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metal-organic compounds
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017264/cv6210sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017264/cv6210Isup2.hkl |
CCDC reference: 222822
![[sigma]](https://journals.iucr.org/logos/entities/sigma_rmgif.gif){kind=small}
(C-C) = 0.012 Å
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trans-(1R,2R)-N,N,N',N'-Tetramethylcyclohexane-1,2-diamine was synthesized from commercially available (1R)-trans-1,2-cyclohexanediamine (Aldrich) using the Eschweiler–Clark methylation of amines method (Remenar et al., 1997). [Cu(CH3CN)4]ClO4 was prepared according to a published procedure (Gill et al., 1995). Equimolar amount of [Cu(CH3CN)4]ClO4 (0.05 g, 0.15 mmol) and L (0.028 ml, 0.15 mmol) were combined in a 10 ml of a dry CH3CN/CH2Cl2 (3:1, v/v) mixture under argon. The resulting colorless solution turned blue–green, while stirring for 1 d at room temperature under argon. The products were tprecipitated with 50 ml of dry diethyl ether to give 0.30 g (66%) of a blue–green powder. Recrystallization from a dichloromethane/acetonitrile (4:1, v/v) mixture, followed by slow diffusion of cyclohexane into a CH3CN solution, afforded dark-blue crystals of the title compound, (I).
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](https://journals.iucr.org/e/issues/2003/09/00/cv6210/cv6210fig1thm.gif)
| Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids, showing the atom-numbering scheme employed. H atoms are shown as small spheres of the arbitrary radii. Fig. 2. The packing diagram for (I), viewed along the c axis. H atoms have been ommited for clarity. |
| [CuCl2(C10H22N2)] | F(000) = 318 |
| Mr = 304.74 | Dx = 1.528 Mg m−3 |
| Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: C 2y | Cell parameters from 24 reflections |
| a = 8.8574 (8) Å | θ = 8.7–17.1° |
| b = 10.595 (1) Å | µ = 2.03 mm−1 |
| c = 8.0634 (5) Å | T = 300 K |
| β = 118.939 (6)° | Prismatic, dark blue |
| V = 662.2 (1) Å3 | 0.44 × 0.31 × 0.25 mm |
| Z = 2 |
| Enraf-Nonius TurboCAD-4 diffractometer | 1225 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.09 |
| Graphite monochromator | θmax = 25.9°, θmin = 2.9° |
| non–profiled ω/2θ scans | h = −10→9 |
| Absorption correction: ψ scan (North et al., 1968) | k = −12→12 |
| Tmin = 0.481, Tmax = 0.603 | l = 0→9 |
| 1379 measured reflections | 2 standard reflections every 60 min |
| 1289 independent reflections | intensity decay: 4% |
| 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)] = 0.039 | H-atom parameters not refined |
| wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0748P)2 + 6.5193P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max < 0.001 |
| 1289 reflections | Δρmax = 0.54 e Å−3 |
| 70 parameters | Δρmin = −0.66 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983) |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.04 (5) |
| [CuCl2(C10H22N2)] | V = 662.2 (1) Å3 |
| Mr = 304.74 | Z = 2 |
| Monoclinic, C2 | Mo Kα radiation |
| a = 8.8574 (8) Å | µ = 2.03 mm−1 |
| b = 10.595 (1) Å | T = 300 K |
