Acta Cryst. (2007). E63, m1630 [ doi:10.1107/S1600536807021654 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N']copper(II)]-![[mu]](/logos/entities/mu_rmgif.gif)
3-chlorido]In the repeat unit of the title compound, [CuCl2(C6H14N2)], there are two chiral C atoms with an S configuration. In the crystal packing, one Cl atom plays an important role, acting as a bridge linking neighboring units, forming a polymeric one-dimensional ladder-like structure. The Cu atom has an approximately square-planar primary coordination geometry, with the bridging Cl atoms forming much longer bonds in the axial positions.
Under solvothermal conditions, the reaction of (1S,2S)-1,2-diaminocyclohexane (0.0228 g, 0.2 mmol) with copper chloride (0.0347 g, 0.2 mmol) in a mixture of methanol and hydrochloric acid (2 ml, volume ratio: 10:1) at 1173 K for one day afforded square blue crystals of title compound.
All carbon-bound H atoms were positioned geometrically, with C—H = 0.97 Å and included in the refinement as riding, with Uiso(H) = 1.2Ueq(C). The H atoms attached to N were visible in the difference Fourier map and were subsequently treated as riding atoms, with N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq (N).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./im2011fig1thm.gif)
| Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./im2011fig2thm.gif)
| Fig. 2. View, approximately down the c axis, of the one-dimensional-dimension ladderlike structure. Symmetry code: (i) -1/2 + x,1/2 - y,-z (ii) 1/2 + x,1/2 - y,-z |
| [CuCl2(C6H14N2)] | F(000) = 508 |
| Mr = 248.63 | Dx = 1.711 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 875 reflections |
| a = 5.704 (1) Å | θ = 2.1–25.2° |
| b = 6.819 (1) Å | µ = 2.76 mm−1 |
| c = 24.823 (4) Å | T = 296 K |
| V = 965.5 (3) Å3 | Square, blue |
| Z = 4 | 0.20 × 0.20 × 0.12 mm |
| Bruker SMART APEX CCD diffractometer | 1884 independent reflections |
| Radiation source: sealed tube | 1766 reflections with I > 2σ(I) |
| graphite | Rint = 0.044 |
| φ and ω scans | θmax = 26.0°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −6→7 |
| Tmin = 0.58, Tmax = 0.72 | k = −8→8 |
| 5714 measured reflections | l = −30→30 |
| 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)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 1884 reflections | Δρmax = 0.69 e Å−3 |
| 100 parameters | Δρmin = −0.55 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 744 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.011 (19) |
| [CuCl2(C6H14N2)] | V = 965.5 (3) Å3 |
| Mr = 248.63 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 5.704 (1) Å | µ = 2.76 mm−1 |
| b = 6.819 (1) Å | T = 296 K |
| c = 24.823 (4) Å | 0.20 × 0.20 × 0.12 mm |
| Bruker SMART APEX CCD diffractometer | 1884 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1766 reflections with I > 2σ(I) |
| Tmin = 0.58, Tmax = 0.72 | Rint = 0.044 |
| 5714 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.082 | Δρmax = 0.69 e Å−3 |
| S = 1.02 | Δρmin = −0.55 e Å−3 |
| 1884 reflections | Absolute structure: Flack (1983), 744 Friedel pairs |
| 100 parameters | Flack parameter: 0.011 (19) |
| 0 restraints |
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 | ||
| C1 | 0.3284 (6) | 0.4129 (4) | −0.12770 (12) | 0.0275 (7) | |
