Poly[[bis­(acetonitrile-κN)bis­[μ2-2,2′-(methyl­enedithio)bis­(1,3,4-thia­diazole)-κ2N4:N4′]copper(II)] bis­(perchlorate) acetonitrile solvate]

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

doi:10.1107/S1600536809008708

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m415

doi:10.1107/S1600536809008708

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Poly[[bis(acetonitrile-κN)bis[μ₂-2,2′-(methylenedithio)bis(1,3,4-thiadiazole)-κ²N⁴:N^4′]copper(II)] bis(perchlorate) acetonitrile solvate]

Jian-Ge Wang,^a Jian-Hua Qin ^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 2 March 2009; accepted 10 March 2009; online 19 March 2009)

In the title compound, {[Cu(C₅H₄N₄S₄)₂(C₂H₃N)₂](ClO₄)₂·C₂H₃N}_n, the Cu^II atom occupies a crystallographic inversion centre and is six-coordinated by six N atoms of four symmetry-related 2,2′-(methylenedithio)bis(1,3,4-thiadiazole) (L) ligands and two acetonitrile molecules in a slightly distorted octahedral geometry. The ligand L adopts an N:N′-bidentate bridging mode in a trans configuration, bridging the Cu atoms via translation symmetry, forming a two-dimensional layer-like structure. The perchlorate ions serve as acceptors for intermolecular C—H⋯O hydrogen bonds, which link the layers into a three-dimensional network. The ClO₄⁻ anion is disordered with an occupation ratio of 0.658:0.342.

Related literature

For literature on Cu—N bonds, see: Huang et al. (2009 ); Qin et al. (2009 ); Wang et al. (2008 ).

Experimental

Crystal data

[Cu(C₅H₄N₄S₄)₂(C₂H₃N)₂](ClO₄)₂·C₂H₃N
M_r = 1764.65
Monoclinic, C 2/c
a = 19.3144 (18) Å
b = 9.9450 (9) Å
c = 18.8722 (18) Å
β = 98.876 (1)°
V = 3581.6 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 294 K
0.43 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.608, T_max = 0.702
12066 measured reflections
3285 independent reflections
2568 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.181
S = 1.07
3285 reflections
216 parameters
304 restraints
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3ⁱ	0.93	2.35	2.955 (8)	123
C3—H3A⋯O1ⁱⁱ	0.97	2.41	3.277 (9)	149
C5—H5⋯O1ⁱⁱⁱ	0.93	2.45	3.169 (9)	135
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536809008708/su2101sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008708/su2101Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound consists of half a Cu^II atom, two independent 2,2'-(methylenedithio)bis(1,3,4-thiadiazole) (L) ligands, one coordinated acetonitrile molecule, one uncoordinated acetonitrile molecule, and one perchlorate ion (Fig. 1). The Cu^II atom is coordinated by six N atoms, from four L ligands and two acetonitrile molecules, in a slightly distorted octahedral geometry. All six Cu—N bond distances are within the range expected for such coordination bonds (Huang et al., 2009; Wang et al., 2008; Qin et al., 2009). The ligand L adopts a N:N'-bidentate bridging mode in trans configuration, so bridging the copper atoms via translation symmetry to form a two-dimensional layer-like structure, with a bridging Cu···Cu distance of 10.6661 (8) Å (Fig. 2). The centroid-centroid separation and dihedral angle of the thiadiazole rings are 6.3928 (5) Å and 81.86 (13)°, respectively.

In the crystal structure the region between the layes is taken up by perchlorate ions and uncoordinated acetonitrile molecules. The perchlorate ions serve as acceptors for C—H···O hydrogen-bonds, which link the chains into a three-dimensional network (Table 1 and Fig. 3).

Related literature top

For literature on Cu—N bonds, see: Huang et al. (2009); Qin et al. (2009); Wang et al. (2008).

