[(2S)-2-(3,5-Dichloro-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/S1600536808007939

. 2008 Mar 29;64(Pt 4):m599–m600. doi: 10.1107/S1600536808007939

[(2S)-2-(3,5-Dichloro-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: PMC2960937 PMID: 21202043

Abstract

In the title complex, [Cu(C₁₆H₁₁Cl₂NO₄)(C₃H₇NO)] , the Cu^II atom is coordinated by two O atoms and one N atom from the tridentate ligand L ²⁻ {LH₂ = (2S)-[2-(3,5-dichloro-2-hydroxybenzylidene)imino]-3-(4-hydroxyphenyl)propionic acid} and one O atom from a dimethylformamide molecule, resulting in a slightly distorted square-planar geometry. The structure forms a one-dimensional chain through weak coordination bonds [Cu⋯O 3.080 (1), Cu⋯Cl 3.269 (1) Å] and a three-dimensional network through O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Li et al. (2008 ▶); Zhang, Li et al. (2007 ▶); Zhang, Feng et al. (2007a ▶,b ▶). For related literature, see: Xia et al. (2007 ▶); Liu et al. (2007 ▶); Cohen et al. (1964 ▶); Desiraju (1989 ▶); Zordan et al. (2005 ▶).

Experimental

Crystal data

[Cu(C₁₆H₁₁Cl₂NO₄)(C₃H₇NO)]
M _r = 488.79
Orthorhombic,
a = 5.8646 (16) Å
b = 13.220 (2) Å
c = 26.850 (3) Å
V = 2081.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 298 (2) K
0.48 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.532, T _max = 0.786
10650 measured reflections
3638 independent reflections
2915 reflections with I > 2σ(I)
R _int = 0.098

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.148
S = 1.04
3638 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.54 e Å⁻³
Absolute structure: Flack (1983 ▶), with 1505 Friedel pairs
Flack parameter: 0.04 (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/S1600536808007939/rt2016sup1.cif

e-64-0m599-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007939/rt2016Isup2.hkl

e-64-0m599-Isup2.hkl^{(178.4KB, hkl)}

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

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

Cu1—O4	1.875 (5)
Cu1—O1	1.931 (5)
Cu1—N1	1.934 (5)
Cu1—O5	1.954 (4)

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O4—Cu1—O1	169.0 (2)
O4—Cu1—N1	94.2 (2)
O1—Cu1—N1	84.5 (2)
O4—Cu1—O5	90.2 (2)
O1—Cu1—O5	91.9 (2)
N1—Cu1—O5	174.3 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	1.87	2.661 (7)	163
C17—H17⋯O4	0.93	2.27	2.743 (8)	111
C18—H18B⋯O1ⁱⁱ	0.96	2.54	3.421 (10)	150

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

Acknowledgments

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

supplementary crystallographic information

Comment

Halogens have a ubiquitous presence in both inorganic and organic chemistry, serving as mondentate or bridging ligands for a wide variety of d-block, f-block, and main group metals as well being common substituents in a large number of organic compounds. Most frequently they lie at the periphery of molecules. The resultant steric accessibility has the potential for halogenated compounds to be attractive targets for use in supramolecular chemistry and crystal engineering wherein the halogen atoms are directly involved in intermolecular interactions. Indeed, interest in packing arrangements of halogenated compounds goes back many years to what Schmidt called the chloro effect, wherein the presence of chloro substituents on aromatic compounds frequently resulted in stacking arrangements with a resultant short (ca 4 Å) crystallographic axis. (Cohen et al., 1964; Zordan et al., 2005; Cohen et al., 1964; Desiraju, 1989; Zhang, Li et al., 2007). Herein, we chose LH₂ as ligand system, and obtained a new mononuclear copper complex [Cu(L)(C₃H₇NO)] (1).

The title compound, (I), is a chiral Cu^II complex containing a dimethylformamide and a chiral ligand constructed from 3,5-Dichloro-2-hydroxy-benzaldehyde and 2-Amino-3-(4-hydroxy-phenyl)-propionic acid. The asymmetric unit of (I) shows a complex consisting of one Cu^II atom, one L^2- ligand and one dimethylformamide (Fig. 1). The Cu atom is coordinated by two oxygen atoms and one N atom from one tridentate L^2- ligand, to yield a slightly distorted planar geometry with bond lengths Cu1—O1, Cu1—O4, Cu1—O5 and Cu1—N1 1.931 (5), 1.875 (5), 1.954 (4) and 1.934 (5) Å, respectively; and bond angles (cis-angles are in the range of 84.5 (2)–91.9 (2) °, but all trans-angles are 169.0 (2)–174.3 (2) °) (Table 2).

As expected, all other bond distances and angles are within normal range. The structure forms a one-dimensional chain (Fig. 2) through weak coordination bonds (Cu1—O2ⁱ, 3.080 (1) Å, Cu1—Cl1ⁱⁱ, 3.269 (1) Å, symmetry codes: i: 1 + x, y, z; ii: -1 + x, y, z) and a three-dimensional network via weak hydrogen bonds: (O3—H3···O2ⁱ, 2.661 (7) Å, symmetry codes: i: 1 - x, 1/2 + y, 3/2 - z) and C—H···O hydrogen bond (C17—H17···O4, 2.743 (8) Å, C18—H18B···O1ⁱⁱ, 2.536 (4) Å, symmetry code: ii: 1/2 + x,-1/2 - y,2 - z) (Fig. 3).

Experimental

3,5-Dichloro-2-hydroxy-benzaldehyde(0.382 g, 2.0 mmol) and 2-Amino-3-(4-hydroxy-phenyl)-propionic acid (0.3624 g, 2.0 mmol) were dissolved in 10 ml absolute methanol. The mixture was stirred for 1 h at room temperature to yield a yellow solution. To this was added a solution of CuSO₄.5H₂O (0.5 g, 2 mmol) in a mixture of 2 ml DMF and 10 ml me thanol. The mixture was refluxed for 1 h, and then the blue solution was filtered. Blue single crystals suitable for X-ray analysis were obtained by slow evaporation of the above filtrate at room temperature. Yield: 89.6% (based on Copper). Elemental analysis for [Cu(C₁₆H₁₁Cl₂NO₄)(C₃H₇NO)] calculated: C 46.69, H 3.71, N 5.73%; found: C 46.61, H 3.84, N 5.67%.