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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021654/im2011sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021654/im2011Isup2.hkl
Contains datablock I

CCDC reference: 650610

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.031
  • wR factor = 0.082
  • Data-to-parameter ratio = 18.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1B ... ?
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.99 From the CIF: _reflns_number_total 1884 Count of symmetry unique reflns 1139 Completeness (_total/calc) 165.41% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 745 Fraction of Friedel pairs measured 0.654 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6 = . S PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.09
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

For related literature, see: Choi et al. (1999); Khokhar et al. (1993); Spingler et al. (2001); Pavlova et al. (2003).

Experimental top

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.

Refinement top

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).

Structure description top

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).

For related literature, see: Choi et al. (1999); Khokhar et al. (1993); Spingler et al. (2001); Pavlova et al. (2003).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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
catena-Poly[[chlorido[(1S,2S)-cyclohexane-1,2-diamine-κ2N,N']copper(II)]- µ3-chlorido] top
Crystal data top
[CuCl2(C6H14N2)]F(000) = 508
Mr = 248.63Dx = 1.711 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 875 reflections
a = 5.704 (1) Åθ = 2.1–25.2°
b = 6.819 (1) ŵ = 2.76 mm1
c = 24.823 (4) ÅT = 296 K
V = 965.5 (3) Å3Square, blue
Z = 40.20 × 0.20 × 0.12 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
1884 independent reflections
Radiation source: sealed tube1766 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
φ and ω scansθmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 67
Tmin = 0.58, Tmax = 0.72k = 88
5714 measured reflectionsl = 3030
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.082 w = 1/[σ2(Fo2) + (0.05P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1884 reflectionsΔρmax = 0.69 e Å3
100 parametersΔρmin = 0.55 e Å3
0 restraintsAbsolute structure: Flack (1983), 744 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.011 (19)
Crystal data top
[CuCl2(C6H14N2)]V = 965.5 (3) Å3
Mr = 248.63Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.704 (1) ŵ = 2.76 mm1
b = 6.819 (1) ÅT = 296 K
c = 24.823 (4) Å0.20 × 0.20 × 0.12 mm
Data collection top
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 = 0.72Rint = 0.044
5714 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.082Δρmax = 0.69 e Å3
S = 1.03Δρmin = 0.55 e Å3
1884 reflectionsAbsolute structure: Flack (1983), 744 Friedel pairs
100 parametersAbsolute structure parameter: 0.011 (19)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3284 (6)0.4129 (4)0.12770 (12)0.0275 (7)
H10.49650.44230.12640.033*
C20.2723 (9)0.3424 (5)0.18417 (11)0.0435 (9)
H2A0.10970.30110.18580.052*
H2B0.36980.23010.19280.052*
C30.3145 (9)0.5042 (6)0.22536 (13)0.0506 (12)
H3A0.48100.53250.22720.061*
H3B0.26470.45930.26060.061*
C40.1835 (8)0.6890 (6)0.21115 (13)0.0455 (10)
H4A0.01630.66470.21350.055*
H4B0.22270.79090.23690.055*
