[(E)-2-(3,5-Dibromo-2-oxidobenzyl­ideneamino)-3-(4-hydroxy­phen­yl)propionato-κ3 O,N,O′](dimethyl­formamide-κO)copper(II)

Ming-Xiong Tan; Zhen-Feng Chen; Zhou Neng; Hong Liang

doi:10.1107/S1600536808007915

. 2008 Mar 29;64(Pt 4):m601–m602. doi: 10.1107/S1600536808007915

[(E)-2-(3,5-Dibromo-2-oxidobenzylideneamino)-3-(4-hydroxyphenyl)propionato-κ³ O,N,O′](dimethylformamide-κO)copper(II)

Ming-Xiong Tan ^a,^b,^*, Zhen-Feng Chen ^c, Zhou Neng ^b, Hong Liang ^a

PMCID: PMC2961003 PMID: 21202044

Abstract

In the title complex, [Cu(C₁₆H₁₁Br₂NO₄)(C₃H₇NO)]₂, there are two unique molecules in the asymmetric unit. Each Cu^II atom is coordinated by two O atoms and one N atom from the tridentate ligand L ²⁻ [LH₂ = (E)-2-(3,5-dibromo-2-hydroxybenzylideneamino)-2-(4-hydroxyphenyl)acetic acid] and the O atom of a dimethylformamide molecule to give a slightly distorted square-planar geometry. The two unique molecules form a dimer through weak C—H⋯O hydrogen bonds. In the dimer, the Cu⋯Cu distance is 3.712 (1) Å. In the crystal structure, molecules form a one-dimensional chain through C—H⋯O hydrogen bonds. These are further aggregated into a three-dimensional network by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Li et al. 2008 ▶; Zhang et al. (2007a ▶,b ▶). For preparative procedures, see: Xia et al. (2007 ▶); Liu et al. (2007 ▶).

Experimental

Crystal data

[Cu(C₁₆H₁₁Br₂NO₄)(C₃H₇NO)]
M _r = 577.71
Triclinic,
a = 11.4316 (19) Å
b = 11.840 (2) Å
c = 15.984 (2) Å
α = 88.998 (3)°
β = 83.562 (2)°
γ = 73.210 (2)°
V = 2057.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.98 mm⁻¹
T = 298 (2) K
0.33 × 0.18 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick,1996 ▶) T _min = 0.267, T _max = 0.498
10763 measured reflections
7143 independent reflections
3697 reflections with > 2s(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.093
S = 1.00
7143 reflections
523 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 global, I. DOI: 10.1107/S1600536808007915/sj2468sup1.cif

e-64-0m601-sup1.cif^{(27.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007915/sj2468Isup2.hkl

e-64-0m601-Isup2.hkl^{(349.5KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—O4	1.874 (4)
Cu1—N1	1.893 (5)
Cu1—O5	1.917 (5)
Cu1—O1	1.932 (4)
Cu2—O9	1.874 (4)
Cu2—N3	1.907 (5)
Cu2—O6	1.922 (4)
Cu2—O10	1.932 (5)

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O4—Cu1—N1	94.3 (2)
O4—Cu1—O5	92.5 (2)
N1—Cu1—O5	173.1 (2)
O4—Cu1—O1	177.0 (2)
N1—Cu1—O1	84.6 (2)
O5—Cu1—O1	88.5 (2)
O9—Cu2—N3	95.0 (2)
O9—Cu2—O6	178.9 (2)
N3—Cu2—O6	85.1 (2)
O9—Cu2—O10	90.9 (2)
N3—Cu2—O10	173.7 (2)
O6—Cu2—O10	89.0 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18C⋯O7	0.96	2.59	3.364 (9)	137
C37—H37C⋯O2	0.96	2.48	3.307 (8)	144
O3—H3⋯O1ⁱ	0.82	1.98	2.772 (6)	163
O8—H8⋯O6ⁱⁱ	0.82	2.07	2.888 (6)	176
C16—H16⋯O7ⁱⁱⁱ	0.93	2.52	3.422 (9)	163
C29—H29⋯O2^iv	0.93	2.45	3.291 (8)	150
C35—H35⋯O2^iv	0.93	2.59	3.408 (8)	147

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

Acknowledgments

We acknowledge financial support by the NSFC (No. 20561001) and the EDF of Guangxi (No. 200607LX067).

supplementary crystallographic information

Comment

Herein, we report the structure of a new mononuclear copper coordination complex [Cu(L)(C₃H₇NO)]₂ (1), Fig. 1, of the chiral ligand (E)-2-(3,5-dibromo-2-oxidobenzylideneamino)-2-(4-hydroxyphenyl)acetate LH₂. The Cu(II) atom coordinates a dimethylformamide molecule and the tridentate anionic ligand L^2- which binds through the N atom and carboxylate and phenolate O atoms. Although the LH₂ ligand is chiral, the compound crystallizes as a racemate with two molecules in the asymmetric unit. The coordination geometry about each copper atom is slightly distorted square planar, Table 1. A s expected all other bond distances and angles are within normal ranges (Zhang et al., 2007a,b).

The two unique molecules form a dimer through weak C18—H18C···O7 and C37—H37C···O2 hydrogen bonds, Table 2. In the dimer, the Cu1···Cu2 distance is 3.712 (1) Å. In the crystal structure, molecules of (I) form a one-dimensional chain along c (Fig. 2) through C3–H3B···O8 and C22–H22B···O3 hydrogen bonds. These chains then form a three-dimensional network through O3—H3···O1 and O8—H8···O6 hydrogen bonds and C29–H29···O2 and C35—H35···O2 interactions (Table 2, Figure 3).

Experimental

Complex (I) was prepared following the procedure described by Liu et al. (2007) and Xia et al. (2007) as follows. 3,5-Dibromo-2-hydroxy-benzaldehyde(0.560 g, 2.0 mmol) and 4-hydroxyl-phenylalanine (0.3624 g, 2.0 mmol) were dissolved in 10 ml absolute methanol. The mixture was stirred for 1 h at room temperature to give a yellow solution. 2 ml DMF and 10 ml of a methanolic solution of CuSO₄.5H₂O (0.5 g, 2 mmol) were added, the mixture was refluxed for another 1 h at 363 K, and the resulting blue solution was filtered. Blue single crystals suitable for X–ray analysis were obtained by slow evaporation of the filtrate at room temperature. Yield: 80.1% (based on copper). Elemental analysis for [Cu(C₁₆H₁₁Br₂NO₄)(C₃H₇NO)]₂ calculated: C 46.69, H 3.71, N 5.73%; found: C 46.65, H 3.81, N 5.71%.