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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): m307.
Published online 2009 February 21. doi:  10.1107/S1600536809005625
PMCID: PMC2968516

Poly[[tris­[μ-2,2′-(butane-1,4-diyl­dithio)bis­(1,3,4-thia­diazole)-κ2 N 4:N 4′]copper(II)] bis­(perchlorate)]

Abstract

In the title compound, {[Cu(C8H10N4S4)3](ClO4)2}n, the CuII 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 CuII 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 [triangle]); Wang et al. (2008 [triangle]).

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Object name is e-65-0m307-scheme1.jpg

Experimental

Crystal data

  • [Cu(C8H10N4S4)3](ClO4)2
  • M r = 1133.76
  • Trigonal, An external file that holds a picture, illustration, etc.
Object name is e-65-0m307-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.133
  • S = 1.05
  • 1673 reflections
  • 90 parameters
  • H-atom parameters constrained
  • Δρmax = 0.82 e Å−3
  • Δρmin = −0.51 e Å−3

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005625/su2097sup1.cif

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

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

Acknowledgments

The authors thank the Luoyang Normal University, for supporting this work.

supplementary crystallographic information

Comment

The asymmetric unit of the title compound consists of one sixth of a CuII 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 CuII 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 CuII atoms to form a three-dimensional network. The bridging Cu···Cu distance is 12.7854 (12) Å (Fig. 2).

Experimental

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.

Refinement

The H-atoms were positioned geometrically and treated as riding: C—H = 0.93 - 0.97 Å and Uiso(H) = 1.2Ueq(parent C-atom).

Figures

Fig. 1.
A view of the coordination around the CuII 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.

Crystal data

[Cu(C8H10N4S4)3](ClO4)2Dx = 1.739 Mg m3
Mr = 1133.76Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 2638 reflections
Hall symbol: -R 3θ = 2.3–24.5°
a = 10.5455 (6) ŵ = 1.27 mm1
c = 33.728 (4) ÅT = 291 K
V = 3248.3 (5) Å3Block, blue
Z = 30.28 × 0.21 × 0.14 mm
F(000) = 1731

Data collection

Bruker SMART CCD area-detector diffractometer1673 independent reflections
Radiation source: fine-focus sealed tube1320 reflections with I > 2σ(I)
graphiteRint = 0.028
[var phi] and ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −13→13
Tmin = 0.717, Tmax = 0.839k = −13→13
9432 measured reflectionsl = −43→43

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0617P)2 + 10.9603P] where P = (Fo2 + 2Fc2)/3
1673 reflections(Δ/σ)max < 0.001
90 parametersΔρmax = 0.82 e Å3
0 restraintsΔρmin = −0.51 e Å3

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

xyzUiso*/Ueq
Cu11.00001.00000.50000.0338 (2)
Cl10.33330.66670.45984 (7)0.0692 (5)
S10.94592 (14)0.59055 (13)0.43361 (3)0.0702 (4)
S20.71904 (11)0.56831 (12)0.37580 (3)0.0608 (3)
O10.3599 (4)0.8063 (4)0.47130 (14)0.1084 (13)
O20.33330.66670.4165 (2)0.124 (3)
N10.8519 (3)0.7722 (3)0.43379 (8)0.0500 (7)
N20.9537 (3)0.8133 (3)0.46412 (8)0.0461 (6)
C11.0099 (4)0.7300 (4)0.46704 (11)0.0578 (9)
H11.08020.74480.48600.069*
C20.8366 (4)0.6570 (4)0.41560 (10)0.0501 (8)
C30.6329 (4)0.6782 (5)0.36973 (12)0.0615 (9)
H3A0.53230.61580.36130.074*
H3B0.63130.72080.39510.074*
C40.7119 (5)0.8003 (5)0.33947 (13)0.0679 (11)
H4A0.80320.87580.35080.082*
H4B0.73510.76130.31630.082*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0332 (3)0.0332 (3)0.0350 (4)0.01660 (15)0.0000.000
Cl10.0537 (6)0.0537 (6)0.1003 (14)0.0269 (3)0.0000.000
S10.0854 (8)0.0764 (7)0.0679 (7)0.0548 (6)−0.0153 (5)−0.0153 (5)
S20.0585 (6)0.0671 (6)0.0537 (6)0.0292 (5)−0.0048 (4)−0.0096 (4)
O10.101 (3)0.073 (2)0.152 (4)0.045 (2)0.015 (3)−0.023 (2)
O20.140 (4)0.140 (4)0.090 (5)0.070 (2)0.0000.000
N10.0441 (15)0.0547 (17)0.0504 (16)0.0242 (13)−0.0014 (12)−0.0007 (13)
N20.0424 (14)0.0526 (16)0.0430 (14)0.0237 (12)0.0009 (11)0.0021 (12)
C10.063 (2)0.067 (2)0.053 (2)0.040 (2)−0.0060 (17)−0.0057 (17)
C20.0449 (17)0.059 (2)0.0434 (17)0.0241 (16)0.0067 (13)0.0052 (15)
C30.051 (2)0.068 (2)0.062 (2)0.0271 (19)−0.0115 (17)−0.0019 (19)
C40.060 (2)0.073 (3)0.075 (3)0.036 (2)−0.004 (2)−0.001 (2)