C50.2436 (8)0.7590 (4)0.15455 (11)0.0356 (7)
H5A0.40740.79690.15310.043*
H5B0.14960.87320.14580.043*
C60.1980 (5)0.5989 (4)0.11358 (12)0.0265 (7)
H60.03000.56900.11460.032*
Cl10.26572 (14)0.09330 (9)0.02474 (3)0.02790 (17)
Cl20.26008 (16)0.55471 (10)0.06844 (3)0.03167 (19)
Cu10.26675 (7)0.40155 (4)0.013331 (12)0.02443 (14)
N10.2789 (6)0.2686 (3)0.08535 (8)0.0272 (6)
H1A0.39150.17610.08520.033*
H1B0.14080.20950.09200.033*
N20.2584 (6)0.6497 (3)0.05747 (9)0.0258 (5)
H2C0.15080.73270.04390.031*
H2D0.39920.70910.05640.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0276 (17)0.0274 (15)0.0276 (15)0.0006 (14)0.0007 (12)0.0000 (12)
C20.063 (3)0.0399 (17)0.0281 (16)0.001 (2)0.000 (2)0.0057 (13)
C30.070 (3)0.054 (2)0.0271 (16)0.003 (2)0.0053 (18)0.0010 (15)
C40.051 (3)0.053 (2)0.0328 (17)0.0051 (19)0.0067 (17)0.0146 (16)
C50.041 (2)0.0326 (15)0.0333 (14)0.003 (2)0.001 (2)0.0071 (12)
C60.0227 (16)0.0284 (15)0.0283 (14)0.0002 (14)0.0010 (12)0.0013 (11)
Cl10.0211 (4)0.0254 (3)0.0372 (4)0.0006 (4)0.0011 (3)0.0069 (2)
Cl20.0316 (4)0.0339 (4)0.0296 (3)0.0027 (4)0.0000 (4)0.0052 (3)
Cu10.0261 (2)0.0227 (2)0.0245 (2)0.00011 (19)0.00035 (16)0.00093 (11)
N10.0291 (16)0.0222 (11)0.0303 (12)0.0012 (13)0.0017 (13)0.0018 (9)
N20.0269 (14)0.0247 (11)0.0259 (11)0.0005 (13)0.0020 (13)0.0030 (9)
Geometric parameters (Å, º) top
C1—N11.467 (4)C5—C61.514 (4)
C1—C61.512 (4)C5—H5A0.9700
C1—C21.516 (4)C5—H5B0.9700
C1—H10.9800C6—N21.476 (4)
C2—C31.524 (5)C6—H60.9800
C2—H2A0.9700Cl1—Cu12.3047 (8)
C2—H2B0.9700Cl2—Cu12.2832 (8)
C3—C41.507 (6)Cu1—N12.006 (2)
C3—H3A0.9700Cu1—N22.016 (2)
C3—H3B0.9700N1—H1A0.9000
C4—C51.523 (4)N1—H1B0.9000
C4—H4A0.9700N2—H2C0.9000
C4—H4B0.9700N2—H2D0.9000
N1—C1—C6107.6 (2)C6—C5—H5B109.5
N1—C1—C2114.1 (3)C4—C5—H5B109.5
C6—C1—C2112.1 (3)H5A—C5—H5B108.1
N1—C1—H1107.6N2—C6—C1107.5 (2)
C6—C1—H1107.6N2—C6—C5115.1 (2)
C2—C1—H1107.6C1—C6—C5111.4 (3)
C1—C2—C3110.9 (3)N2—C6—H6107.5
C1—C2—H2A109.5C1—C6—H6107.5
C3—C2—H2A109.4C5—C6—H6107.5
C1—C2—H2B109.4N1—Cu1—N284.03 (9)
C3—C2—H2B109.4N1—Cu1—Cl2178.92 (9)
H2A—C2—H2B108.0N2—Cu1—Cl295.67 (6)
C4—C3—C2111.7 (3)N1—Cu1—Cl187.31 (7)
C4—C3—H3A109.3N2—Cu1—Cl1171.15 (7)
C2—C3—H3A109.3Cl2—Cu1—Cl193.02 (3)
C4—C3—H3B109.3C1—N1—Cu1109.99 (18)
C2—C3—H3B109.3C1—N1—H1A109.7
H3A—C3—H3B107.9Cu1—N1—H1A109.7
C3—C4—C5111.5 (3)C1—N1—H1B109.7
C3—C4—H4A109.3Cu1—N1—H1B109.7
C5—C4—H4A109.3H1A—N1—H1B108.2
C3—C4—H4B109.3C6—N2—Cu1108.75 (16)
C5—C4—H4B109.3C6—N2—H2C109.9
H4A—C4—H4B108.0Cu1—N2—H2C109.9
C6—C5—C4110.8 (3)C6—N2—H2D109.9
C6—C5—H5A109.5Cu1—N2—H2D109.9
C4—C5—H5A109.5H2C—N2—H2D108.3

Experimental details

Crystal data
Chemical formula[CuCl2(C6H14N2)]
Mr248.63
Crystal system, space groupOrthorhombic, P212121
Temperature (K)296
a, b, c (Å)5.704 (1), 6.819 (1), 24.823 (4)
V3)965.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.76
Crystal size (mm)0.20 × 0.20 × 0.12
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.58, 0.72
No. of measured, independent and
observed [I > 2σ(I)] reflections
5714, 1884, 1766
Rint0.044
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.082, 1.03
No. of reflections1884
No. of parameters100
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.69, 0.55
Absolute structureFlack (1983), 744 Friedel pairs
Absolute structure parameter0.011 (19)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

 

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