Experimental top

The reaction of 2,2'-(methylenedithio)bis(1,3,4-thiadiazole) (0.2 mmol) with Cu(ClO₄)₂ (0.1 mmol) in an acetonitrile solution (20 ml) afforded a light blue solid after a few minutes. It was filtered off, washed with acetone, and dried in air. Single crystals, suitable for X-ray analysis, were obtained by slow diffusion of Et₂O into an 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 molecular structure of the cation in the title compound. Displacement ellipsoids are drawn at the 30% probability level. The H atoms, perchlorate ion, and uncoordinated acetonitrile molecules were omitted for clarity [symmetry operations: A: 1/2-x, 3/2-y, -z; B: 1/2-x, -1/2+y, 1/2-z; C: x, 2-y, -1/2+z].
	Fig. 2. A view of the two-dimensional network in the title compound.
	Fig. 3. A view down the b axis of the crystal packing of the title compound.

Poly[[bis(acetonitrile-κN)bis[µ₂-2,2'-(methylenedithio)bis(1,3,4- thiadiazole)-κ²N⁴:N^4']copper(II)] bis(perchlorate) acetonitrile solvate] top

Crystal data top

[Cu(C₅H₄N₄S₄)₂(C₂H₃N)₂](ClO₄)₂·C₂H₃N	F(000) = 1780
M_r = 1764.65	D_x = 1.636 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5001 reflections
a = 19.3144 (18) Å	θ = 2.3–28.0°
b = 9.9450 (9) Å	µ = 1.28 mm⁻¹
c = 18.8722 (18) Å	T = 294 K
β = 98.876 (1)°	Block, blue
V = 3581.6 (6) Å³	0.43 × 0.32 × 0.30 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	3285 independent reflections
Radiation source: fine-focus sealed tube	2568 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −23→23
T_min = 0.608, T_max = 0.702	k = −12→12
12066 measured reflections	l = −22→22

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1007P)² + 13.6762P] where P = (F_o² + 2F_c²)/3
3285 reflections	(Δ/σ)_max < 0.001
216 parameters	Δρ_max = 0.86 e Å⁻³
304 restraints	Δρ_min = −0.83 e Å⁻³

Crystal data top

[Cu(C₅H₄N₄S₄)₂(C₂H₃N)₂](ClO₄)₂·C₂H₃N	V = 3581.6 (6) Å³
M_r = 1764.65	Z = 2
Monoclinic, C2/c	Mo Kα radiation
a = 19.3144 (18) Å	µ = 1.28 mm⁻¹
b = 9.9450 (9) Å	T = 294 K
c = 18.8722 (18) Å	0.43 × 0.32 × 0.30 mm
β = 98.876 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3285 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2568 reflections with I > 2σ(I)
T_min = 0.608, T_max = 0.702	R_int = 0.021
12066 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	304 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1007P)² + 13.6762P] where P = (F_o² + 2F_c²)/3
3285 reflections	Δρ_max = 0.86 e Å⁻³
216 parameters	Δρ_min = −0.83 e Å⁻³