Geometric parameters (Å, °)

Cu1—N2i2.149 (3)S2—C21.748 (4)
Cu1—N22.149 (3)S2—C31.807 (4)
Cu1—N2ii2.149 (3)N1—C21.298 (4)
Cu1—N2iii2.149 (3)N1—N21.386 (4)
Cu1—N2iv2.149 (3)N2—C11.286 (4)
Cu1—N2v2.149 (3)C1—H10.9300
Cl1—O11.409 (4)C3—C41.523 (6)
Cl1—O1vi1.409 (4)C3—H3A0.9700
Cl1—O1vii1.409 (4)C3—H3B0.9700
Cl1—O21.463 (8)C4—C4viii1.494 (8)
S1—C11.702 (4)C4—H4A0.9700
S1—C21.731 (4)C4—H4B0.9700
N2i—Cu1—N291.39 (10)C2—N1—N2110.8 (3)
N2i—Cu1—N2ii91.40 (10)C1—N2—N1113.1 (3)
N2—Cu1—N2ii91.39 (10)C1—N2—Cu1127.7 (2)
N2i—Cu1—N2iii88.61 (10)N1—N2—Cu1119.2 (2)
N2—Cu1—N2iii88.61 (10)N2—C1—S1114.9 (3)
N2ii—Cu1—N2iii179.998 (1)N2—C1—H1122.6
N2i—Cu1—N2iv88.61 (10)S1—C1—H1122.6
N2—Cu1—N2iv179.999 (2)N1—C2—S1114.7 (3)
N2ii—Cu1—N2iv88.61 (10)N1—C2—S2125.9 (3)
N2iii—Cu1—N2iv91.39 (10)S1—C2—S2119.4 (2)
N2i—Cu1—N2v179.999 (1)C4—C3—S2112.3 (3)
N2—Cu1—N2v88.61 (10)C4—C3—H3A109.1
N2ii—Cu1—N2v88.60 (10)S2—C3—H3A109.1
N2iii—Cu1—N2v91.39 (10)C4—C3—H3B109.1
N2iv—Cu1—N2v91.39 (10)S2—C3—H3B109.1
O1—Cl1—O1vi112.77 (18)H3A—C3—H3B107.9
O1—Cl1—O1vii112.77 (18)C4viii—C4—C3111.9 (4)
O1vi—Cl1—O1vii112.77 (18)C4viii—C4—H4A109.2
O1—Cl1—O2105.9 (2)C3—C4—H4A109.2
O1vi—Cl1—O2105.9 (2)C4viii—C4—H4B109.2
O1vii—Cl1—O2105.9 (2)C3—C4—H4B109.2
C1—S1—C286.55 (18)H4A—C4—H4B107.9
C2—S2—C3101.18 (18)
C2—N1—N2—C10.6 (4)Cu1—N2—C1—S1179.51 (16)
C2—N1—N2—Cu1−179.3 (2)C2—S1—C1—N20.1 (3)
N2i—Cu1—N2—C184.4 (4)N2—N1—C2—S1−0.6 (4)
N2ii—Cu1—N2—C1175.8 (3)N2—N1—C2—S2179.7 (2)
N2iii—Cu1—N2—C1−4.2 (3)C1—S1—C2—N10.3 (3)
N2v—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—S1179.4 (2)
N2iii—Cu1—N2—N1175.7 (2)C2—S2—C3—C493.0 (3)
N2v—Cu1—N2—N184.24 (17)S2—C3—C4—C4viii165.9 (4)
N1—N2—C1—S1−0.4 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2097).

References

  • Bruker (1997). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Huang, H.-M., Ju, F.-Y., Wang, J.-G. & Qin, J.-H. (2009). Acta Cryst. E65, m80–m81. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, J. G., Qin, J. H., Hu, P. Z. & Zhao, B. T. (2008). Z. Kristallogr. New Cryst. Struct.223, 225–227.

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