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

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

doi:10.1107/S1600536809005625

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m307

doi:10.1107/S1600536809005625

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

Pu-Zhou Hu,^a ^* Jian-Hua Qin ^a and Jian-Ge Wang ^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 11 February 2009; accepted 17 February 2009; online 21 February 2009)

In the title compound, {[Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂}_n, the Cu^II atom is located on a threefold inversion axis coordinated by six N atoms of symmetry-equivalent 2,2′-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligands in a slightly distorted octahedral geometry. Adjacent Cu^II atoms are linked by the bridging bidentate thiadiazole ligands, which are situated about inversion centers. This leads to the formation of a three-dimensional network structure.

Related literature

For copper(II) complexes involving the same ligand, see: Huang et al. (2009 ); Wang et al. (2008 ).

Experimental

Crystal data

[Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂
M_r = 1133.76
Trigonal, $[R \overline 3]$
a = 10.5455 (6) Å
c = 33.728 (4) Å
V = 3248.3 (5) Å³
Z = 3
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 291 K
0.28 × 0.21 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.717, T_max = 0.839
9432 measured reflections
1673 independent reflections
1320 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.133
S = 1.05
1673 reflections
90 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.51 e Å⁻³

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/S1600536809005625/su2097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005625/su2097Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound consists of one sixth of a Cu^II atom, which is located on a three-fold inversion axis, half a 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligand which possesses an inversion center, and one third of a perchlorate ion, which is situated on a three-fold rotation axis. As depicted in Fig. 1, the Cu^II atom is coordinated by six N atoms from six symmetry equivalent 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligands, in a slightly distorted octahedral geometry of the central atom. The Cu—N bond distance is 2.149 (3) Å, within the range expected for such coordination bonds (Huang et al., 2009; Wang et al., 2008). The centrosymmetric 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligand adopts a N,N'-bidentate bridging mode in a trans configuration and links the Cu^II atoms to form a three-dimensional network. The bridging Cu···Cu distance is 12.7854 (12) Å (Fig. 2).

Related literature top

For copper(II) complexes involving the same ligand, see: Huang et al. (2009); Wang et al. (2008).

Experimental top

The reaction of 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) (0.3 mmol) with Cu(ClO₄)₂ (0.1 mmol) in MeOH(10 ml) for a few minutes gave a light blue solid, which 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 coordination around the Cu^II atom in the cation of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The H atoms and perchlorate ion were omitted for clarity.
	Fig. 2. A view down the b axis of the crystal packing of the title compound.

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

Crystal data top

[Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂	D_x = 1.739 Mg m⁻³
M_r = 1133.76	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2638 reflections
Hall symbol: -R 3	θ = 2.3–24.5°
a = 10.5455 (6) Å	µ = 1.27 mm⁻¹
c = 33.728 (4) Å	T = 291 K
V = 3248.3 (5) Å³	Block, blue
Z = 3	0.28 × 0.21 × 0.14 mm
F(000) = 1731

Data collection top

Bruker SMART CCD area-detector diffractometer	1673 independent reflections
Radiation source: fine-focus sealed tube	1320 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −13→13
T_min = 0.717, T_max = 0.839	k = −13→13
9432 measured reflections	l = −43→43

