Acta Cryst. (2007). E63, m2385 [ doi:10.1107/S1600536807039967 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-1,4-bis(pyrimidin-2-ylsulfanylmethyl)benzene-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N:N']In the title complex, [CuCl2(C16H14N4S2)]n, the Cu atom lies on a center of inversion and is bridged by two adjacent pyrimidine N atoms and two chloride counter-ions to give a square-planar coordination geometry. The bidentate thioether ligands link adjacent Cu atoms into an infinite chain.
Bis(2-pyrimidinesulfanylmethyl)benzene was synthesized using a reported procedure (Peng et al., 2006). A mixture of CuCl (0.01 g, 0.1 mmol), bis(2-pyrimidinesulfanylmethyl)benzene (0.033 g, 0.1 mmol), CHCl3 (2.0 ml) and acetonitrile (4.0 ml) was stirred for 15 min in air and then transferred to a 13 ml Teflon-lined reactor and sealed, then heated in an oven to 393 K for 48 h, and cooled to room temperature at a rate of 3 K 0.5 h−1. The reaction mixture was filtered to give a yellow-red solution. Black block-shaped crystals of (I) were obtained by slow diffusion of diethyl ether into the solution after one week (yield 36%, based on Cu). Analysis calculated for C16H14Cl2CuN4S2: C 41.66, H 3.04, N 12.15%; found: C 41.81, H 3.13, N 11.97%.
The H atoms were placed at calculated positions [aromatic C–H = 0.93 Å and methylene C–H = 0.97 Å; Uiso(H) = 1.2 times Ueq(C)].
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: publCIF (Westrip, 2007).
![[Figure 1]](./ez2094fig1thm.gif)
| Fig. 1. View of a fragment of the chain motif in (I) showing the atom numbering scheme of the asymmetric unit and 30% displacement ellipsoids for the non-hydrogen atoms. |
| [CuCl2(C16H14N4S2)] | F000 = 466 |
| Mr = 460.87 | Dx = 1.670 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1784 reflections |
| a = 8.9243 (9) Å | θ = 2.8–25.7º |
| b = 9.9867 (9) Å | µ = 1.72 mm−1 |
| c = 10.4339 (10) Å | T = 295 (2) K |
| β = 99.667 (2)º | Block, black |
| V = 916.71 (15) Å3 | 0.29 × 0.11 × 0.09 mm |
| Z = 2 |
| Bruker APEX CCD diffractometer | 2034 independent reflections |
| Radiation source: fine-focus sealed tube | 1517 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.032 |
| T = 295(2) K | θmax = 27.5º |
| φ and ω scans | θmin = 2.8º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→11 |
| Tmin = 0.636, Tmax = 0.861 | k = −12→12 |
| 4908 measured reflections | l = −13→13 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0589P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 2034 reflections | Δρmax = 0.60 e Å−3 |
| 115 parameters | Δρmin = −0.43 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [CuCl2(C16H14N4S2)] | V = 916.71 (15) Å3 |
| Mr = 460.87 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 8.9243 (9) Å | µ = 1.72 mm−1 |
| b = 9.9867 (9) Å | T = 295 (2) K |
| c = 10.4339 (10) Å | 0.29 × 0.11 × 0.09 mm |
| β = 99.667 (2)º |
| Bruker APEX CCD diffractometer | 2034 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1517 reflections with I > 2σ(I) |
| Tmin = 0.636, Tmax = 0.861 | Rint = 0.032 |
| 4908 measured reflections |
| R[F2 > 2σ(F2)] = 0.047 | 115 parameters |
| wR(F2) = 0.111 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.60 e Å−3 |
| 2034 reflections | Δρmin = −0.43 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0398 (2) | |