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.40159 (11)	0.1887 (3)	0.92446 (12)	0.1040 (7)	0.658 (6)
O1	0.3842 (4)	0.3266 (6)	0.9249 (4)	0.135 (2)	0.658 (6)
O2	0.3626 (4)	0.1399 (7)	0.8620 (4)	0.146 (3)	0.658 (6)
O3	0.4718 (3)	0.1679 (9)	0.9382 (4)	0.139 (2)	0.658 (6)
O4	0.3720 (5)	0.1390 (8)	0.9838 (4)	0.150 (3)	0.658 (6)
Cl1'	0.40159 (11)	0.1887 (3)	0.92446 (12)	0.1040 (7)	0.342 (6)
O1'	0.3333 (3)	0.2118 (9)	0.9325 (5)	0.135 (2)	0.342 (6)
O2'	0.4400 (4)	0.0929 (7)	0.9670 (4)	0.146 (3)	0.342 (6)
O3'	0.4391 (4)	0.3116 (7)	0.9371 (5)	0.139 (2)	0.342 (6)
O4'	0.4083 (5)	0.1678 (8)	0.8518 (3)	0.150 (3)	0.342 (6)
Cu1	0.2500	0.7500	0.0000	0.0403 (3)
S1	0.41916 (9)	0.9410 (2)	0.16187 (11)	0.0858 (6)
S2	0.32021 (8)	1.10571 (14)	0.23555 (7)	0.0551 (4)
S3	0.18788 (8)	0.94899 (14)	0.24653 (6)	0.0542 (4)
S4	0.17640 (9)	0.85456 (14)	0.39769 (7)	0.0584 (4)
N1	0.3156 (2)	0.8589 (4)	0.07448 (19)	0.0424 (9)
N2	0.2872 (2)	0.9444 (4)	0.12019 (19)	0.0421 (9)
N3	0.2193 (2)	1.0883 (4)	0.36936 (19)	0.0445 (9)
N4	0.2208 (2)	1.0822 (4)	0.44266 (19)	0.0425 (9)
N5	0.1534 (3)	0.7792 (6)	0.0641 (3)	0.0662 (13)
C1	0.3821 (3)	0.8491 (7)	0.0899 (3)	0.0651 (16)
H1	0.4084	0.7955	0.0637	0.078*
C2	0.3356 (3)	0.9939 (5)	0.1685 (2)	0.0454 (11)
C3	0.2265 (3)	1.1032 (5)	0.2201 (3)	0.0498 (12)
H3A	0.2105	1.1181	0.1694	0.060*
H3B	0.2095	1.1773	0.2461	0.060*
C4	0.1974 (3)	0.9770 (5)	0.3392 (2)	0.0410 (10)
C5	0.1996 (3)	0.9686 (5)	0.4642 (3)	0.0509 (13)
H5	0.1973	0.9505	0.5121	0.061*
C6	0.1050 (4)	0.7464 (9)	0.0852 (4)	0.088 (2)
C7	0.0400 (6)	0.6925 (15)	0.1112 (7)	0.144 (4)
H7A	−0.0006	0.7375	0.0865	0.216*
H7B	0.0434	0.7083	0.1618	0.216*
H7C	0.0361	0.5977	0.1019	0.216*
N6	1.000 (2)	−0.171 (2)	0.2314 (17)	0.212 (10)	0.50
C8	0.9970 (14)	−0.059 (2)	0.2284 (11)	0.208 (11)	0.50
C9	0.993 (2)	0.093 (2)	0.2242 (18)	0.204 (11)	0.50
H9A	1.0400	0.1296	0.2300	0.306*	0.50
H9B	0.9696	0.1270	0.2617	0.306*	0.50
H9C	0.9682	0.1199	0.1785	0.306*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0787 (12)	0.1298 (17)	0.0987 (14)	0.0298 (12)	−0.0016 (10)	−0.0166 (13)
