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Acta Cryst. (2007). E63, m1657-m1658    [ doi:10.1107/S1600536807022684 ]

Hexakis(1H-imidazole-[kappa]N3)copper(II) dichloride tetrahydrate

Y.-M. Yang, T.-T. Zhu, P.-C. Lu and C.-H. Liu

Abstract top

The centrosymmetric title complex, [Cu(C3H4N2)6]Cl2·4H2O, has a distorted octahedral coordination geometry. There is extensive hydrogen bonding involving the cations, anions and water molecules.

Comment top

Organic compounds containing an imidazole group are widespread in nature. In recent years, many transition metal complexes with imidazole molecules or anions, or their analogues, were reported. They include complexes of copper(II) (Zhu et al., 2000, 1998; Zhu, Hang et al., 1999; Zhu, Tong et al., 1999; Zhu, Bu et al., 1999; Liu et al., 1999), silver(I) (Yang et al., 2000; Liu et al., 2005), zinc(II) (Zhu, Zheng et al., 1999), iron(II) (Yang et al., 2001a), manganese(II) (Yang et al., 2001b) and cobalt(II) (Zhu et al., 2003). We report here the crystal structure of the title copper(II) complex, (I).

The title complex is a mononuclear copper(II) complex, similar to the cobalt(II) complex reported by Zhu et al. (2003). The asymmetric unit consists of half the complex dication, a chloride anion and two water molecules; the cation is centrosymmetric. In the cation, the central copper(II) atom is coordinated by six nitrogen atoms from six imidazole ligands, forming a slightly distorted octahedral geometry around the metal. The average Mn—N bond length is 2.168 (3) Å. The dihedral angles between pairs of imidazole rings in the asymmetric unit are 89.3 (3), 85.0 (3) and 84.4 (3)°, the ligands being almost perpendicular to one another.

All the non-coordinated nitrogen atoms in imidazole ligands, the water molecules and chloride anions participate in the stabilization of the crystal structure by the formation of hydrogen bonds, which form a hydrophilic chain along the a axis, these chains being connected in a two-dimensional layer in the ab plane.

Related literature top

For related literature, see: Liu & Zhu (2005); Liu et al. (1999); Yang et al. (2000, 2001); Zhu et al. (1998, 1999a,b,c, 2000, 2003).

For related literature, see: Bu (1999).

Experimental top

In a similar procedure to that of Zhu et al. (2003) the title complex was prepared as follows. CuCl2.6H2O and six equivalents of imidazole were dissoved in water, with stirring for a few minutes to obtain a clear pale-pink solution. After allowing the resulting solution to stand in air for 3 days, dark blue crystals were formed. These crystals were isolated, washed with water three times and dried in a vacuum desiccator using CaCl2 (yield 56%).

