.4384 (3)	−0.3003 (3)	0.8092 (3)	0.0418 (7)
C10	0.3970 (5)	−0.2527 (4)	1.0086 (3)	0.0651 (11)
H10A	0.3613	−0.2815	1.0893	0.078*
H10B	0.4945	−0.2750	1.0011	0.078*
C11	0.3601 (5)	−0.1024 (4)	0.9580 (3)	0.0645 (11)
H11A	0.4071	−0.0620	0.9898	0.077*
H11B	0.3898	−0.0730	0.8764	0.077*
C12	0.2129 (5)	−0.0586 (4)	0.9817 (4)	0.0760 (13)
H12A	0.1868	−0.0778	1.0630	0.091*
H12B	0.1665	−0.1103	0.9608	0.091*
C13	0.1830 (4)	0.1885 (4)	0.9971 (3)	0.0544 (9)
C14	0.1852 (4)	0.3311 (4)	1.0921 (4)	0.0614 (10)
H14	0.1762	0.3984	1.1203	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0416 (3)	0.0211 (2)	0.0251 (2)	0.00102 (19)	−0.0102 (2)	−0.00926 (19)
Cl1	0.0481 (5)	0.0429 (4)	0.0516 (5)	−0.0084 (4)	−0.0051 (4)	−0.0196 (4)
S1	0.0611 (6)	0.0441 (5)	0.0574 (5)	0.0031 (4)	−0.0342 (4)	−0.0256 (4)
S2	0.0904 (8)	0.0534 (6)	0.1059 (9)	0.0226 (5)	−0.0577 (7)	−0.0569 (6)
S3	0.0360 (4)	0.0434 (5)	0.0709 (6)	−0.0081 (4)	−0.0010 (4)	−0.0186 (4)
S4	0.0479 (5)	0.0579 (6)	0.0659 (6)	−0.0016 (4)	0.0071 (4)	−0.0358 (5)
S5	0.0629 (5)	0.0276 (4)	0.0415 (4)	0.0035 (4)	−0.0184 (4)	−0.0068 (3)
S6	0.0777 (7)	0.0484 (5)	0.0432 (5)	−0.0163 (5)	0.0037 (5)	−0.0036 (4)
S7	0.1475 (13)	0.0572 (7)	0.0988 (10)	0.0182 (8)	−0.0737 (10)	−0.0357 (7)
S8	0.1132 (10)	0.0470 (6)	0.0778 (8)	0.0187 (6)	−0.0536 (7)	−0.0231 (5)
O1	0.136 (4)	0.153 (4)	0.130 (3)	0.027 (3)	−0.063 (3)	−0.107 (3)
O2	0.191 (5)	0.200 (5)	0.137 (4)	−0.153 (5)	0.053 (4)	−0.098 (4)
O3	0.072 (2)	0.086 (2)	0.125 (3)	0.0190 (18)	0.004 (2)	−0.045 (2)
O4	0.104 (3)	0.091 (3)	0.107 (3)	0.038 (2)	−0.002 (2)	0.005 (2)
N1	0.0351 (13)	0.0263 (12)	0.0310 (12)	0.0002 (10)	−0.0080 (10)	−0.0118 (10)
N2	0.0408 (14)	0.0289 (12)	0.0397 (14)	0.0025 (10)	−0.0136 (11)	−0.0183 (11)
N3	0.0336 (13)	0.0342 (13)	0.0441 (15)	−0.0026 (10)	−0.0057 (11)	−0.0162 (11)
N4	0.0381 (14)	0.0330 (13)	0.0433 (15)	−0.0018 (11)	−0.0092 (11)	−0.0155 (12)
N5	0.0445 (14)	0.0261 (12)	0.0295 (13)	−0.0005 (10)	−0.0091 (11)	−0.0103 (10)
N6	0.0473 (15)	0.0330 (13)	0.0338 (14)	−0.0022 (11)	−0.0054 (11)	−0.0085 (11)
N7	0.071 (2)	0.0506 (18)	0.0563 (19)	0.0094 (16)	−0.0230 (17)	−0.0175 (16)
N8	0.086 (3)	0.064 (2)	0.064 (2)	0.0160 (19)	−0.0347 (19)	−0.0300 (18)
C1	0.0423 (17)	0.0323 (15)	0.0371 (16)	0.0015 (13)	−0.0144 (13)	−0.0140 (13)
C2	0.0447 (18)	0.0357 (16)	0.0486 (18)	0.0006 (14)	−0.0164 (14)	−0.0228 (15)
C3	0.053 (2)	0.0424 (19)	0.064 (2)	0.0020 (16)	−0.0183 (18)	−0.0267 (18)
C4	0.066 (2)	0.0387 (19)	0.070 (3)	0.0057 (17)	−0.024 (2)	−0.0267 (18)
C5	0.051 (2)	0.0367 (17)	0.056 (2)	−0.0069 (15)	−0.0110 (16)	−0.0183 (16)
C6	0.0355 (16)	0.0337 (16)	0.0398 (17)	0.0008 (13)	−0.0064 (13)	−0.0123 (13)
C7	0.050 (2)	0.0391 (18)	0.054 (2)	0.0009 (15)	−0.0135 (16)	−0.0217 (16)
C8	0.0463 (18)	0.0332 (16)	0.0357 (16)	0.0015 (13)	−0.0133 (13)	−0.0135 (13)
C9	0.054 (2)	0.0306 (16)	0.0377 (17)	−0.0075 (14)	−0.0097 (14)	−0.0073 (13)
C10	0.078 (3)	0.064 (3)	0.046 (2)	0.000 (2)	−0.0054 (19)	−0.0201 (19)
C11	0.084 (3)	0.064 (3)	0.049 (2)	−0.021 (2)	−0.001 (2)	−0.024 (2)
C12	0.088 (3)	0.052 (2)	0.087 (3)	0.001 (2)	−0.020 (3)	−0.027 (2)
C13	0.065 (2)	0.0404 (19)	0.053 (2)	0.0016 (17)	−0.0184 (18)	−0.0126 (17)
C14	0.071 (3)	0.054 (2)	0.062 (2)	0.004 (2)	−0.020 (2)	−0.025 (2)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	2.021 (2)	N3—N4	1.390 (4)
Cu1—N1	2.021 (2)	N4—C7	1.293 (4)
Cu1—N5ⁱ	2.053 (2)	N4—Cu1^iv	2.445 (3)
Cu1—N5	2.053 (2)	N5—C8	1.299 (4)
Cu1—N4ⁱⁱ	2.445 (3)	N5—N6	1.375 (3)
Cu1—N4ⁱⁱⁱ	2.445 (3)	N6—C9	1.304 (4)
Cl1—O2	1.370 (4)	N7—C13	1.291 (5)
Cl1—O4	1.398 (4)	N7—N8	1.387 (5)
Cl1—O3	1.404 (3)	N8—C14	1.271 (5)
Cl1—O1	1.400 (4)	C1—H1	0.9300
S1—C1	1.696 (3)	C3—C4	1.517 (5)
S1—C2	1.735 (3)	C3—H3A	0.9700
S2—C2	1.727 (3)	C3—H3B	0.9700
S2—C3	1.806 (4)	C4—C5	1.514 (5)
S3—C6	1.746 (3)	C4—H4A	0.9700
S3—C5	1.815 (4)	C4—H4B	0.9700
S4—C7	1.714 (4)	C5—H5A	0.9700
S4—C6	1.735 (3)	C5—H5B	0.9700
S5—C8	1.695 (3)	C7—H7	0.9300
S5—C9	1.719 (3)	C8—H8	0.9300
S6—C9	1.767 (3)	C10—C11	1.530 (6)
S6—C10	1.829 (5)	C10—H10A	0.9700
S7—C13	1.742 (4)	C10—H10B	0.9700
S7—C12	1.816 (5)	C11—C12	1.483 (6)
S8—C14	1.703 (4)	C11—H11A	0.9700
S8—C13	1.727 (4)	C11—H11B	0.9700
N1—C1	1.293 (4)	C12—H12A	0.9700
N1—N2	1.388 (3)	C12—H12B	0.9700
N2—C2	1.302 (4)	C14—H14	0.9300
N3—C6	1.299 (4)