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0617P)² + 10.9603P] where P = (F_o² + 2F_c²)/3
1673 reflections	(Δ/σ)_max < 0.001
90 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂	Z = 3
M_r = 1133.76	Mo Kα radiation
Trigonal, R3	µ = 1.27 mm⁻¹
a = 10.5455 (6) Å	T = 291 K
c = 33.728 (4) Å	0.28 × 0.21 × 0.14 mm
V = 3248.3 (5) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1673 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1320 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.839	R_int = 0.028
9432 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0617P)² + 10.9603P] where P = (F_o² + 2F_c²)/3
1673 reflections	Δρ_max = 0.82 e Å⁻³
90 parameters	Δρ_min = −0.51 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Cu1	1.0000	1.0000	0.5000	0.0338 (2)
Cl1	0.3333	0.6667	0.45984 (7)	0.0692 (5)
S1	0.94592 (14)	0.59055 (13)	0.43361 (3)	0.0702 (4)
S2	0.71904 (11)	0.56831 (12)	0.37580 (3)	0.0608 (3)
O1	0.3599 (4)	0.8063 (4)	0.47130 (14)	0.1084 (13)
O2	0.3333	0.6667	0.4165 (2)	0.124 (3)
N1	0.8519 (3)	0.7722 (3)	0.43379 (8)	0.0500 (7)
N2	0.9537 (3)	0.8133 (3)	0.46412 (8)	0.0461 (6)
C1	1.0099 (4)	0.7300 (4)	0.46704 (11)	0.0578 (9)
H1	1.0802	0.7448	0.4860	0.069*
C2	0.8366 (4)	0.6570 (4)	0.41560 (10)	0.0501 (8)
C3	0.6329 (4)	0.6782 (5)	0.36973 (12)	0.0615 (9)
H3A	0.5323	0.6158	0.3613	0.074*
H3B	0.6313	0.7208	0.3951	0.074*
C4	0.7119 (5)	0.8003 (5)	0.33947 (13)	0.0679 (11)
H4A	0.8032	0.8758	0.3508	0.082*
H4B	0.7351	0.7613	0.3163	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0332 (3)	0.0332 (3)	0.0350 (4)	0.01660 (15)	0.000	0.000
Cl1	0.0537 (6)	0.0537 (6)	0.1003 (14)	0.0269 (3)	0.000	0.000
S1	0.0854 (8)	0.0764 (7)	0.0679 (7)	0.0548 (6)	−0.0153 (5)	−0.0153 (5)
S2	0.0585 (6)	0.0671 (6)	0.0537 (6)	0.0292 (5)	−0.0048 (4)	−0.0096 (4)
O1	0.101 (3)	0.073 (2)	0.152 (4)	0.045 (2)	0.015 (3)	−0.023 (2)
O2	0.140 (4)	0.140 (4)	0.090 (5)	0.070 (2)	0.000	0.000
N1	0.0441 (15)	0.0547 (17)	0.0504 (16)	0.0242 (13)	−0.0014 (12)	−0.0007 (13)
N2	0.0424 (14)	0.0526 (16)	0.0430 (14)	0.0237 (12)	0.0009 (11)	0.0021 (12)
C1	0.063 (2)	0.067 (2)	0.053 (2)	0.040 (2)	−0.0060 (17)	−0.0057 (17)
C2	0.0449 (17)	0.059 (2)	0.0434 (17)	0.0241 (16)	0.0067 (13)	0.0052 (15)
C3	0.051 (2)	0.068 (2)	0.062 (2)	0.0271 (19)	−0.0115 (17)	−0.0019 (19)
C4	0.060 (2)	0.073 (3)	0.075 (3)	0.036 (2)	−0.004 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Cu1—N2ⁱ	2.149 (3)	S2—C2	1.748 (4)
Cu1—N2	2.149 (3)	S2—C3	1.807 (4)
Cu1—N2ⁱⁱ	2.149 (3)	N1—C2	1.298 (4)
Cu1—N2ⁱⁱⁱ	2.149 (3)	N1—N2	1.386 (4)
Cu1—N2^iv	2.149 (3)	N2—C1	1.286 (4)
Cu1—N2^v	2.149 (3)	C1—H1	0.9300
Cl1—O1	1.409 (4)	C3—C4	1.523 (6)
Cl1—O1^vi	1.409 (4)	C3—H3A	0.9700
Cl1—O1^vii	1.409 (4)	C3—H3B	0.9700
Cl1—O2	1.463 (8)	C4—C4^viii	1.494 (8)
S1—C1	1.702 (4)	C4—H4A	0.9700
S1—C2	1.731 (4)	C4—H4B	0.9700