| H1 | 0.4965 | 0.4423 | −0.1264 | 0.033* | |
| C2 | 0.2723 (9) | 0.3424 (5) | −0.18417 (11) | 0.0435 (9) | |
| H2A | 0.1097 | 0.3011 | −0.1858 | 0.052* | |
| H2B | 0.3698 | 0.2301 | −0.1928 | 0.052* | |
| C3 | 0.3145 (9) | 0.5042 (6) | −0.22536 (13) | 0.0506 (12) | |
| H3A | 0.4810 | 0.5325 | −0.2272 | 0.061* | |
| H3B | 0.2647 | 0.4593 | −0.2606 | 0.061* | |
| C4 | 0.1835 (8) | 0.6890 (6) | −0.21115 (13) | 0.0455 (10) | |
| H4A | 0.0163 | 0.6647 | −0.2135 | 0.055* | |
| H4B | 0.2227 | 0.7909 | −0.2369 | 0.055* | |
| C5 | 0.2436 (8) | 0.7590 (4) | −0.15455 (11) | 0.0356 (7) | |
| H5A | 0.4074 | 0.7969 | −0.1531 | 0.043* | |
| H5B | 0.1496 | 0.8732 | −0.1458 | 0.043* | |
| C6 | 0.1980 (5) | 0.5989 (4) | −0.11358 (12) | 0.0265 (7) | |
| H6 | 0.0300 | 0.5690 | −0.1146 | 0.032* | |
| Cl1 | 0.26572 (14) | 0.09330 (9) | 0.02474 (3) | 0.02790 (17) | |
| Cl2 | 0.26008 (16) | 0.55471 (10) | 0.06844 (3) | 0.03167 (19) | |
| Cu1 | 0.26675 (7) | 0.40155 (4) | −0.013331 (12) | 0.02443 (14) | |
| N1 | 0.2789 (6) | 0.2686 (3) | −0.08535 (8) | 0.0272 (6) | |
| H1A | 0.3915 | 0.1761 | −0.0852 | 0.033* | |
| H1B | 0.1408 | 0.2095 | −0.0920 | 0.033* | |
| N2 | 0.2584 (6) | 0.6497 (3) | −0.05747 (9) | 0.0258 (5) | |
| H2C | 0.1508 | 0.7327 | −0.0439 | 0.031* | |
| H2D | 0.3992 | 0.7091 | −0.0564 | 0.031* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0276 (17) | 0.0274 (15) | 0.0276 (15) | 0.0006 (14) | 0.0007 (12) | 0.0000 (12) |
| C2 | 0.063 (3) | 0.0399 (17) | 0.0281 (16) | −0.001 (2) | 0.000 (2) | −0.0057 (13) |
| C3 | 0.070 (3) | 0.054 (2) | 0.0271 (16) | −0.003 (2) | 0.0053 (18) | −0.0010 (15) |
| C4 | 0.051 (3) | 0.053 (2) | 0.0328 (17) | −0.0051 (19) | −0.0067 (17) | 0.0146 (16) |
| C5 | 0.041 (2) | 0.0326 (15) | 0.0333 (14) | 0.003 (2) | 0.001 (2) | 0.0071 (12) |
| C6 | 0.0227 (16) | 0.0284 (15) | 0.0283 (14) | 0.0002 (14) | −0.0010 (12) | 0.0013 (11) |
| Cl1 | 0.0211 (4) | 0.0254 (3) | 0.0372 (4) | 0.0006 (4) | 0.0011 (3) | 0.0069 (2) |
| Cl2 | 0.0316 (4) | 0.0339 (4) | 0.0296 (3) | −0.0027 (4) | 0.0000 (4) | −0.0052 (3) |
| Cu1 | 0.0261 (2) | 0.0227 (2) | 0.0245 (2) | 0.00011 (19) | −0.00035 (16) | 0.00093 (11) |
| N1 | 0.0291 (16) | 0.0222 (11) | 0.0303 (12) | 0.0012 (13) | −0.0017 (13) | −0.0018 (9) |
| N2 | 0.0269 (14) | 0.0247 (11) | 0.0259 (11) | 0.0005 (13) | 0.0020 (13) | −0.0030 (9) |
| C1—N1 | 1.467 (4) | C5—C6 | 1.514 (4) |
| C1—C6 | 1.512 (4) | C5—H5A | 0.9700 |
| C1—C2 | 1.516 (4) | C5—H5B | 0.9700 |
| C1—H1 | 0.9800 | C6—N2 | 1.476 (4) |
| C2—C3 | 1.524 (5) | C6—H6 | 0.9800 |
| C2—H2A | 0.9700 | Cl1—Cu1 | 2.3047 (8) |
| C2—H2B | 0.9700 | Cl2—Cu1 | 2.2832 (8) |
| C3—C4 | 1.507 (6) | Cu1—N1 | 2.006 (2) |
| C3—H3A | 0.9700 | Cu1—N2 | 2.016 (2) |
| C3—H3B | 0.9700 | N1—H1A | 0.9000 |
| C4—C5 | 1.523 (4) | N1—H1B | 0.9000 |
| C4—H4A | 0.9700 | N2—H2C | 0.9000 |
| C4—H4B | 0.9700 | N2—H2D | 0.9000 |
| N1—C1—C6 | 107.6 (2) | C6—C5—H5B | 109.5 |
| N1—C1—C2 | 114.1 (3) | C4—C5—H5B | 109.5 |
| C6—C1—C2 | 112.1 (3) | H5A—C5—H5B | 108.1 |
| N1—C1—H1 | 107.6 | N2—C6—C1 | 107.5 (2) |
| C6—C1—H1 | 107.6 | N2—C6—C5 | 115.1 (2) |
| C2—C1—H1 | 107.6 | C1—C6—C5 | 111.4 (3) |
| C1—C2—C3 | 110.9 (3) | N2—C6—H6 | 107.5 |
| C1—C2—H2A | 109.5 | C1—C6—H6 | 107.5 |
| C3—C2—H2A | 109.4 | C5—C6—H6 | 107.5 |
| C1—C2—H2B | 109.4 | N1—Cu1—N2 | 84.03 (9) |