N1ⁱ—Cu1—N1	180.0	C4—C3—H3B	110.5
N1ⁱ—Cu1—N5ⁱ	88.01 (9)	S2—C3—H3B	110.5
N1—Cu1—N5ⁱ	91.99 (9)	H3A—C3—H3B	108.7
N1ⁱ—Cu1—N5	91.99 (9)	C3—C4—C5	112.1 (3)
N1—Cu1—N5	88.01 (9)	C3—C4—H4A	109.2
N5ⁱ—Cu1—N5	180.0	C5—C4—H4A	109.2
N1ⁱ—Cu1—N4ⁱⁱ	91.50 (9)	C3—C4—H4B	109.2
N1—Cu1—N4ⁱⁱ	88.50 (9)	C5—C4—H4B	109.2
N5ⁱ—Cu1—N4ⁱⁱ	87.34 (9)	H4A—C4—H4B	107.9
N5—Cu1—N4ⁱⁱ	92.66 (9)	C4—C5—S3	111.8 (3)
N1ⁱ—Cu1—N4ⁱⁱⁱ	88.50 (9)	C4—C5—H5A	109.3
N1—Cu1—N4ⁱⁱⁱ	91.50 (9)	S3—C5—H5A	109.3
N5ⁱ—Cu1—N4ⁱⁱⁱ	92.66 (9)	C4—C5—H5B	109.3
N5—Cu1—N4ⁱⁱⁱ	87.34 (9)	S3—C5—H5B	109.3
N4ⁱⁱ—Cu1—N4ⁱⁱⁱ	180.0	H5A—C5—H5B	107.9
O2—Cl1—O4	108.6 (4)	N3—C6—S4	114.1 (2)
O2—Cl1—O3	110.1 (3)	N3—C6—S3	125.0 (2)
O4—Cl1—O3	107.8 (2)	S4—C6—S3	120.83 (18)
O2—Cl1—O1	108.9 (3)	N4—C7—S4	114.8 (3)
O4—Cl1—O1	109.3 (3)	N4—C7—H7	122.6
O3—Cl1—O1	112.2 (3)	S4—C7—H7	122.6
C1—S1—C2	86.96 (14)	N5—C8—S5	113.6 (2)
C2—S2—C3	103.64 (16)	N5—C8—H8	123.2
C6—S3—C5	101.32 (16)	S5—C8—H8	123.2
C7—S4—C6	86.73 (16)	N6—C9—S5	114.4 (2)
C8—S5—C9	87.49 (15)	N6—C9—S6	122.9 (3)
C9—S6—C10	99.43 (18)	S5—C9—S6	122.70 (18)
C13—S7—C12	102.4 (2)	C11—C10—S6	115.4 (3)
C14—S8—C13	86.78 (19)	C11—C10—H10A	108.4
C1—N1—N2	113.7 (2)	S6—C10—H10A	108.4
C1—N1—Cu1	124.3 (2)	C11—C10—H10B	108.4
N2—N1—Cu1	121.73 (17)	S6—C10—H10B	108.4
C2—N2—N1	110.3 (2)	H10A—C10—H10B	107.5
C6—N3—N4	111.9 (2)	C12—C11—C10	111.8 (4)
C7—N4—N3	112.5 (3)	C12—C11—H11A	109.2
C7—N4—Cu1^iv	133.3 (2)	C10—C11—H11A	109.2
N3—N4—Cu1^iv	109.59 (17)	C12—C11—H11B	109.2
C8—N5—N6	113.8 (2)	C10—C11—H11B	109.2
C8—N5—Cu1	128.7 (2)	H11A—C11—H11B	107.9
N6—N5—Cu1	117.31 (18)	C11—C12—S7	115.4 (4)
C9—N6—N5	110.7 (3)	C11—C12—H12A	108.4
C13—N7—N8	111.7 (3)	S7—C12—H12A	108.4
C14—N8—N7	112.8 (3)	C11—C12—H12B	108.4
N1—C1—S1	114.4 (2)	S7—C12—H12B	108.4
N1—C1—H1	122.8	H12A—C12—H12B	107.5
S1—C1—H1	122.8	N7—C13—S8	113.8 (3)
N2—C2—S2	127.1 (2)	N7—C13—S7	126.1 (3)
N2—C2—S1	114.6 (2)	S8—C13—S7	120.0 (2)
S2—C2—S1	118.30 (18)	N8—C14—S8	114.9 (3)
C4—C3—S2	106.2 (2)	N8—C14—H14	122.5
C4—C3—H3A	110.5	S8—C14—H14	122.5
S2—C3—H3A	110.5