O1	0.118 (4)	0.147 (4)	0.137 (4)	0.040 (4)	0.012 (4)	−0.018 (4)
O2	0.136 (5)	0.150 (4)	0.141 (4)	0.019 (4)	−0.016 (4)	−0.013 (4)
O3	0.105 (4)	0.156 (4)	0.156 (5)	0.017 (4)	0.018 (4)	−0.001 (4)
O4	0.141 (5)	0.173 (5)	0.138 (4)	0.009 (4)	0.036 (4)	0.000 (4)
Cl1'	0.0787 (12)	0.1298 (17)	0.0987 (14)	0.0298 (12)	−0.0016 (10)	−0.0166 (13)
O1'	0.118 (4)	0.147 (4)	0.137 (4)	0.040 (4)	0.012 (4)	−0.018 (4)
O2'	0.136 (5)	0.150 (4)	0.141 (4)	0.019 (4)	−0.016 (4)	−0.013 (4)
O3'	0.105 (4)	0.156 (4)	0.156 (5)	0.017 (4)	0.018 (4)	−0.001 (4)
O4'	0.141 (5)	0.173 (5)	0.138 (4)	0.009 (4)	0.036 (4)	0.000 (4)
Cu1	0.0650 (6)	0.0348 (4)	0.0214 (4)	0.0057 (3)	0.0075 (3)	−0.0001 (3)
S1	0.0569 (9)	0.1161 (16)	0.0808 (12)	0.0020 (9)	−0.0006 (8)	−0.0383 (11)
S2	0.0796 (9)	0.0467 (7)	0.0378 (7)	−0.0078 (6)	0.0053 (6)	−0.0117 (5)
S3	0.0840 (10)	0.0491 (7)	0.0300 (6)	−0.0130 (6)	0.0106 (6)	−0.0096 (5)
S4	0.0932 (11)	0.0443 (7)	0.0401 (7)	−0.0216 (7)	0.0176 (7)	−0.0046 (5)
N1	0.058 (3)	0.042 (2)	0.0291 (18)	0.0056 (18)	0.0118 (17)	0.0004 (16)
N2	0.058 (2)	0.039 (2)	0.0292 (18)	0.0026 (18)	0.0076 (17)	−0.0023 (15)
N3	0.067 (3)	0.041 (2)	0.0275 (18)	−0.0069 (19)	0.0127 (17)	−0.0023 (16)
N4	0.064 (3)	0.040 (2)	0.0253 (18)	−0.0051 (18)	0.0104 (17)	−0.0005 (15)
N5	0.072 (3)	0.082 (3)	0.049 (3)	0.001 (3)	0.022 (2)	−0.006 (2)
C1	0.061 (4)	0.078 (4)	0.057 (3)	0.007 (3)	0.011 (3)	−0.020 (3)
C2	0.063 (3)	0.040 (2)	0.033 (2)	−0.002 (2)	0.007 (2)	0.0015 (19)
C3	0.085 (4)	0.037 (2)	0.029 (2)	0.006 (2)	0.013 (2)	−0.0002 (19)
C4	0.054 (3)	0.041 (2)	0.029 (2)	−0.003 (2)	0.0103 (19)	−0.0025 (19)
C5	0.078 (4)	0.046 (3)	0.030 (2)	−0.011 (3)	0.013 (2)	−0.004 (2)
C6	0.085 (4)	0.112 (5)	0.066 (4)	−0.001 (4)	0.012 (3)	−0.008 (3)
C7	0.116 (6)	0.184 (8)	0.138 (7)	−0.028 (6)	0.037 (5)	0.012 (7)
N6	0.208 (12)	0.212 (11)	0.217 (14)	−0.002 (10)	0.033 (10)	0.002 (9)
C8	0.202 (12)	0.209 (12)	0.213 (14)	0.002 (9)	0.030 (9)	0.003 (9)
C9	0.197 (14)	0.205 (12)	0.211 (15)	0.003 (10)	0.036 (10)	0.002 (9)