| Cl1 | 0.57709 (10) | 0.70107 (9) | 0.44428 (9) | 0.0612 (3) | |
| S1 | 0.20657 (10) | 0.64387 (9) | 0.57216 (8) | 0.0565 (3) | |
| N1 | 0.3033 (3) | 0.5254 (2) | 0.3782 (3) | 0.0411 (6) | |
| N2 | 0.0592 (3) | 0.6232 (3) | 0.3285 (2) | 0.0518 (7) | |
| C1 | 0.2880 (4) | 0.4759 (3) | 0.2575 (3) | 0.0504 (8) | |
| H1 | 0.3661 | 0.4249 | 0.2338 | 0.060* | |
| C2 | 0.1601 (4) | 0.4987 (4) | 0.1686 (3) | 0.0633 (11) | |
| H2 | 0.1487 | 0.4636 | 0.0849 | 0.076* | |
| C3 | 0.0499 (4) | 0.5753 (4) | 0.2079 (3) | 0.0625 (10) | |
| H3 | −0.0363 | 0.5953 | 0.1477 | 0.075* | |
| C4 | 0.1860 (3) | 0.5945 (3) | 0.4089 (3) | 0.0391 (7) | |
| C5 | 0.0246 (4) | 0.7224 (3) | 0.5817 (3) | 0.0485 (8) | |
| H5B | −0.0553 | 0.6716 | 0.5286 | 0.058* | |
| H5A | 0.0072 | 0.7180 | 0.6709 | 0.058* | |
| C6 | 0.0134 (3) | 0.8652 (3) | 0.5382 (3) | 0.0404 (7) | |
| C7 | −0.0903 (3) | 0.9039 (3) | 0.4302 (3) | 0.0439 (7) | |
| H7 | −0.1515 | 0.8397 | 0.3826 | 0.053* | |
| C8 | −0.1037 (3) | 1.0371 (3) | 0.3923 (3) | 0.0445 (8) | |
| H8 | −0.1739 | 1.0612 | 0.3197 | 0.053* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0352 (3) | 0.0342 (3) | 0.0486 (3) | −0.0014 (2) | 0.0032 (2) | −0.0005 (2) |
| Cl1 | 0.0574 (5) | 0.0444 (6) | 0.0783 (6) | −0.0115 (4) | 0.0015 (4) | 0.0115 (4) |
| S1 | 0.0658 (6) | 0.0556 (6) | 0.0436 (5) | 0.0203 (4) | −0.0035 (4) | −0.0068 (4) |
| N1 | 0.0394 (13) | 0.0373 (15) | 0.0459 (14) | −0.0035 (11) | 0.0052 (11) | 0.0001 (11) |
| N2 | 0.0468 (15) | 0.0571 (18) | 0.0479 (15) | 0.0075 (13) | −0.0025 (12) | −0.0003 (13) |
| C1 | 0.0462 (18) | 0.057 (2) | 0.0504 (19) | −0.0045 (15) | 0.0162 (15) | −0.0070 (16) |
| C2 | 0.060 (2) | 0.092 (3) | 0.0366 (17) | −0.011 (2) | 0.0051 (16) | −0.0100 (17) |
| C3 | 0.054 (2) | 0.083 (3) | 0.0458 (19) | −0.0016 (19) | −0.0043 (15) | 0.0035 (19) |
| C4 | 0.0429 (15) | 0.0329 (17) | 0.0398 (15) | −0.0017 (13) | 0.0018 (12) | 0.0014 (13) |
| C5 | 0.058 (2) | 0.038 (2) | 0.0535 (19) | 0.0023 (15) | 0.0204 (15) | −0.0011 (15) |
| C6 | 0.0402 (16) | 0.0373 (18) | 0.0482 (16) | 0.0029 (13) | 0.0205 (13) | −0.0008 (14) |
| C7 | 0.0395 (15) | 0.041 (2) | 0.0527 (18) | −0.0059 (13) | 0.0105 (13) | −0.0082 (15) |
| C8 | 0.0414 (17) | 0.044 (2) | 0.0485 (17) | 0.0021 (14) | 0.0082 (13) | −0.0012 (15) |
| Cu1—N1 | 2.003 (2) | C2—C3 | 1.363 (5) |
| Cu1—N1i | 2.003 (2) | C2—H2 | 0.9300 |
| Cu1—Cl1i | 2.2311 (8) | C3—H3 | 0.9300 |
| Cu1—Cl1 | 2.2311 (8) | C5—C6 | 1.495 (4) |
| S1—C4 | 1.754 (3) | C5—H5B | 0.9700 |
| S1—C5 | 1.821 (3) | C5—H5A | 0.9700 |
| N1—C4 | 1.336 (4) | C6—C7 | 1.387 (4) |
| N1—C1 | 1.339 (4) | C6—C8ii | 1.390 (4) |
| N2—C4 | 1.322 (4) | C7—C8 | 1.387 (4) |
| N2—C3 | 1.335 (4) | C7—H7 | 0.9300 |
| C1—C2 | 1.364 (5) | C8—C6ii | 1.390 (4) |
| C1—H1 | 0.9300 | C8—H8 | 0.9300 |
| N1—Cu1—N1i | 180.0 | C2—C3—H3 | 118.3 |
| N1—Cu1—Cl1i | 90.20 (7) | N2—C4—N1 | 125.6 (3) |
| N1i—Cu1—Cl1i | 89.80 (7) | N2—C4—S1 | 119.6 (2) |
| N1—Cu1—Cl1 | 89.80 (7) | N1—C4—S1 | 114.8 (2) |
| N1i—Cu1—Cl1 | 90.20 (7) | C6—C5—S1 | 114.2 (2) |
| Cl1i—Cu1—Cl1 | 180.0 | C6—C5—H5B | 108.7 |
| C4—S1—C5 | 103.02 (14) | S1—C5—H5B | 108.7 |
| C4—N1—C1 | 117.1 (3) | C6—C5—H5A | 108.7 |
| C4—N1—Cu1 | 123.5 (2) | S1—C5—H5A | 108.7 |
| C1—N1—Cu1 | 119.4 (2) | H5B—C5—H5A | 107.6 |
| C4—N2—C3 | 115.5 (3) | C7—C6—C8ii | 118.5 (3) |
| N1—C1—C2 | 121.4 (3) | C7—C6—C5 | 120.9 (3) |