N5ⁱ—Cu1—N1—C1	−137.6 (3)	S2—C3—C4—C5	175.9 (3)
N5—Cu1—N1—C1	42.4 (3)	C3—C4—C5—S3	163.0 (3)
N4ⁱⁱ—Cu1—N1—C1	−50.3 (3)	C6—S3—C5—C4	74.5 (3)
N4ⁱⁱⁱ—Cu1—N1—C1	129.7 (3)	N4—N3—C6—S4	0.6 (3)
N5ⁱ—Cu1—N1—N2	36.6 (2)	N4—N3—C6—S3	178.9 (2)
N5—Cu1—N1—N2	−143.4 (2)	C7—S4—C6—N3	−0.2 (3)
N4ⁱⁱ—Cu1—N1—N2	123.9 (2)	C7—S4—C6—S3	−178.5 (2)
N4ⁱⁱⁱ—Cu1—N1—N2	−56.1 (2)	C5—S3—C6—N3	12.7 (3)
C1—N1—N2—C2	0.6 (4)	C5—S3—C6—S4	−169.1 (2)
Cu1—N1—N2—C2	−174.2 (2)	N3—N4—C7—S4	0.7 (4)
C6—N3—N4—C7	−0.8 (4)	Cu1^iv—N4—C7—S4	−151.87 (18)
C6—N3—N4—Cu1^iv	158.3 (2)	C6—S4—C7—N4	−0.3 (3)
N1ⁱ—Cu1—N5—C8	65.1 (3)	N6—N5—C8—S5	−0.5 (3)
N1—Cu1—N5—C8	−114.9 (3)	Cu1—N5—C8—S5	173.93 (14)
N4ⁱⁱ—Cu1—N5—C8	−26.5 (3)	C9—S5—C8—N5	0.4 (3)
N4ⁱⁱⁱ—Cu1—N5—C8	153.5 (3)	N5—N6—C9—S5	−0.1 (3)
N1ⁱ—Cu1—N5—N6	−120.6 (2)	N5—N6—C9—S6	178.9 (2)
N1—Cu1—N5—N6	59.4 (2)	C8—S5—C9—N6	−0.1 (3)
N4ⁱⁱ—Cu1—N5—N6	147.8 (2)	C8—S5—C9—S6	−179.1 (2)
N4ⁱⁱⁱ—Cu1—N5—N6	−32.2 (2)	C10—S6—C9—N6	−78.7 (3)
C8—N5—N6—C9	0.4 (4)	C10—S6—C9—S5	100.2 (2)
Cu1—N5—N6—C9	−174.7 (2)	C9—S6—C10—C11	69.0 (3)
C13—N7—N8—C14	0.8 (6)	S6—C10—C11—C12	66.9 (4)
N2—N1—C1—S1	−0.6 (3)	C10—C11—C12—S7	−171.5 (3)
Cu1—N1—C1—S1	174.06 (14)	C13—S7—C12—C11	−83.7 (4)
C2—S1—C1—N1	0.3 (3)	N8—N7—C13—S8	−0.6 (5)
N1—N2—C2—S2	−179.2 (2)	N8—N7—C13—S7	−179.1 (3)
N1—N2—C2—S1	−0.4 (3)	C14—S8—C13—N7	0.2 (4)
C3—S2—C2—N2	1.0 (4)	C14—S8—C13—S7	178.8 (3)
C3—S2—C2—S1	−177.8 (2)	C12—S7—C13—N7	11.3 (5)
C1—S1—C2—N2	0.1 (3)	C12—S7—C13—S8	−167.1 (3)
C1—S1—C2—S2	179.0 (2)	N7—N8—C14—S8	−0.6 (5)
C2—S2—C3—C4	166.7 (3)	C13—S8—C14—N8	0.2 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O3^v	0.97	2.47	3.357 (6)	153
C7—H7···O3^vi	0.93	2.51	3.172 (6)	128
C8—H8···O4ⁱⁱⁱ	0.93	2.47	3.010 (6)	117
C10—H10A···O2^vii	0.97	2.50	3.423 (7)	159
C14—H14···O1^viii	0.93	2.51	3.419 (7)	167