| c = 8.0634 (5) Å | 0.44 × 0.31 × 0.25 mm |
| β = 118.939 (6)° |
| Enraf-Nonius TurboCAD-4 diffractometer | 1225 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.09 |
| Tmin = 0.481, Tmax = 0.603 | 2 standard reflections every 60 min |
| 1379 measured reflections | intensity decay: 4% |
| 1289 independent reflections |
| R[F2 > 2σ(F2)] = 0.039 | H-atom parameters not refined |
| wR(F2) = 0.151 | Δρmax = 0.54 e Å−3 |
| S = 1.02 | Δρmin = −0.66 e Å−3 |
| 1289 reflections | Absolute structure: Flack (1983) |
| 70 parameters | Absolute structure parameter: −0.04 (5) |
| 1 restraint |
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 | ||
| Cu | 1.0000 | 0.78932 (10) | 1.0000 | 0.0326 (4) | |
| Cl | 0.9030 (6) | 0.64034 (19) | 0.7735 (4) | 0.0741 (12) | |
| N | 0.8845 (11) | 0.9334 (6) | 0.8097 (10) | 0.0304 (15) | |
| C1 | 0.9094 (8) | 1.0539 (6) | 0.9134 (9) | 0.0305 (14) | |
| H1 | 0.8263 | 1.0551 | 0.9609 | 0.037* | |
| C2 | 0.8805 (11) | 1.1746 (8) | 0.7960 (12) | 0.050 (2) | |
| H2A | 0.9591 | 1.1755 | 0.7442 | 0.060* | |
| H2B | 0.7636 | 1.1752 | 0.6910 | 0.060* | |
| C3 | 0.9097 (9) | 1.2909 (12) | 0.9165 (11) | 0.0548 (18) | |
| H3A | 0.8930 | 1.3659 | 0.8405 | 0.082* | |
| H3B | 0.8264 | 1.2929 | 0.9619 | 0.082* | |
| C4 | 0.6974 (9) | 0.9123 (8) | 0.6817 (10) | 0.0441 (18) | |
| H4A | 0.6505 | 0.9820 | 0.5955 | 0.066* | |
| H4B | 0.6393 | 0.9055 | 0.7556 | 0.066* | |
| H4C | 0.6814 | 0.8357 | 0.6114 | 0.066* | |
| C5 | 0.9686 (11) | 0.9368 (9) | 0.6849 (12) | 0.0486 (19) | |
| H5A | 0.9181 | 1.0032 | 0.5932 | 0.073* | |
| H5B | 0.9508 | 0.8574 | 0.6206 | 0.073* | |
| H5C | 1.0900 | 0.9519 | 0.7616 | 0.073* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu | 0.0299 (5) | 0.0320 (6) | 0.0300 (6) | 0.000 | 0.0099 (4) | 0.000 |
| Cl | 0.104 (3) | 0.0439 (15) | 0.0505 (16) | −0.0036 (15) | 0.0186 (16) | −0.0174 (11) |
| N | 0.033 (3) | 0.035 (3) | 0.017 (3) | 0.001 (3) | 0.007 (3) | 0.000 (2) |
| C1 | 0.024 (3) | 0.035 (4) | 0.028 (3) | 0.003 (2) | 0.009 (3) | 0.004 (3) |
| C2 | 0.042 (4) | 0.045 (5) | 0.050 (5) | 0.008 (3) | 0.012 (4) | 0.019 (4) |
| C3 | 0.053 (4) | 0.038 (3) | 0.078 (5) | 0.003 (7) | 0.035 (4) | 0.011 (7) |
| C4 | 0.027 (4) | 0.063 (5) | 0.028 (4) | −0.003 (3) | 0.002 (3) | 0.005 (3) |
| C5 | 0.044 (4) | 0.063 (5) | 0.041 (4) | 0.007 (4) | 0.022 (4) | 0.000 (4) |
| Cu—Ni | 2.052 (7) | C1—H1 | 1.00 |
| Cu—N | 2.052 (7) | C2—H2A | 1.00 |
| Cu—Cl | 2.247 (2) | C2—H2B | 1.00 |
| Cu—Cli | 2.247 (2) | C3—H3A | 1.00 |
| N—C1 | 1.483 (9) | C3—H3B | 1.00 |
| N—C4 | 1.486 (10) | C4—H4A | 1.00 |
| N—C5 | 1.515 (10) | C4—H4B | 1.00 |
| C1—C2 | 1.537 (9) | C4—H4C | 1.00 |
| C1—C1i | 1.535 (12) | C5—H5A | 1.00 |
| C2—C3 | 1.513 (15) | C5—H5B | 1.00 |
| C3—C3i | 1.512 (15) | C5—H5C | 1.00 |
| Ni—Cu—N | 83.9 (4) | C1—C2—H2A | 115.5 |
| Ni—Cu—Cl | 170.6 (3) | C1—C2—H2B | 108.3 |
| N—Cu—Cl | 93.36 (17) | C3—C2—H2A | 104.6 |
| Ni—Cu—Cli | 93.36 (17) | C3—C2—H2B | 112.7 |
| N—Cu—Cli | 170.6 (3) | H2A—C2—H2B | 104.3 |
| Cl—Cu—Cli | 90.73 (16) | C2—C3—H3A | 118.7 |
| C1—N—C4 | 109.4 (6) | C2—C3—H3B | 110.2 |