Refinement top

C– and N-bound H atoms were included in the riding model approximation with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). H atoms of water were located in a difference map and refined as riding in their as-found relative positions, with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); 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: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. [Symmetry code for unlabelled atoms: -x, -y, -z.]
Hexakis(1H-imidazole-κN3)copper(II) dichloride tetrahydrate top
Crystal data top
[Cu(C3H4N2)6]Cl2·4H2OZ = 1
Mr = 615.00F(000) = 319
Triclinic, P1Dx = 1.423 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.783 (4) ÅCell parameters from 718 reflections
b = 9.064 (4) Åθ = 3.4–26.1°
c = 10.576 (5) ŵ = 0.99 mm−1
α = 75.156 (5)°T = 298 K
β = 83.105 (6)°Prism, dark blue
γ = 61.848 (5)°0.42 × 0.35 × 0.21 mm
V = 717.6 (5) Å3
Data collection top
Bruker APEX area-detector
diffractometer		2498 independent reflections
Radiation source: fine-focus sealed tube2190 reflections with I > 2σ(I)
graphiteRint = 0.021
φ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→9
Tmin = 0.680, Tmax = 0.819k = −10→6
3756 measured reflectionsl = −12→12
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.0908P)2 + 0.8952P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.005
2498 reflectionsΔρmax = 0.51 e Å−3
170 parametersΔρmin = −0.87 e Å−3
48 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.049 (6)
Crystal data top
[Cu(C3H4N2)6]Cl2·4H2Oγ = 61.848 (5)°
Mr = 615.00V = 717.6 (5) Å3
Triclinic, P1Z = 1
a = 8.783 (4) ÅMo Kα radiation
b = 9.064 (4) ŵ = 0.99 mm−1
c = 10.576 (5) ÅT = 298 K
α = 75.156 (5)°0.42 × 0.35 × 0.21 mm
β = 83.105 (6)°
Data collection top
Bruker APEX area-detector
diffractometer		2498 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2190 reflections with I > 2σ(I)
Tmin = 0.680, Tmax = 0.819Rint = 0.021
3756 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.150Δρmax = 0.51 e Å−3
S = 1.06Δρmin = −0.87 e Å−3
2498 reflectionsAbsolute structure: ?
170 parametersFlack parameter: ?
48 restraintsRogers parameter: ?
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
Cu10.00000.00000.00000.0332 (2)
Cl10.69768 (12)0.79338 (11)0.50423 (8)0.0418 (3)
O10.0404 (4)0.8257 (5)0.5269 (4)0.0714 (10)
O20.6643 (5)0.4581 (5)0.5131 (5)0.0899 (13)
N1−0.1959 (3)0.1465 (4)0.1260 (3)0.0319 (6)
N2−0.3870 (4)0.2053 (5)0.2829 (3)0.0519 (9)
H2A−0.44610.19020.35140.062*
N3−0.0032 (4)0.2346 (3)−0.1173 (3)0.0332 (6)
N4−0.0732 (5)0.4703 (4)−0.2703 (3)0.0504 (8)
H4A−0.12350.5506−0.33770.061*
N50.2019 (4)−0.0357 (4)0.1215 (3)0.0332 (6)
N60.3312 (5)−0.0241 (5)0.2801 (3)0.0539 (9)
H6A0.34520.00260.34870.065*
C1−0.2612 (5)0.0824 (5)0.2301 (3)0.0410 (8)
H1A−0.2245−0.03460.26330.049*