Symmetry codes: (iii) x, y−1, z; (v) x−1, y, z; (vi) x−1, y+1, z; (vii) −x+1, −y, −z+2; (viii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₈N₄S₄)₄](ClO₄)₂
M_r	1368.10
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	10.321 (3), 11.122 (3), 12.908 (4)
α, β, γ (°)	67.213 (3), 76.602 (3), 76.675 (3)
V (Å³)	1312.3 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.22
Crystal size (mm)	0.39 × 0.28 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.646, 0.756
No. of measured, independent and observed [I > 2σ(I)] reflections	9833, 4857, 4081
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.03
No. of reflections	4857
No. of parameters	322
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.50

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	2.021 (2)	Cu1—N4ⁱ	2.445 (3)
Cu1—N5	2.053 (2)

Symmetry code: (i) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O3ⁱⁱ	0.97	2.47	3.357 (6)	153.00
C7—H7···O3ⁱⁱⁱ	0.93	2.51	3.172 (6)	128.00
C8—H8···O4ⁱ	0.93	2.47	3.010 (6)	117.00
C10—H10A···O2^iv	0.97	2.50	3.423 (7)	159.00
C14—H14···O1^v	0.93	2.51	3.419 (7)	167.00

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

Acknowledgements

The authors thank Luoyang Normal University for supporting this work.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Huang, H.-M., Ju, F.-Y., Wang, J.-G. & Qin, J.-H. (2009). Acta Cryst. E65, m80–m81. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J. G., Qin, J. H., Hu, P. Z. & Zhao, B. T. (2008). Z. Kristallogr. New Cryst, Struct. 223, 225–227. Google Scholar

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