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ISSN: 2056-9890

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

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 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[Huang, H.-M., Ju, F.-Y., Wang, J.-G. & Qin, J.-H. (2009). Acta Cryst. E65, m80-m81.]); Wang et al. (2008[Wang, J. G., Qin, J. H., Hu, P. Z. & Zhao, B. T. (2008). Z. Kristallogr. New Cryst. Struct. 223, 225-227.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C8H10N4S4)3](ClO4)2

  • Mr = 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[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.717, Tmax = 0.839

  • 9432 measured reflections

  • 1673 independent reflections

  • 1320 reflections with I > 2σ(I)

  • Rint = 0.028

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 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[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

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.

Refinement top

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).

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
[Figure 1] 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.
[Figure 2] 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:N4']copper(II)] bis(perchlorate)] top
Crystal data top
[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 top
Bruker SMART CCD area-detector
diffractometer
1673 independent reflections
Radiation source: fine-focus sealed tube1320 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ϕ and ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1313
Tmin = 0.717, Tmax = 0.839k = 1313
9432 measured reflectionsl = 4343
Refinement top
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 = 1.05 w = 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
Crystal data top
[Cu(C8H10N4S4)3](ClO4)2Z = 3
Mr = 1133.76Mo Kα radiation
Trigonal, R3µ = 1.27 mm1
a = 10.5455 (6) ÅT = 291 K
c = 33.728 (4) Å0.28 × 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)
Tmin = 0.717, Tmax = 0.839Rint = 0.028
9432 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0617P)2 + 10.9603P]
where P = (Fo2 + 2Fc2)/3
1673 reflectionsΔρmax = 0.82 e Å3
90 parametersΔρmin = 0.51 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, º) top
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—Cu1179.3 (2)C2—S1—C1—N20.1 (3)
N2i—Cu1—N2—C184.4 (4)N2—N1—C2—S10.6 (4)
N2ii—Cu1—N2—C1175.8 (3)N2—N1—C2—S2179.7 (2)
N2iii—Cu1—N2—C14.2 (3)C1—S1—C2—N10.3 (3)
N2v—Cu1—N2—C195.6 (4)C1—S1—C2—S2179.9 (2)
N2i—Cu1—N2—N195.76 (17)C3—S2—C2—N10.8 (4)
N2ii—Cu1—N2—N14.3 (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—S10.4 (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.

Experimental details

Crystal data
Chemical formula[Cu(C8H10N4S4)3](ClO4)2
Mr1133.76
Crystal system, space groupTrigonal, R3
Temperature (K)291
a, c (Å)10.5455 (6), 33.728 (4)
V3)3248.3 (5)
Z3
Radiation typeMo Kα
µ (mm1)1.27
Crystal size (mm)0.28 × 0.21 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.717, 0.839
No. of measured, independent and
observed [I > 2σ(I)] reflections
9432, 1673, 1320
Rint0.028
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.133, 1.05
No. of reflections1673
No. of parameters90
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0617P)2 + 10.9603P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)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

First citationBruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHuang, 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
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, 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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