Bis[μ-3-ethyl-4-phenyl-5-(2-pyrid­yl)-4H-1,2,4-triazole]bis­[dichloridocopper(II)]

Zuoxiang Wang; Chunyi Liu; Xiaoming Zhang; Xiaoning Gong

doi:10.1107/S160053680804035X

. 2008 Dec 6;65(Pt 1):m22. doi: 10.1107/S160053680804035X

Bis[μ-3-ethyl-4-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole]bis[dichloridocopper(II)]

Zuoxiang Wang ^a,^*, Chunyi Liu ^a, Xiaoming Zhang ^a, Xiaoning Gong ^a

PMCID: PMC2967870 PMID: 21581496

Abstract

The asymmetric unit of the title compound, [Cu₂Cl₄(C₁₅H₁₄N₄)₂], contains two halves of two centrosymmetric dinuclear molecules, A and B. The conformations of the two crystallographically independent molecules are slightly different: in A, the Cu⋯Cu separation is 4.174 (9) Å and the dihedral angle between the triazole and phenyl rings is 74.23 (11)°; these values are 4.137 (9) Å and 68.58 (13)°, respectively, in B. In each molecule, the copper(II) ions have a distorted trigonal–bipyramidal coordination geometry with a CuCl₂NN′N′′ chromophore. The crystal packing exhibits weak intermolecular C—H⋯Cl interactions.

Related literature

For the magnetic and spin-crossover properties of 1,2,4-triazole complexes, see: Kahn & Martinez (1998 ▶); Klingele et al. (2005 ▶); Matouzenko et al. (2004 ▶); Moliner et al. (2001 ▶); For the fluorescent properties of 1,2,4-triazole complexes, see: Chen et al. (2008 ▶); Matsukizono et al. (2008 ▶).

Experimental

Crystal data

[Cu₂Cl₄(C₁₅H₁₄N₄)₂]
M _r = 769.48
Triclinic,
a = 9.3395 (11) Å
b = 12.8096 (14) Å
c = 13.9234 (16) Å
α = 92.533 (2)°
β = 94.596 (2)°
γ = 90.452 (2)°
V = 1658.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 273 (2) K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.62, T _max = 0.68
8289 measured reflections
5716 independent reflections
4065 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.069
S = 1.05
5716 reflections
399 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680804035X/cv2472sup1.cif

e-65-00m22-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804035X/cv2472Isup2.hkl

e-65-00m22-Isup2.hkl^{(279.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cl2ⁱ	0.93	2.78	3.445 (4)	129
C15—H15⋯Cl3ⁱⁱ	0.93	2.78	3.579 (4)	145
C16—H16⋯Cl1ⁱⁱⁱ	0.93	2.76	3.518 (4)	139
C19—H19⋯Cl4^iv	0.93	2.69	3.365 (4)	130

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

Acknowledgments

We are grateful to Jingye Pharmachemical Pilot Plant for financial assistance though project No. 8507041056.

supplementary crystallographic information

Comment

As the 1,2,4-triazole ring posesses strong electron donors and coordination capability to transition metal ions, the coordination chemistry of 1,2,4-triazole derivatives has gained great attention in recent years (Klingele et al., 2005; Chen et al., 2008; Matsukizono et al., 2008). Some complexes of 1,2,4-triazoles with iron(II) have spin-crossover properties, which can be used as molecular-based memory devices, displays and optical switches (Kahn & Martinez, 1998; Moliner et al., 2001; Matouzenko et al., 2004). We report here the crystal structure analysis of the title compound, (I) (Fig. 1).

The asymmetric unit of the title compound contains two halves of two centrosymmetric dinuclear molecules, A and B, respectively. In A, the dihedral angle between the triazole and pyridine rings is 11.21 (16)°, and that between the triazole and benzene rings is 74.22 (11)°; those values in B are 9.02 (16)° and 68.58 (13)°, respectively.

The crystal packing exhibits weak intermolecular C—H···Cl interactions (Table 1).

Experimental

The title compound was prepared by reaction of 3-ethyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole with copper(II) chloride in ethanol and water. To a warm solution of 0.501 grams of 3-ethyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole (2.0 mmol) in 10 ml e thanol, 0.682 grams of copper(II) chloride dihydrate (4.0 mmol) in 10 ml water was added. The filtrate was left to stand at room temperature for several days, and single crystals suitable for X-ray diffraction were collected.