N2ⁱ—Cu1—N2	91.39 (10)	C2—N1—N2	110.8 (3)
N2ⁱ—Cu1—N2ⁱⁱ	91.40 (10)	C1—N2—N1	113.1 (3)
N2—Cu1—N2ⁱⁱ	91.39 (10)	C1—N2—Cu1	127.7 (2)
N2ⁱ—Cu1—N2ⁱⁱⁱ	88.61 (10)	N1—N2—Cu1	119.2 (2)
N2—Cu1—N2ⁱⁱⁱ	88.61 (10)	N2—C1—S1	114.9 (3)
N2ⁱⁱ—Cu1—N2ⁱⁱⁱ	179.998 (1)	N2—C1—H1	122.6
N2ⁱ—Cu1—N2^iv	88.61 (10)	S1—C1—H1	122.6
N2—Cu1—N2^iv	179.999 (2)	N1—C2—S1	114.7 (3)
N2ⁱⁱ—Cu1—N2^iv	88.61 (10)	N1—C2—S2	125.9 (3)
N2ⁱⁱⁱ—Cu1—N2^iv	91.39 (10)	S1—C2—S2	119.4 (2)
N2ⁱ—Cu1—N2^v	179.999 (1)	C4—C3—S2	112.3 (3)
N2—Cu1—N2^v	88.61 (10)	C4—C3—H3A	109.1
N2ⁱⁱ—Cu1—N2^v	88.60 (10)	S2—C3—H3A	109.1
N2ⁱⁱⁱ—Cu1—N2^v	91.39 (10)	C4—C3—H3B	109.1
N2^iv—Cu1—N2^v	91.39 (10)	S2—C3—H3B	109.1
O1—Cl1—O1^vi	112.77 (18)	H3A—C3—H3B	107.9
O1—Cl1—O1^vii	112.77 (18)	C4^viii—C4—C3	111.9 (4)
O1^vi—Cl1—O1^vii	112.77 (18)	C4^viii—C4—H4A	109.2
O1—Cl1—O2	105.9 (2)	C3—C4—H4A	109.2
O1^vi—Cl1—O2	105.9 (2)	C4^viii—C4—H4B	109.2
O1^vii—Cl1—O2	105.9 (2)	C3—C4—H4B	109.2
C1—S1—C2	86.55 (18)	H4A—C4—H4B	107.9
C2—S2—C3	101.18 (18)

C2—N1—N2—C1	0.6 (4)	Cu1—N2—C1—S1	179.51 (16)
C2—N1—N2—Cu1	−179.3 (2)	C2—S1—C1—N2	0.1 (3)
N2ⁱ—Cu1—N2—C1	84.4 (4)	N2—N1—C2—S1	−0.6 (4)
N2ⁱⁱ—Cu1—N2—C1	175.8 (3)	N2—N1—C2—S2	179.7 (2)
N2ⁱⁱⁱ—Cu1—N2—C1	−4.2 (3)	C1—S1—C2—N1	0.3 (3)
N2^v—Cu1—N2—C1	−95.6 (4)	C1—S1—C2—S2	−179.9 (2)
N2ⁱ—Cu1—N2—N1	−95.76 (17)	C3—S2—C2—N1	−0.8 (4)
N2ⁱⁱ—Cu1—N2—N1	−4.3 (2)	C3—S2—C2—S1	179.4 (2)
N2ⁱⁱⁱ—Cu1—N2—N1	175.7 (2)	C2—S2—C3—C4	93.0 (3)
N2^v—Cu1—N2—N1	84.24 (17)	S2—C3—C4—C4^viii	165.9 (4)
N1—N2—C1—S1	−0.4 (4)

Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) x−y+1, x, −z+1; (iv) −x+2, −y+2, −z+1; (v) y, −x+y+1, −z+1; (vi) −x+y, −x+1, z; (vii) −y+1, x−y+1, z; (viii) −x+4/3, −y+5/3, −z+2/3.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂
M_r	1133.76
Crystal system, space group	Trigonal, R3
Temperature (K)	291
a, c (Å)	10.5455 (6), 33.728 (4)
V (Å³)	3248.3 (5)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.28 × 0.21 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.717, 0.839
No. of measured, independent and observed [I > 2σ(I)] reflections	9432, 1673, 1320
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.133, 1.05
No. of reflections	1673
No. of parameters	90
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0617P)² + 10.9603P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.51

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

Acknowledgements

The authors thank the 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. CAS Google Scholar

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