| N1—C1—H1 | 119.3 | C8ii—C6—C5 | 120.5 (3) |
| C2—C1—H1 | 119.3 | C8—C7—C6 | 120.8 (3) |
| C3—C2—C1 | 116.9 (3) | C8—C7—H7 | 119.6 |
| C3—C2—H2 | 121.6 | C6—C7—H7 | 119.6 |
| C1—C2—H2 | 121.6 | C7—C8—C6ii | 120.6 (3) |
| N2—C3—C2 | 123.4 (3) | C7—C8—H8 | 119.7 |
| N2—C3—H3 | 118.3 | C6ii—C8—H8 | 119.7 |
| Cl1i—Cu1—N1—C4 | 97.7 (2) | Cu1—N1—C4—N2 | 174.1 (2) |
| Cl1—Cu1—N1—C4 | −82.3 (2) | C1—N1—C4—S1 | 174.6 (2) |
| Cl1i—Cu1—N1—C1 | −85.0 (2) | Cu1—N1—C4—S1 | −8.0 (3) |
| Cl1—Cu1—N1—C1 | 95.0 (2) | C5—S1—C4—N2 | 2.1 (3) |
| C4—N1—C1—C2 | 2.0 (5) | C5—S1—C4—N1 | −175.9 (2) |
| Cu1—N1—C1—C2 | −175.4 (2) | C4—S1—C5—C6 | −82.9 (3) |
| N1—C1—C2—C3 | 0.7 (5) | S1—C5—C6—C7 | 116.1 (3) |
| C4—N2—C3—C2 | 1.7 (6) | S1—C5—C6—C8ii | −65.9 (3) |
| C1—C2—C3—N2 | −2.7 (6) | C8ii—C6—C7—C8 | 0.0 (5) |
| C3—N2—C4—N1 | 1.4 (5) | C5—C6—C7—C8 | 178.0 (3) |
| C3—N2—C4—S1 | −176.4 (2) | C6—C7—C8—C6ii | 0.0 (5) |
| C1—N1—C4—N2 | −3.3 (4) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1. |
| Cu1—N1 | 2.003 (2) | Cu1—Cl1 | 2.2311 (8) |
| N1—Cu1—N1i | 180.0 | N1—Cu1—Cl1 | 89.80 (7) |
| N1—Cu1—Cl1i | 90.20 (7) | Cl1i—Cu1—Cl1 | 180.0 |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
We thank the National Natural Science Foundation of China (20571050 and 20271031) and the Natural Science Foundation of Guangdong Province (021240).
Bruker (2002). SMART (Version 6.36A) and SAINT (Version 6.36A). Bruker AXS Inc., Madison, Winconsin, USA. Version is the same for both programs?
Caradoc-Davies, P. L. & Hanton, L. R. (2003). Dalton Trans. pp. 1754–1758.
Hanton, L. R. & Lee, K. (2000). J. Chem. Soc. Dalton Trans. pp. 1161–1166.
Hong, M., Zhao, Y., Su, W., Cao, R., Fujita, M., Zhou, Z. & Chan, A. S. C. (2000). Angew. Chem. Int. Ed. 39, 2468–2470.
Peng, R., Li, D., Wu, T., Zhou, X.-P. & Ng, S. W. (2006). Inorg. Chem. 45, 4035-4046.
Peng, R., Wu, T. & Li, D. (2005). CrystEngComm, 7, 595–598.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Westrip, S. P. (2007). publCIF. In preparation.
The coordination chemistry of flexible thioether ligands has attracted considerable attention recently (Caradoc-Davies & Hanton, 2003; Hanton & Lee, 2000; Hong et al., 2000). We are currently involved in the synthesis and study of Cu(I) complexes of a series of N-containing heterocyclic thioether ligands. We have found that the ligand geometry and counteranions play an essential role in the framework formation of the Cu(I) complexes (Peng et al., 2005; Peng et al., 2006). The title compound is obtained from the solvothermal reaction of copper(I) chloride and bis(2-pyrimidinesulfanylmethyl)benzene in the presence of chloroform and acetonitrile solvents. X-ray structure analysis of the crystals shows that atom Cu1 lies on a center of inversion and is coordinated by two chloride anions and two N atoms from two adjacent thioether ligands. The bond angles about the copper atom [exactly 180° for Cl–Cu–Cl and N–Cu–N, and 89.80 (7) and 90.20 (7)° for N–Cu–Cl] confirm that it is in a regular square-planar CuCl2N2 geometry. The necessity to balance charges and the geometrical preferences of metal ions indicate the divalent state of the copper ions, which result from Cu(I) being oxidized in air. The thioether ligands, acting as bidentate connectors, link adjacent Cu(II) ions into a zigzag one-dimensional chain.