Geometric parameters (Å, º) top

Cl1—O3	1.356 (5)	N1—C1	1.277 (8)
Cl1—O2	1.385 (5)	N1—N2	1.382 (5)
Cl1—O1	1.411 (5)	N2—C2	1.298 (6)
Cl1—O4	1.422 (5)	N3—C4	1.286 (6)
Cl1'—O1'	1.371 (5)	N3—N4	1.380 (5)
Cl1'—O2'	1.385 (5)	N4—C5	1.288 (6)
Cl1'—O4'	1.413 (5)	N4—Cu1^iv	2.021 (4)
Cl1'—O3'	1.422 (5)	N5—C6	1.119 (8)
Cu1—N4ⁱ	2.021 (4)	C1—H1	0.9300
Cu1—N4ⁱⁱ	2.021 (4)	C3—H3A	0.9700
Cu1—N1ⁱⁱⁱ	2.050 (4)	C3—H3B	0.9700
Cu1—N1	2.050 (4)	C5—H5	0.9300
Cu1—N5ⁱⁱⁱ	2.393 (5)	C6—C7	1.515 (11)
Cu1—N5	2.393 (5)	C7—H7A	0.9600
S1—C1	1.700 (6)	C7—H7B	0.9600
S1—C2	1.720 (6)	C7—H7C	0.9600
S2—C2	1.744 (5)	N6—C8	1.114 (6)
S2—C3	1.789 (6)	C8—C9	1.523 (8)
S3—C4	1.752 (4)	C9—H9A	0.9600
S3—C3	1.809 (5)	C9—H9B	0.9600
S4—C5	1.699 (5)	C9—H9C	0.9600
S4—C4	1.734 (5)

O3—Cl1—O2	120.3	N2—N1—Cu1	119.4 (3)
O3—Cl1—O1	112.3	C2—N2—N1	111.1 (4)
O2—Cl1—O1	104.3	C4—N3—N4	111.1 (4)
O3—Cl1—O4	107.9	C5—N4—N3	113.3 (4)
O2—Cl1—O4	108.5	C5—N4—Cu1^iv	129.1 (3)
O1—Cl1—O4	102.0	N3—N4—Cu1^iv	117.5 (3)
O1'—Cl1'—O2'	119.3	C6—N5—Cu1	154.6 (6)
O1'—Cl1'—O4'	111.4	N1—C1—S1	115.2 (4)
O2'—Cl1'—O4'	109.9	N1—C1—H1	122.4
O1'—Cl1'—O3'	108.2	S1—C1—H1	122.4
O2'—Cl1'—O3'	106.3	N2—C2—S1	114.5 (4)
O4'—Cl1'—O3'	99.7	N2—C2—S2	124.6 (4)
N4ⁱ—Cu1—N4ⁱⁱ	180.0	S1—C2—S2	121.0 (3)
N4ⁱ—Cu1—N1ⁱⁱⁱ	91.30 (15)	S2—C3—S3	114.6 (3)
N4ⁱⁱ—Cu1—N1ⁱⁱⁱ	88.70 (15)	S2—C3—H3A	108.6
N4ⁱ—Cu1—N1	88.70 (15)	S3—C3—H3A	108.6
N4ⁱⁱ—Cu1—N1	91.30 (15)	S2—C3—H3B	108.6
N1ⁱⁱⁱ—Cu1—N1	180.0	S3—C3—H3B	108.6
N4ⁱ—Cu1—N5ⁱⁱⁱ	89.75 (18)	H3A—C3—H3B	107.6
N4ⁱⁱ—Cu1—N5ⁱⁱⁱ	90.25 (18)	N3—C4—S4	114.6 (3)
N1ⁱⁱⁱ—Cu1—N5ⁱⁱⁱ	92.10 (17)	N3—C4—S3	123.8 (3)
N1—Cu1—N5ⁱⁱⁱ	87.90 (17)	S4—C4—S3	121.7 (3)
N4ⁱ—Cu1—N5	90.25 (18)	N4—C5—S4	114.4 (4)
N4ⁱⁱ—Cu1—N5	89.75 (18)	N4—C5—H5	122.8
N1ⁱⁱⁱ—Cu1—N5	87.90 (17)	S4—C5—H5	122.8
N1—Cu1—N5	92.10 (17)	N5—C6—C7	176.0 (10)
N5ⁱⁱⁱ—Cu1—N5	180.0	C6—C7—H7A	109.5
C1—S1—C2	86.5 (3)	C6—C7—H7B	109.5
C2—S2—C3	98.9 (2)	H7A—C7—H7B	109.5
C4—S3—C3	99.0 (2)	C6—C7—H7C	109.5
C5—S4—C4	86.6 (2)	H7A—C7—H7C	109.5
C1—N1—N2	112.7 (4)	H7B—C7—H7C	109.5
C1—N1—Cu1	127.6 (4)	N6—C8—C9	180.0

