Acta Cryst. (2009). E65, m307 [ doi:10.1107/S1600536809005625 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole)-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N4:N4']copper(II)] bis(perchlorate)]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.
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.
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).
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).
![[Figure 1]](./su2097fig1thm.gif)
| 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]](./su2097fig2thm.gif)
| Fig. 2. A view down the b axis of the crystal packing of the title compound. |
| [Cu(C8H10N4S4)3](ClO4)2 | Dx = 1.739 Mg m−3 |
| Mr = 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 |
| Bruker SMART CCD area-detector diffractometer | 1673 independent reflections |
| Radiation source: fine-focus sealed tube | 1320 reflections with I > 2σ(I) |
| graphite | Rint = 0.028 |
| φ and ω scans | θmax = 27.5°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −13→13 |
| Tmin = 0.717, Tmax = 0.839 | k = −13→13 |
| 9432 measured reflections | l = −43→43 |
| 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(Fo2) + (0.0617P)2 + 10.9603P] where P = (Fo2 + 2Fc2)/3 |
| 1673 reflections | (Δ/σ)max < 0.001 |
| 90 parameters | Δρmax = 0.82 e Å−3 |
| 0 restraints | Δρmin = −0.51 e Å−3 |
| [Cu(C8H10N4S4)3](ClO4)2 | Z = 3 |
| Mr = 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 |
| 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 = 0.839 | Rint = 0.028 |
| 9432 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0617P)2 + 10.9603P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.133 | Δρmax = 0.82 e Å−3 |
| S = 1.05 | Δρmin = −0.51 e Å−3 |
| 1673 reflections | Absolute structure: ? |
| 90 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| H-atom parameters constrained |
| x | y | z | Uiso*/Ueq | ||
| 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* |
| 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) |
| 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—N2iv | 2.149 (3) | N2—C1 | 1.286 (4) |
| Cu1—N2v | 2.149 (3) | C1—H1 | 0.9300 |
| Cl1—O1 | 1.409 (4) | C3—C4 | 1.523 (6) |
| Cl1—O1vi | 1.409 (4) | C3—H3A | 0.9700 |
| Cl1—O1vii | 1.409 (4) | C3—H3B | 0.9700 |
| Cl1—O2 | 1.463 (8) | C4—C4viii | 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—N2iv | 88.61 (10) | S1—C1—H1 | 122.6 |
| N2—Cu1—N2iv | 179.999 (2) | N1—C2—S1 | 114.7 (3) |
| N2ii—Cu1—N2iv | 88.61 (10) | N1—C2—S2 | 125.9 (3) |
| N2iii—Cu1—N2iv | 91.39 (10) | S1—C2—S2 | 119.4 (2) |
| N2i—Cu1—N2v | 179.999 (1) | C4—C3—S2 | 112.3 (3) |
| N2—Cu1—N2v | 88.61 (10) | C4—C3—H3A | 109.1 |
| N2ii—Cu1—N2v | 88.60 (10) | S2—C3—H3A | 109.1 |
| N2iii—Cu1—N2v | 91.39 (10) | C4—C3—H3B | 109.1 |
| N2iv—Cu1—N2v | 91.39 (10) | S2—C3—H3B | 109.1 |
| O1—Cl1—O1vi | 112.77 (18) | H3A—C3—H3B | 107.9 |
| O1—Cl1—O1vii | 112.77 (18) | C4viii—C4—C3 | 111.9 (4) |
| O1vi—Cl1—O1vii | 112.77 (18) | C4viii—C4—H4A | 109.2 |
| O1—Cl1—O2 | 105.9 (2) | C3—C4—H4A | 109.2 |
| O1vi—Cl1—O2 | 105.9 (2) | C4viii—C4—H4B | 109.2 |
| O1vii—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) |
| 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—S1 | 179.4 (2) |
| N2iii—Cu1—N2—N1 | 175.7 (2) | C2—S2—C3—C4 | 93.0 (3) |
| N2v—Cu1—N2—N1 | 84.24 (17) | S2—C3—C4—C4viii | 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. |
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.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wang, J. G., Qin, J. H., Hu, P. Z. & Zhao, B. T. (2008). Z. Kristallogr. New Cryst. Struct. 223, 225–227.
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).