Aqua­chlorido(4-methyl­benzoato-κO)(1,10-phenanthroline-κ2 N,N′)copper(II)

Wen-Dong Song; Hao Wang; Yan-Li Miao

doi:10.1107/S1600536808010945

. 2008 Apr 26;64(Pt 5):m716. doi: 10.1107/S1600536808010945

Aquachlorido(4-methylbenzoato-κO)(1,10-phenanthroline-κ² N,N′)copper(II)

Wen-Dong Song ^a,^*, Hao Wang ^a, Yan-Li Miao ^a

PMCID: PMC2961304 PMID: 21202243

Abstract

In the title mononuclear complex, [Cu(C₈H₇O₂)Cl(C₁₂H₈N₂)(H₂O)], the Cu^II atom is coordinated by one carboxylate O atom from a monodentate 4-methylbenzoate ligand, two N atoms from the 1,10-phenanthroline ligand, one chloride ion and one water molecule in a square-pyramidal geometry. The crystal structure exhibits inter- and intramolecular C—H⋯Cl, C—H⋯O, O—H⋯Cl and O—H⋯O hydrogen bonds, as well as C—H⋯π interactions of phenanthroline and methyl H atoms towards the π-systems of neighboring 4-methylbenzoate units and the pyridine rings of the phenanthroline system [centroid–centroid distances are 2.706 (2) and 2.992 (1) Å, respectively].

Related literature

For related literature, see: Song et al. (2007 ▶).

Experimental

Crystal data

[Cu(C₈H₇O₂)Cl(C₁₂H₈N₂)(H₂O)]
M _r = 432.35
Monoclinic,
a = 10.9095 (4) Å
b = 11.0546 (4) Å
c = 15.2059 (6) Å
β = 103.578 (2)°
V = 1782.58 (12) Å³
Z = 4
Mo Kα radiation
μ = 1.40 mm⁻¹
T = 296 (2) K
0.30 × 0.29 × 0.25 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.679, T _max = 0.721
17233 measured reflections
4096 independent reflections
3470 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.087
S = 1.05
4096 reflections
251 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010945/zl2109sup1.cif

e-64-0m716-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010945/zl2109Isup2.hkl

e-64-0m716-Isup2.hkl^{(200.8KB, 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
C10—H10⋯Cl1ⁱ	0.93	2.76	3.654 (2)	162
C1—H1⋯O1	0.93	2.52	2.988 (3)	112
O1W—H2W⋯Cl1ⁱ	0.816 (10)	2.259 (10)	3.0709 (17)	174 (3)
O1W—H1W⋯O2	0.812 (10)	1.788 (14)	2.526 (2)	150 (3)
C3—H3⋯Cg1ⁱⁱ	0.93	2.71	3.413 (2)	133
C20—H20B⋯Cg2ⁱⁱⁱ	0.93	2.99	3.627 (2)	125

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of the C14–C19 and C1–C4,C12,N1 rings, respectively.

Acknowledgments

The authors acknowledge Guang Dong Ocean University for supporting this work.

supplementary crystallographic information

Comment

In the structural investigation of 4-methylbenzoate complexes, it has been found that the 4-methylbenzoic acid functions as a multidentate ligand [Song et al. (2007)], with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Cu complex obtained by the reaction of 4-methylbenzoic acid, 1,10-phenanthroline and copper chloride in an alkaline aqueous solution.

As illustrated in Figure 1, the Cu^II atom exists in a square pyramidal environment, defined by one carboxyl O atom from a monodentate 4-methylbenzate ligand, two N atoms from the 1,10-phenanthroline ligand, one chlorine ion and a water molecule. The crystal structure exhibits inter and intramolecular C—H···Cl, C—H···O, O—H···Cl and O—H···O hydrogen bonding and C—H···π interactions of phenanthroline and methyl H atoms towards the π-systems of neighboring 4-methylbenzate units and of pyridine rings of the phenanthroline system. Centroid to centroid distances are 2.706 (2)Å and 2.992 (1) Å, respectively. (Table 1, Fig. 2, Cg1 = Ring (C14-C19) ; Cg2 = Ring (C1-C4 ,C12, N1)).

Experimental

A mixture of copper chloride (1 mmol), 4-methylbenzoic acid (1 mmol), phen (1 mmol), NaOH (1.5 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dryed in air.