| C3—C2—H2B | 109.4 | N1—Cu1—Cl2 | 178.92 (9) |
| H2A—C2—H2B | 108.0 | N2—Cu1—Cl2 | 95.67 (6) |
| C4—C3—C2 | 111.7 (3) | N1—Cu1—Cl1 | 87.31 (7) |
| C4—C3—H3A | 109.3 | N2—Cu1—Cl1 | 171.15 (7) |
| C2—C3—H3A | 109.3 | Cl2—Cu1—Cl1 | 93.02 (3) |
| C4—C3—H3B | 109.3 | C1—N1—Cu1 | 109.99 (18) |
| C2—C3—H3B | 109.3 | C1—N1—H1A | 109.7 |
| H3A—C3—H3B | 107.9 | Cu1—N1—H1A | 109.7 |
| C3—C4—C5 | 111.5 (3) | C1—N1—H1B | 109.7 |
| C3—C4—H4A | 109.3 | Cu1—N1—H1B | 109.7 |
| C5—C4—H4A | 109.3 | H1A—N1—H1B | 108.2 |
| C3—C4—H4B | 109.3 | C6—N2—Cu1 | 108.75 (16) |
| C5—C4—H4B | 109.3 | C6—N2—H2C | 109.9 |
| H4A—C4—H4B | 108.0 | Cu1—N2—H2C | 109.9 |
| C6—C5—C4 | 110.8 (3) | C6—N2—H2D | 109.9 |
| C6—C5—H5A | 109.5 | Cu1—N2—H2D | 109.9 |
| C4—C5—H5A | 109.5 | H2C—N2—H2D | 108.3 |
The authors are grateful to the Starter Fund of Southeast University for financial support.
Bruker (2000). SMART (Version 5.625), SAINT (Version 6.01), SHELXTL (Version 6.10) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
Choi, K. Y., Kim, Y. J., Ryu, H. & Suh, I. H. (1999). Inorg. Chem. Commun. 2, 176–180.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Khokhar, A. R., Xu, Q. & Al-Baker, S. (1993). J. Inorg. Biochem. 52, 51–58.
Pavlova, S. V., Wen, Y.-S. & Chan, S. I. (2003). Acta Cryst. E59, m792–m793.
Spingler, B., Whittington, D. A. & Lippard, S. J. (2001). Inorg. Chem. 40, 5596–5602.
cis-Diamminedichloroplatinum(II) received FDA approval in 1979 for use as an anticancer drug (Spingler, et al., 2001). Since then, scientists have paid much attention to coordination compounds including diamino coordination sites. Diaminocyclohexane is one of the ligands strongly attracting scientists (Khokhar, et al., 1993). A number of coordination compounds were synthesized by using diaminocyclohexane reacting with all kinds of metals (Choi, et al., 1999). Furthermore, diaminocyclohexane is an excellent chiral source, so its coordination compounds are broadly applied in catalysis. Herein we describe the crystal structure of title compound(I).
The molecule of the title complex, (I) (Fig. 1), is unsymmetrical. The Cu atoms in (I) are coordinated by the two amino groups of the organic ligand as well as by two chloro ligands in an almost square planar geometry. The bond lengths and angles in (I) are within normal ranges (Pavlova, et al., 2003). In (I) the Cu1–N1 and Cu1–N2 bond lengths of 2.006 (2) and 2.016 (2) Å are slightly shorter than that of Dichloro-(trans-(1R,2R)-N,N,N',N'-tetramethylcyclohexane-1,2-diamine)- copper(ii) (II) (Pavlova, et al., 2002), but the Cu1–Cl1 and Cu1–Cl2 bond lengths of 2.3047 (8) and 2.2832 (8) Å are slightly longer than that of (II). This is considered to be caused by the different packing type and different coordination mode of the chloro ligands. In the molecule there are two chiral carbon atoms C1 and C6 both adopting S configuration. In the crystal packing the Cl1 atom plays an important role acting as a bridge linking neighboring molecular units to form a polymeric one-dimensional ladderlike structure (Fig.2). The corresponding copper chlorine bond lengths are significantly longer than the bonds described above leading to a highly Jahn–Teller distorted octahedral coordination mode of the copper atoms in the crystal structure of (I).