2-Bromo-4-chloro-6-[(2,6-diisopropyl­phen­yl)imino­meth­yl]phenol

K Kanmani Raja; I Mohammed Bilal; S Thambidurai; G Rajagopal; A SubbiahPandi

doi:10.1107/S1600536808035071

. 2008 Nov 8;64(Pt 12):o2265. doi: 10.1107/S1600536808035071

2-Bromo-4-chloro-6-[(2,6-diisopropylphenyl)iminomethyl]phenol

K Kanmani Raja ^a, I Mohammed Bilal ^a, S Thambidurai ^b, G Rajagopal ^c, A SubbiahPandi ^d,^*

PMCID: PMC2959941 PMID: 21581246

Abstract

There are two molecules in the asymmetric unit of the title compound, C₁₉H₂₁BrClNO, with dihedral angles between the aromatic rings of 70.0 (2) and 81.9 (3)°. The crystal structure is stabilized by intermolecular C—H⋯π and C—Br⋯π interactions. In additional, the stacked molecules exhibit intramolecular O—H⋯N hydrogen bonds.

Related literature

For the synthesis, see: Chang et al. (1998 ▶). For Schiff base compounds in coordination chemistry, see: Pu (2008 ▶). For Schiff base compounds containing salicylidene, see: Figuet et al. (2001 ▶); Kennedy & Reglinski (2001 ▶); Thamotharan et al. (2003 ▶). For related structures, see: Lin et al. (2005 ▶); Chen & Ye (2008 ▶).

Experimental

Crystal data

C₁₉H₂₁BrClNO
M _r = 394.73
Monoclinic,
a = 11.356 (2) Å
b = 15.045 (3) Å
c = 22.660 (5) Å
β = 91.36 (3)°
V = 3870.4 (13) Å³
Z = 8
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 293 (2) K
0.26 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.672, T _max = 0.712
36408 measured reflections
6820 independent reflections
4111 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.146
S = 1.04
6820 reflections
424 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, (1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035071/lx2070sup1.cif

e-64-o2265-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035071/lx2070Isup2.hkl

e-64-o2265-Isup2.hkl^{(333.8KB, 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
O1—H1A⋯N1	0.82	1.87	2.598 (4)	147
O2—H2A⋯N2	0.82	1.88	2.610 (4)	147
C28—H28A⋯Cg1ⁱ	0.96	2.96	3.773 (6)	144
C16—Br1⋯Cg4ⁱ	1.88	3.53	4.75 (2)	120

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the C14–C19 benzene ring and Cg4 is the centroid of the C33–C38 benzene ring..

Acknowledgments

The authors are grateful to Dr. J. Jothi Kumar, Principle of Presidency College (Autonomous), Chennai, for providing the computer and internet facilities. Dr Babu Varghese, SAIF, IIT, Madras, India, is thanked for collecting the X-ray intensity data.

supplementary crystallographic information

Comment

Schiff base compounds have been of great interest for many years. These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures (Pu, 2008). As a part of our ongoing investigation in this field we have determined the crystal structure of the title compound, (I).

Fig.1 shows the asymmetric unit consisting of two molecules of (I) viz. unit A and unit B. The two crystallographically independent molecules have the same geometrical parameters within the precision of the experiments. The bond lengths and angles in (I) are comparable to the corresponding values in the related structure, 2-Bezyliminomethyl-6-bromo-4-chloro-phenol (Pu, 2008). Like other Schiff base compounds containing salicylidene (Figuet et al., 2001; Kennedy & Reglinski, 2001; Thamotharan et al., 2003) the hydroxyl groups form intramolecular hydrogen bonds with the N atoms, thereby completing six-membered rings (Fig. 2). The molecular packing is stabilized by intermolecular C—H···π and C—Br···π interactions, with a C28—H28A···Cg1ⁱ separation of 2.96 Å and a C16—Br1···Cg2ⁱ separation of 3.532 (5) Å (Fig. 2 and Table 1; Cg1 and Cg2 are the centroids of the C14-C19 and C33-C38 benzene rings, respectively, symmetry code as in Fig. 2). In addition, the molecular packing is further stabilized by two intramolecular O—H···N hydrogen bonds (Table 1).

Experimental

The title compound was synthesized by refluxing an ethanol solution (20 ml) of 5-bromo-3-chloro-2-hydroxybenzaldehyde (1.72 g, 10 mmol) and 2,6-diisopropylaniline (1.72 g, 10 mmol), at 80°C for 2 h. Upon cooling to 0°C, a yellow solid crystalline product was obtained. The precipitate was filtered off and washed with cold ethanol. Single crystal of good diffraction quality was obtained by the recrystallization of compound with ethanol solution by slow evaporation method.