Aqua­(3-formyl-2-oxidobenzoato-κ2 O 1,O 2)(1,10-phenanthroline-κ2 N,N′)copper(II) dimethyl­formamide solvate

Zhao-Wen Yu; Ling Chang; Peng Song; Min-Hui He

doi:10.1107/S1600536809011659

. 2009 Apr 8;65(Pt 5):m485. doi: 10.1107/S1600536809011659

Aqua(3-formyl-2-oxidobenzoato-κ² O ¹,O ²)(1,10-phenanthroline-κ² N,N′)copper(II) dimethylformamide solvate

Zhao-Wen Yu ^a,^*, Ling Chang ^a, Peng Song ^a, Min-Hui He ^a

PMCID: PMC2977551 PMID: 21583737

Abstract

In the structure of the title complex, [Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·C₃H₇NO, the Cu^II ion is pentacoordinated in a distorted square-pyramidal geometry by two O atoms of a 3-formyl-2-oxidobenzoate dianion and two N atoms of a 1,10-phenanthroline ligand occupying the basal plane and a water O atom located at the apical site. The structure displays O—H⋯O hydrogen bonding and intermolecular π–π stacking interactions between 1,10-phenantroline ligands [interplanar distance of 3.448 (5) Å].

Related literature

For the structure of the methanol solvate of aqua(3-formyl-2-oxidobenzoato-κ² O ¹,O ²)(1,10-phenanthroline-κ² N,N′)copper(II), see: Zhang et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₈H₄O₄)(C₁₂H₈N₂)(H₂O)]·C₃H₇NO
M _r = 498.97
Triclinic,
a = 9.6936 (6) Å
b = 10.9020 (12) Å
c = 11.2800 (7) Å
α = 103.834 (1)°
β = 109.764 (1)°
γ = 98.604 (1)°
V = 1054.09 (15) Å³
Z = 2
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 296 K
0.39 × 0.35 × 0.28 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.677, T _max = 0.751
5440 measured reflections
3687 independent reflections
3452 reflections with I > 2σ(I)
R _int = 0.011

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.112
S = 1.08
3687 reflections
301 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.48 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011659/gk2199sup1.cif

e-65-0m485-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011659/gk2199Isup2.hkl

e-65-0m485-Isup2.hkl^{(180.7KB, 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
O1W—H1WB⋯O4ⁱ	0.85	1.91	2.741 (3)	167
O1W—H1WA⋯O5	0.85	1.96	2.794 (3)	167

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful for financial support from the Henan Administration of Science and Technology (grant No. 0111030700).

supplementary crystallographic information

Comment

Recently we have reported the crystal structure of the methanol solvate of the title coordination compound. Here we report the crystal structure of its dimethylformamide solvate.

In the complex, the Cu²⁺ ion is pentacoordinated, with two O atoms of 3-carboxylsalicylaldehyde anion and two N atoms from 1,10-phenanthroline ligand in the basal plane and the O atom of water molecule completing the square-pyramidal geometry from the apical site (Fig. 1). The atoms N1, N2, O3 and O2 are nearly coplanar, and the Cu atom is displaced by 0.137 Å from this plane towards the apical O atom, giving the N1–Cu1–O2 angle of 172.36 (8)° and N2–Cu1–O3 angle of 166.78 (9) °. The structure of the complex molecule is very similar to that observed in the methanol solvate (Zhang et al., 2008).

There are two kinds of intermolecular hydrogen bonds in the crystal. One is between the H1WA atom of the water molecule and the O5 atom of the DMF molecule and the other is between the H1WB atom of the water molecule and the uncoordinated O4 atom (O4ⁱ: (i) = -x + 1, -y, -z + 1) of the carboxylate group. Intermolecular hydrogen bonds and π–π stacking interactions phenanthroline ligands (the interplanar distance of 3.448 Å) generate one-dimensional structure shown in Fig. 2.

Experimental

3-Carboxylsalicylaldehyde (0.166 g, 1.0 mmol) was dissolved in 10 ml of aqueous solution containing 0.080 g (2.0 mmol) NaOH. To this solution, 15 ml of DMF solution containing 1,10-phenanthroline (0.1982 g, 1 mmol) and CuCl₂.2H₂O (0.1705 g, 1 mmol) was added. The mixture was stirred at room temperature for 2 h, then filtered to give a green solution. The filtrate was airproofed and kept at room temperature. Two weeks later, green block-shaped crystal of X-ray quality were obtained.