(Dimethyl­formamide-κO){4,4′,6,6′-tetra­bromo-2,2′-[o-phenyl­enebis(nitrilo­methyl­idyne)]diphenolato-κ4 O,N,N′,O′}copper(II) dimethyl­formamide solvate

Yu Wu; Bin Xie; Li-Ke Zou; Wei-Ping Wu; Lu Lu

doi:10.1107/S160053680902162X

. 2009 Jun 10;65(Pt 7):m758. doi: 10.1107/S160053680902162X

(Dimethylformamide-κO){4,4′,6,6′-tetrabromo-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenolato-κ⁴ O,N,N′,O′}copper(II) dimethylformamide solvate

Yu Wu ^a,^*, Bin Xie ^a, Li-Ke Zou ^a, Wei-Ping Wu ^a, Lu Lu ^a

PMCID: PMC2969304 PMID: 21582693

Abstract

In the title compound, [Cu(C₂₀H₁₀Br₄N₂O₂)(C₃H₇NO)]·C₃H₇NO, the Cu^II ion is coordinated by two N atoms and two O atoms from a tetradentate Schiff base ligand and the O atom of one dimethylformamide ligand in an almost square-pyramidal geometry. The uncoordinated dimethylformamide solvent molecule is disordered over two sets of positions with occupancies of 0.741 (4) and 0.259 (4). The crystal packing is stabilized by C—H⋯O interactions.

Related literature

For the preparation of 3,5-dibromosalicylaldehyde, see: Elzbieta et al. (1964 ▶). For a related structure, see: Bei et al. (2003 ▶).

Experimental

Crystal data

[Cu(C₂₀H₁₀Br₄N₂O₂)(C₃H₇NO)]·C₃H₇NO
M _r = 839.67
Triclinic,
a = 7.3742 (10) Å
b = 11.9542 (19) Å
c = 17.212 (2) Å
α = 94.207 (9)°
β = 100.310 (6)°
γ = 104.117 (5)°
V = 1436.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 6.36 mm⁻¹
T = 93 K
0.25 × 0.25 × 0.25 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2004 ▶) T _min = 0.299, T _max = 0.299 (expected range = 0.204–0.204)
11906 measured reflections
6330 independent reflections
5305 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.063
S = 1.02
6330 reflections
392 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680902162X/ci2819sup1.cif

e-65-0m758-sup1.cif^{(27.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902162X/ci2819Isup2.hkl

e-65-0m758-Isup2.hkl^{(309.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.910 (2)
Cu1—O2	1.9174 (19)
Cu1—N1	1.954 (2)
Cu1—N2	1.958 (2)
Cu1—O3	2.501 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O3ⁱ	0.95	2.47	3.319 (4)	148
C7—H7⋯O3ⁱ	0.95	2.37	3.243 (4)	153
C14—H14⋯O4ⁱⁱ	0.95	2.33	3.226 (14)	156
C22—H22A⋯O1	0.98	2.54	3.378 (4)	143

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

Acknowledgments

The authors acknowledge financial assistance from Sichuan University of Science and Engineering (grant No. 2007 ZR005), the Education Committee of Sichuan Province of China (grant Nos. 2006 A110 and 07ZA161) and the Science and Technology Office of Zigong City, China (grant No. 08X01).

supplementary crystallographic information

Comment

The crystal structure and some properties of 1,2-N,N'-disalicylidenephenylaminato-nickel(II) was previously reported by Bei et al. (2003). We report here the synthesis and crystal structure of the title complex, [Cu(C₁₄H₈N₂O₃Br₂)(C₃H₇NO)](C₃H₇NO).

The contents of the asymmetric unit are shown in Fig.1. The Cu^II ion is coordinated by two N atoms and two O atoms from one 4,4',6,6'-tetrabromo-2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenolate dianion and one O atom of N,N-dimethylformamide ligand in a square-pyramidal geometry (Table 1). The crystal packing is stabilized by C—H···O interactions (Table 2).

Experimental

The title complex was synthesized in two stages. In the first stage, 3,5- dibromosalicylaldehyde was prepared according to Elzbieta et al. (1964). Two mole equivalents of 3,5-dibromosalicylaldehyde in ethanol (50 ml) was slowly added to 1,2-phenylenediamine (6 g) in ethanol (100 ml) with continuous stirring. The Schiff base molecule, viz. 4,4',6,6'-tetrabromo-2,2'-[1,2-phenylenebis(nitrilomethylidyne)] diphenol, precipitated immediately. In the second stage, the ligand (1 mmol), Cu(OAc)₂ (1 mmol) and DMF (25 ml) were refluxed for 1 h. The hot solution was filtered and allowed to stand at room temperature undisturbed for about three weeks, resulting in dark green crystals.