Chloridobis[2-(1,5-dimethyl-1H-pyrazol-3-yl-κN 2)-1-methyl-1H-imidazole-κN 3]copper(II) chloride methanol hemisolvate tetra­hydrate

Lhoussaine El Ghayati; El Mostafa Tjiou; Lahcen El Ammari

doi:10.1107/S1600536810000048

. 2010 Jan 9;66(Pt 2):m134–m135. doi: 10.1107/S1600536810000048

Chloridobis[2-(1,5-dimethyl-1H-pyrazol-3-yl-κN ²)-1-methyl-1H-imidazole-κN ³]copper(II) chloride methanol hemisolvate tetrahydrate

Lhoussaine El Ghayati ^a, El Mostafa Tjiou ^a, Lahcen El Ammari ^b,^*

PMCID: PMC2979776 PMID: 21579617

Abstract

In the title compound, [CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₃OH·4H₂O, the Cu^II ion adopts a distorted trigonal-bipyramidal coordination arising from two bidentate ligands and a Cl⁻ anion. The two heterocyclic ligands are planar with dihedral angles of 3.4 (1) and 0.7 (1)° between the pyrazole and imidazole rings. In the crystal, water molecules and uncoordinated chloride anions form an O—H⋯Cl and O—H⋯O hydrogen-bonded sheet parallel to (100) which lies between two layers of complex molecules. The packing is further stabilized by C—H⋯Cl and C—H⋯O hydrogen bonds. The methanol solvent molecule is disordered across a centre of inversion.

Related literature

For applications of transition metal complexes with biheterocyclic ligands, see: Allen & Wilson (1963 ▶); El-Khawass & Bistawroos (1990 ▶); Pearson (1975 ▶); Trofimenko (1993 ▶); Tsuboi et al. (1994 ▶); Hartfiel et al. (1993 ▶). For the preparation of biheterocyclic ligands, see: Tjiou et al. (1989 ▶); Bouhaddioui (1993 ▶).

Experimental

Crystal data

[CuCl(C₉H₁₂N₄)₂]Cl·0.5CH₄O·4H₂O
M _r = 574.98
Monoclinic,
a = 12.5213 (3) Å
b = 15.5386 (4) Å
c = 14.1806 (4) Å
β = 100.883 (1)°
V = 2709.40 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 298 K
0.44 × 0.33 × 0.19 mm

Data collection

Bruker X8 APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.668, T _max = 0.820
47954 measured reflections
7884 independent reflections
5480 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.124
S = 1.01
7884 reflections
323 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia,1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810000048/ci2996sup1.cif

e-66-0m134-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000048/ci2996Isup2.hkl

e-66-0m134-Isup2.hkl^{(385.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cu1—N1	1.9531 (17)
Cu1—N5	1.9545 (17)
Cu1—N4	2.2161 (14)
Cu1—N8	2.2415 (14)
Cu1—Cl1	2.2739 (6)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl2ⁱ	0.85	2.33	3.162 (2)	167
O1—H1B⋯Cl2	0.84	2.34	3.186 (2)	175
O2—H2A⋯Cl2	0.83	2.39	3.205 (3)	165
O3—H3B⋯Cl2ⁱⁱ	0.85	2.38	3.234 (3)	174
O4—H4A⋯O1	0.84	1.98	2.793 (3)	165
O4—H4B⋯O2ⁱⁱⁱ	0.83	1.89	2.706 (4)	165
C11—H11⋯Cl2^iv	0.93	2.75	3.592 (2)	151
C18—H18C⋯Cl1^v	0.96	2.76	3.708 (3)	177

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for making this work possible. They also thank H. Zouihri for his helpful technical assistance during the X-ray measurements.

supplementary crystallographic information

Comment

The ability of biheterocycles to form stable and biochemically interesting complexes, with transition metals has prompted several researchers to test them in several areas: medicine (El-Khawass & Bistawroos, 1990, Trofimenko, 1993), agriculture (Tsuboi et al., 1994, Hartfiel et al., 1993) and the photography industry (Allen & Wilson, 1963; Pearson, 1975). To contribute to the understanding of interaction of these heterocyclic compounds with transition metals, we have studied a copper complex of a biheterocycle prepared by Tjiou et al. (1989) and methylated using phase transfer catalysis process (Bouhaddioui, 1993).

The Cu^II ion adopts a distorted trigonal bipyramidal coordination arising from two bidentate ligands and a Cl^- anion (Fig. 1). The axial positions are occupied by N1 and N5 [N1—Cu1—N5 = 173.03 (7)°], while atoms Cu1, Cl1, N4 and N8 lie in the equatorial plane [N4—Cu1—Cl1 = 128.60 (4)°, N8—Cu1—Cl1 = 132.50 (4)° and N4—Cu1—N8 = 98.90 (6)°]. The two organic ligands are almost planar; the dihedral angle between N1/C1/C2/N2/C3 and N3/N4/C4-C6 planes is 3.4 (1)° and that between N5/C10/C11/N6/C12 and N7/N8/C13-C15 planes is 0.7 (1)°.

In the crystal, the water molecules and uncoordinated chloride ions form a O—H···Cl and O—H···O hydrogen-bonded sheet parallel to the (100) and it lies between two layers of complex molecules. The packing is further stabilized by C—H···Cl and C—H···O hydrogen bonds (Table 2 and Fig.2).

Experimental

The title compound was synthesized by mixing a solution of biheterocycle in methanol and an aqueous solution of cupric chloride with a ligand/metal ratio of 2. Heating was maintained for few minutes until dissolution of all ligand. Then a pinch of NaCl was added and the heating was continued. When the solution became clear, it was left to stand at room temperature. After a few days, green crystals were collected by filtration. They were dried over P₂O₅ in a desiccator for 48 h.