N4ⁱ—Cu1—N1—C1	63.0 (5)	C2—S1—C1—N1	−0.1 (5)
N4ⁱⁱ—Cu1—N1—C1	−117.0 (5)	N1—N2—C2—S1	0.3 (5)
N5ⁱⁱⁱ—Cu1—N1—C1	−26.8 (5)	N1—N2—C2—S2	179.9 (3)
N5—Cu1—N1—C1	153.2 (5)	C1—S1—C2—N2	−0.1 (4)
N4ⁱ—Cu1—N1—N2	−109.4 (3)	C1—S1—C2—S2	−179.8 (4)
N4ⁱⁱ—Cu1—N1—N2	70.6 (3)	C3—S2—C2—N2	6.9 (5)
N5ⁱⁱⁱ—Cu1—N1—N2	160.8 (3)	C3—S2—C2—S1	−173.5 (3)
N5—Cu1—N1—N2	−19.2 (3)	C2—S2—C3—S3	71.7 (3)
C1—N1—N2—C2	−0.4 (6)	C4—S3—C3—S2	78.6 (3)
Cu1—N1—N2—C2	173.1 (3)	N4—N3—C4—S4	0.2 (5)
C4—N3—N4—C5	−0.6 (6)	N4—N3—C4—S3	179.3 (4)
C4—N3—N4—Cu1^iv	−177.6 (3)	C5—S4—C4—N3	0.2 (4)
N4ⁱ—Cu1—N5—C6	−53.6 (14)	C5—S4—C4—S3	−179.0 (4)
N4ⁱⁱ—Cu1—N5—C6	126.4 (14)	C3—S3—C4—N3	6.7 (5)
N1ⁱⁱⁱ—Cu1—N5—C6	37.7 (14)	C3—S3—C4—S4	−174.2 (3)
N1—Cu1—N5—C6	−142.3 (14)	N3—N4—C5—S4	0.8 (6)
N2—N1—C1—S1	0.3 (7)	Cu1^iv—N4—C5—S4	177.3 (3)
Cu1—N1—C1—S1	−172.5 (3)	C4—S4—C5—N4	−0.6 (5)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x, −y+2, z−1/2; (iii) −x+1/2, −y+3/2, −z; (iv) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3^v	0.93	2.35	2.955 (8)	123
C3—H3A···O1^vi	0.97	2.41	3.277 (9)	149
C5—H5···O1^vii	0.93	2.45	3.169 (9)	135

Symmetry codes: (v) −x+1, −y+1, −z+1; (vi) −x+1/2, −y+3/2, −z+1; (vii) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₅H₄N₄S₄)₂(C₂H₃N)₂](ClO₄)₂·C₂H₃N
M_r	1764.65
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	19.3144 (18), 9.9450 (9), 18.8722 (18)
β (°)	98.876 (1)
V (Å³)	3581.6 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.43 × 0.32 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.608, 0.702
No. of measured, independent and observed [I > 2σ(I)] reflections	12066, 3285, 2568
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.181, 1.07
No. of reflections	3285
No. of parameters	216
No. of restraints	304
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1007P)² + 13.6762P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.83

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.93	2.35	2.955 (8)	123
C3—H3A···O1ⁱⁱ	0.97	2.41	3.277 (9)	149
C5—H5···O1ⁱⁱⁱ	0.93	2.45	3.169 (9)	135

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, −y+3/2, −z+1; (iii) −x+1/2, y+1/2, −z+3/2.

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
Qin, J.-H., Wang, J.-G. & Hu, P.-Z. (2009). Acta Cryst. E65, m349–m350. 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. CAS Google Scholar

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