2,4-Dichloro-6-({2-[(3,5-dichloro-2-hy­droxy­benzyl­idene)amino]­eth­yl}imino­meth­yl)phenol

Ali Ourari; Lotfi Baameur; Sofiane Bouacida; Bouet Gilles; Allain Magali

doi:10.1107/S1600536812020235

. 2012 May 12;68(Pt 6):o1700. doi: 10.1107/S1600536812020235

2,4-Dichloro-6-({2-[(3,5-dichloro-2-hydroxybenzylidene)amino]ethyl}iminomethyl)phenol

Ali Ourari ^a, Lotfi Baameur ^a, Sofiane Bouacida ^b,^*, Bouet Gilles ^c, Allain Magali ^d

PMCID: PMC3379294 PMID: 22719492

Abstract

The title molecule, C₁₆H₁₂Cl₄N₂O₂, lies about an inversion center. The symmetry-unique part of the molecule contains an intramolecular O—H⋯N hydrogen bond. In the crystal, molecules are arranged in corrugated layers parallel to (-101). Weak π–π stacking interactions, with a centroid–centroid diatance of 3.7923 (13) Å, are present.

Related literature

For the preparation of the title compound, see: Lu & Xia (2006 ▶); Trivedi et al. (1992 ▶). For the synthesis of similar compounds, see: Kadish et al. (1990 ▶); Taylor et al. (1991 ▶); Moutet & Ourari (1997 ▶) Ourari et al. (2008b ▶, 2011 ▶). For their applications, see: Ourari et al. (2008a ▶); Kadish et al. (1990 ▶). graphic file with name e-68-o1700-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₂Cl₄N₂O₂
M _r = 406.08
Monoclinic,
a = 7.529 (1) Å
b = 10.718 (2) Å
c = 10.759 (2) Å
β = 101.40 (2)°
V = 851.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 295 K
0.50 × 0.23 × 0.19 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: gaussian (ABSGAUSS in PLATON; Spek, 2009 ▶) T _min = 0.794, T _max = 0.893
8137 measured reflections
1671 independent reflections
1192 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.081
S = 0.94
1671 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: EXPOSE (Stoe & Cie, 1999 ▶); cell refinement: SELECT and CELL (Stoe & Cie, 1999 ▶); data reduction: INTEGRATE (Stoe & Cie, 1999 ▶); program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812020235/lh5465sup1.cif

e-68-o1700-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020235/lh5465Isup2.hkl

e-68-o1700-Isup2.hkl^{(80.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812020235/lh5465Isup3.cml

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
O9—H9⋯N2	0.82	1.84	2.562 (2)	147

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Acknowledgments

The authors thank the Algerian Ministère de l’Enseignement Supérieur et de la Recherche Scientifique for financial support and Jean-Claude Daran, Laboratoire de Chimie de Coordination, UPR-CNRS 8241, Toulouse, France, for his valuable input and insightful discussions.

supplementary crystallographic information

Comment

The synthesis of new chelating agents such as Schiff bases became an extensive area of research owing to their high structural versatility. This is due to their high ability to coordinate transition metals leading to the corresponding complexes. This class of compounds may be involved in many applications as in coordination chemistry, biology, analysis, catalysis and electrocatalysis (Ourari et al., 2008a; Kadish et al., 1990). Herein, we report the preparation and crystal structure the of the title compound. These type of polyhalogenated ligands are endowed with high resistance towards oxidation reactions seeing that the chlorine atoms are adequately grafted at ortho and para-positions of the phenolic entities, preventing their further oxidation reactions as it was early reported for the porphyrinic complexes (Kadish et al., 1990; Taylor et al., 1991; Moutet et al., 1997). Some mononuclear complexes of Schiff base-Mn(III) compounds have been synthesized and used as catalysts towards epoxidation of olefins. This showed that the dihalogenated complexes behaved as the most efficient catalysts. Recently, we have as confirmed this observation when studying their analogues such as as those of iron(III) (Ourari et al., 2008b) and ruthenium(III) (Ourari et al., 2011) for the same oxidation reactions.

The molecular structure of (I) is shown in Fig. 1. The asymmetric unit of the title compound, consists of one-half of the molecule, with the other half generated by a crystallographic inversion centre. The crystal packing can be described as corrugated layers paralel to (-101) (Fig. 2). Fig. 3 shows the crystal structure with helical chains of molecules as a result of the 2₁ screw axes. There are two intramolecular O—H···N hydrogen bonds in the molecule (Table 1, Fig. 2). Weak π–π stacking interactions with a centroid to centroid distance 3.7923 (13) Å are present between inversion related molecules.

Experimental

All reagents were AR grade, obtained from Alfa Aesar Chemical Company. 3, 5-Dichlorosalicylaldehyde, 1,2-diaminoethane and anhydrous ethanol were used without any further purification. The ligand prepared in this work was performed according the literature (Lu et al., 2006; Trivedi et al., 1992). Thus, a solution of 3, 5-dichlorosalicylaldehyde 382 mg (2.10^-3 mole) in anhydrous ethanol (10 ml) was dropwise added to a stirring ethanolic solution (10 ml), containing 60 mg (1.10^-3 mole) of ethylenediamine. The reaction mixture was refluxed for about 2 h leading to the formation of a yellow precipitate. This precipitate was collected by filtration, washed several times with ethanol and then dried on phosphoric anhydride (P₂O₅), its yield is of 90%. The resulting compound (I) was re-crystallized from a solvent mixture dichloromethane/acetone with the volume proportions 90 and 10, respectively. Under the slow evaporation, suitable crystals for X-ray diffraction were obtained.