C2−0.4041 (6)0.3573 (6)0.2089 (5)0.0577 (11)
H2B−0.48170.46580.22190.069*
C3−0.2864 (5)0.3210 (5)0.1122 (4)0.0448 (9)
H3−0.26930.40210.04630.054*
C4−0.0987 (5)0.3335 (5)−0.2216 (4)0.0414 (8)
H4B−0.17500.3103−0.25690.050*
C50.0465 (7)0.4602 (6)−0.1943 (5)0.0612 (12)
H50.09070.5378−0.20520.073*
C60.0887 (6)0.3155 (5)−0.0997 (4)0.0471 (9)
H6B0.16780.2764−0.03290.057*
C70.1798 (5)0.0280 (5)0.2244 (3)0.0421 (8)
H70.07300.09990.25470.051*
C80.4565 (6)−0.1244 (7)0.2111 (5)0.0621 (12)
H80.5745−0.17820.22760.075*
C90.3774 (5)−0.1326 (5)0.1113 (4)0.0483 (10)
H90.4332−0.19370.04710.058*
H2C0.75830.36680.50130.058*
H2D0.68720.54390.51680.058*
H1B−0.05230.81610.50770.058*
H1C0.05800.89510.45350.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0342 (4)0.0354 (4)0.0281 (4)−0.0153 (3)−0.0008 (2)−0.0049 (2)
Cl10.0435 (5)0.0408 (5)0.0364 (5)−0.0184 (4)−0.0006 (4)−0.0030 (4)
O10.060 (2)0.078 (2)0.089 (3)−0.0377 (18)0.0101 (18)−0.032 (2)
O20.066 (2)0.060 (2)0.149 (4)−0.0246 (18)−0.017 (2)−0.032 (2)
N10.0310 (14)0.0371 (15)0.0268 (14)−0.0147 (12)0.0018 (11)−0.0087 (11)
N20.0462 (19)0.070 (2)0.0433 (19)−0.0285 (18)0.0206 (15)−0.0249 (17)
N30.0340 (14)0.0312 (14)0.0311 (15)−0.0142 (12)0.0022 (11)−0.0044 (11)
N40.056 (2)0.0385 (17)0.0444 (19)−0.0190 (16)−0.0075 (15)0.0091 (14)
N50.0336 (14)0.0370 (15)0.0293 (14)−0.0173 (12)−0.0038 (11)−0.0043 (12)
N60.063 (2)0.078 (3)0.0386 (18)−0.042 (2)−0.0065 (16)−0.0184 (17)
C10.044 (2)0.049 (2)0.0308 (18)−0.0229 (17)0.0067 (15)−0.0102 (16)
C20.049 (2)0.051 (2)0.062 (3)−0.011 (2)0.014 (2)−0.025 (2)
C30.048 (2)0.0379 (19)0.041 (2)−0.0154 (17)0.0072 (17)−0.0102 (16)
C40.042 (2)0.0377 (19)0.0373 (19)−0.0174 (16)−0.0045 (15)0.0026 (15)
C50.081 (3)0.047 (2)0.063 (3)−0.040 (2)−0.008 (2)0.002 (2)
C60.057 (2)0.044 (2)0.044 (2)−0.0297 (19)−0.0087 (18)0.0009 (17)
C70.048 (2)0.049 (2)0.0325 (19)−0.0238 (18)−0.0025 (15)−0.0122 (16)
C80.043 (2)0.092 (4)0.058 (3)−0.032 (2)−0.010 (2)−0.020 (3)
C90.0352 (19)0.062 (3)0.046 (2)−0.0175 (18)−0.0042 (16)−0.0167 (19)
Geometric parameters (Å, °) top
Cu1—N3i2.159 (3)N4—H4A0.860
Cu1—N32.159 (3)N5—C71.312 (5)
Cu1—N52.167 (3)N5—C91.375 (5)
Cu1—N5i2.167 (3)N6—C81.331 (6)
Cu1—N12.168 (3)N6—C71.338 (5)
Cu1—N1i2.168 (3)N6—H6A0.860
O1—H1B0.9101C1—H1A0.930
O1—H1C0.9139C2—C31.349 (6)
O2—H2C0.8751C2—H2B0.930
O2—H2D0.9011C3—H30.930
N1—C11.309 (5)C4—H4B0.930
N1—C31.371 (5)C5—C61.348 (6)
N2—C11.335 (5)C5—H50.930
N2—C21.347 (6)C6—H6B0.930
N2—H2A0.860C7—H70.930
N3—C41.315 (5)C8—C91.367 (6)
N3—C61.375 (5)C8—H80.930
N4—C41.327 (5)C9—H90.930
N4—C51.354 (6)
N3i—Cu1—N3180C9—N5—Cu1128.2 (2)
N3i—Cu1—N589.82 (11)C8—N6—C7108.4 (3)
N3—Cu1—N590.18 (11)C8—N6—H6A125.8
N3i—Cu1—N5i90.18 (11)C7—N6—H6A125.8
N3—Cu1—N5i89.82 (11)N1—C1—N2111.8 (4)
N5—Cu1—N5i180N1—C1—H1A124.1
N3i—Cu1—N190.37 (11)N2—C1—H1A124.1
N3—Cu1—N189.63 (11)N2—C2—C3106.4 (4)