| C1—N—C5 | 111.6 (6) | N—C4—H4A | 116.3 |
| C4—N—C5 | 106.5 (6) | N—C4—H4B | 116.2 |
| C1—N—Cu | 109.5 (5) | N—C4—H4C | 111.3 |
| C4—N—Cu | 113.1 (5) | H4A—C4—H4B | 107.8 |
| C5—N—Cu | 106.7 (5) | H4A—C4—H4C | 102.0 |
| N—C1—C2 | 115.7 (6) | H4B—C4—H4C | 101.4 |
| N—C1—C1i | 108.5 (5) | N—C5—H5A | 95.3 |
| C2—C1—C1i | 110.4 (5) | N—C5—H5B | 110.1 |
| C3—C2—C1 | 110.9 (7) | N—C5—H5C | 117.9 |
| C3i—C3—C2 | 110.5 (5) | H5A—C5—H5B | 134.5 |
| N—C1—H1 | 108.9 | H5A—C5—H5C | 87.1 |
| C2—C1—H1 | 99.1 |
| Symmetry code: (i) −x+2, y, −z+2. |
Experimental details
| Crystal data | |
| Chemical formula | [CuCl2(C10H22N2)] |
| Mr | 304.74 |
| Crystal system, space group | Monoclinic, C2 |
| Temperature (K) | 300 |
| a, b, c (Å) | 8.8574 (8), 10.595 (1), 8.0634 (5) |
| β (°) | 118.939 (6) |
| V (Å3) | 662.2 (1) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 2.03 |
| Crystal size (mm) | 0.44 × 0.31 × 0.25 |
| Data collection | |
| Diffractometer | Enraf-Nonius TurboCAD-4 diffractometer |
| Absorption correction | ψ scan (North et al., 1968) |
| Tmin, Tmax | 0.481, 0.603 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 1379, 1289, 1225 |
| Rint | 0.09 |
| (sin θ/λ)max (Å−1) | 0.615 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.151, 1.02 |
| No. of reflections | 1289 |
| No. of parameters | 70 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters not refined |
| Δρmax, Δρmin (e Å−3) | 0.54, −0.66 |
| Absolute structure | Flack (1983) |
| Absolute structure parameter | −0.04 (5) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Copper(I) complexes with biologically relevant amine or mixed pyridyl/amine donors ligands have attracted much attention in recent years as simple models for the biomimetic chemistry of copper-containing proteins, which bind or activate dioxygen (Tolman, 1997; Schindler, 2000; Solomon, 2001). trans-(1R,2R)-N,N,N',N'-Tetramethylcyclohexane-1,2-diamine (L) is of interest because of its preorganized nature for binding a single metal and its chirality. Under argon conditions, L stabilizes copper(I) as a mononuclear trigonal-planar complex, formulated as [LCu(CH3CN)](OTf) (OTf is trifluoromethanesulfonate, which was isolated but has not been structurally characterized (Cole et al., 1996). Our attemps to isolate the [LCu(CH3CN)]ClO4 complex from the reaction of L with [Cu(CH3CN)4]ClO4, resulted in a redox reaction, which produced the title compound, (I), as a major product. The molecular structure of (I) is shown in Fig. 1.
The copper(II) metal center resides at a special twofold symmetry site and displays a distorted square-planar coordination geometry. The Cu—Cl bond length is 2.247 (2) Å and Cu—N is 2.052 (7) Å. The bond angles of the Cu center are: N—Cu—Ni 83.9 (4)°, N—Cu—Cl 93.4 (2)°, N—Cu—Cli 170.6 (3)° and Cl—Cu—Cli 90.7 (2)°. The torsion angle of C1—N—Cu—Cl is 174.9 (3)°. The packing diagram of (I) is illustrated in Fig. 2. As can be seen, the unit cell contains two distinct molecules of (I). According to the interatomic distances there are no hydrogen bonds between adjacent molecules.