Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ2 N,N′)copper(II)

B S Wang; H Zhong

doi:10.1107/S1600536809034187

. 2009 Sep 5;65(Pt 10):m1156. doi: 10.1107/S1600536809034187

Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ² N,N′)copper(II)

B S Wang ^a,^*, H Zhong ^b

PMCID: PMC2970365 PMID: 21577696

Abstract

In the title compound, [CuCl₂(C₁₄H₁₂N₂)], the complex molecule has m symmetry, with the mirror plane oriented parallel to the planar molecule and the ligated Cu^II atom. The metal centre has a distorted tetrahedral coordination formed by two N atoms from one 2,9-dimethyl-1,10-phenanthroline ligand and two Cl atoms. There is intermolecular π–π stacking between adjacent 2,9-dimethyl-1,10-phenanthroline ligands, with a centroid–centroid distance of 3.733 (2)Å.

Related literature

For backgroud to π-π stacking in metal complexes of phenanthroline and its derivatives, benzimidazole and quinoline, see: Wall et al. (1999 ▶); Wu et al. (2003 ▶); Pan & Xu (2004 ▶); Li et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[CuCl₂(C₁₄H₁₂N₂)]
M _r = 342.70
Orthorhombic,
a = 11.239 (2) Å
b = 7.4651 (18) Å
c = 17.663 (5) Å
V = 1481.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.82 mm⁻¹
T = 273 K
0.30 × 0.28 × 0.21 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.611, T _max = 0.701
10738 measured reflections
1951 independent reflections
1601 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.083
S = 1.00
1951 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (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 global. DOI: 10.1107/S1600536809034187/at2860sup1.cif

e-65-m1156-sup1.cif^{(15.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034187/at2860Isup2.hkl

e-65-m1156-Isup2.hkl^{(96.1KB, hkl)}

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

Acknowledgments

We thank the Youth Program of Jingdezhen Comprehesive College for financial support of this work.

supplementary crystallographic information

Comment

In recent years, simple metal complexes of phenanthroline and its derivatives with π-π stacking have attracted great interest because they can be used to study the hydrolysis of biologically important phosphate diesters with poor leaving groups (Wall et al., 1999). A series of metal complexes incorporating different aromatic ligands such as phenanthroline(phen), benzimidazole and quinoline have been prepared and their crystal structures provide useful information about π-π stacking (Wu et al., 2003; Pan & Xu, 2004; Li et al., 2005). We report herein the crystal structure of the title compound, (I).

In the molecule of the title compound, (I), (Fig. 1), the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The two N atoms of one phen ligand and two Cl atoms are coordinated to Cu^II atom, in a distorted tetrahedron arrangement. The Cu—N bonds [average 2.0665 Å] are somewhat shorter than the Cu—Cl distances [average 2.1958 Å].

In the crystal structure, there is intermolecular π-π stacking between adjacent phen, with a centroid-centroid distance of 3.733 Å (symmetry code: –x, y+1/2, -z). These π-π stacking interactions lead to a supramolecular network structure (Fig. 2).

Experimental

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Copper chloride dihydrate (170.5 mg, 1 mmol), 2,9-Dimethyl-1,10-phenanthroline (416.5 mg, 2 mmol) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 433 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small blue crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.