N5—Cu1—N190.61 (11)N2—C2—H2B126.8
N5i—Cu1—N189.39 (11)C3—C2—H2B126.8
N3i—Cu1—N1i89.63 (11)C2—C3—N1109.6 (4)
N3—Cu1—N1i90.37 (11)C2—C3—H3125.2
N5—Cu1—N1i89.39 (11)N1—C3—H3125.2
N5i—Cu1—N1i90.61 (11)N3—C4—N4111.8 (3)
N1—Cu1—N1i180N3—C4—H4B124.1
H1B—O1—H1C104.9N4—C4—H4B124.1
H2C—O2—H2D111.6C6—C5—N4106.4 (4)
C1—N1—C3104.9 (3)C6—C5—H5126.8
C1—N1—Cu1125.6 (3)N4—C5—H5126.8
C3—N1—Cu1129.4 (2)C5—C6—N3109.4 (4)
C1—N2—C2107.3 (3)C5—C6—H6B125.3
C1—N2—H2A126.4N3—C6—H6B125.3
C2—N2—H2A126.4N5—C7—N6111.0 (3)
C4—N3—C6104.9 (3)N5—C7—H7124.5
C4—N3—Cu1126.5 (3)N6—C7—H7124.5
C6—N3—Cu1128.6 (2)N6—C8—C9106.4 (4)
C4—N4—C5107.4 (3)N6—C8—H8126.8
C4—N4—H4A126.3C9—C8—H8126.8
C5—N4—H4A126.3C8—C9—N5108.8 (4)
C7—N5—C9105.5 (3)C8—C9—H9125.6
C7—N5—Cu1126.3 (2)N5—C9—H9125.6
N3i—Cu1—N1—C11.5 (3)N3—Cu1—N5—C9−95.5 (3)
N3—Cu1—N1—C1−178.5 (3)N5i—Cu1—N5—C9−51 (8)
N5—Cu1—N1—C1−88.3 (3)N1—Cu1—N5—C9174.9 (3)
N5i—Cu1—N1—C191.7 (3)N1i—Cu1—N5—C9−5.1 (3)
N1i—Cu1—N1—C1119.8 (3)C3—N1—C1—N2−0.1 (4)
N3i—Cu1—N1—C3−173.6 (3)Cu1—N1—C1—N2−176.1 (2)
N3—Cu1—N1—C36.4 (3)C2—N2—C1—N10.0 (5)
N5—Cu1—N1—C396.6 (3)C1—N2—C2—C30.0 (5)
N5i—Cu1—N1—C3−83.4 (3)N2—C2—C3—N10.0 (5)
N1i—Cu1—N1—C3−55.2 (3)C1—N1—C3—C20.1 (5)
N3i—Cu1—N3—C457 (100)Cu1—N1—C3—C2175.9 (3)
N5—Cu1—N3—C4177.5 (3)C6—N3—C4—N40.0 (4)
N5i—Cu1—N3—C4−2.5 (3)Cu1—N3—C4—N4178.8 (2)
N1—Cu1—N3—C4−91.9 (3)C5—N4—C4—N30.4 (5)
N1i—Cu1—N3—C488.1 (3)C4—N4—C5—C6−0.6 (5)
N3i—Cu1—N3—C6−125 (100)N4—C5—C6—N30.5 (5)
N5—Cu1—N3—C6−4.0 (3)C4—N3—C6—C5−0.3 (5)
N5i—Cu1—N3—C6176.0 (3)Cu1—N3—C6—C5−179.1 (3)
N1—Cu1—N3—C686.7 (3)C9—N5—C7—N6−0.4 (4)
N1i—Cu1—N3—C6−93.3 (3)Cu1—N5—C7—N6177.6 (2)
N3i—Cu1—N5—C7−93.0 (3)C8—N6—C7—N50.3 (5)
N3—Cu1—N5—C787.0 (3)C7—N6—C8—C9−0.1 (5)
N5i—Cu1—N5—C7131 (8)N6—C8—C9—N5−0.2 (5)
N1—Cu1—N5—C7−2.6 (3)C7—N5—C9—C80.3 (5)
N1i—Cu1—N5—C7177.4 (3)Cu1—N5—C9—C8−177.6 (3)
N3i—Cu1—N5—C984.5 (3)
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2D···Cl10.902.283.165 (4)169
O2—H2C···O1ii0.881.872.743 (5)179
O1—H1C···O1iii0.912.312.805 (7)113
O1—H1B···Cl1iv0.912.313.201 (4)168
N6—H6A···Cl1ii0.862.583.383 (4)156
N4—H4A···Cl1v0.862.363.214 (3)170
N2—H2A···Cl1vi0.862.503.320 (4)161
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y+2, −z+1; (iv) x−1, y, z; (v) x−1, y, z−1; (vi) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2D···Cl10.902.283.165 (4)169
O2—H2C···O1i0.881.872.743 (5)179
O1—H1C···O1ii0.912.312.805 (7)113
O1—H1B···Cl1iii0.912.313.201 (4)168
N6—H6A···Cl1i0.862.583.383 (4)156
N4—H4A···Cl1iv0.862.363.214 (3)170
N2—H2A···Cl1v0.862.503.320 (4)161
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) x−1, y, z; (iv) x−1, y, z−1; (v) −x, −y+1, −z+1.
Acknowledgements top

The work was supported by the Analytical Test Fund for Dr Chang-Hong Liu in Nanjing University.

references
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