2-Bromo-4-chloro-6-(4-fluoro­phenyl­imino­meth­yl)phenol

G Puthilibai; S Vasudhevan; G Rajagopal

doi:10.1107/S1600536808017443

. 2008 Jun 25;64(Pt 7):o1333. doi: 10.1107/S1600536808017443

2-Bromo-4-chloro-6-(4-fluorophenyliminomethyl)phenol

G Puthilibai ^a,^*, S Vasudhevan ^b, G Rajagopal ^c

PMCID: PMC2961884 PMID: 21202957

Abstract

The two molecules of the title compound, C₁₃H₈BrClFNO, in the asymmetric unit are interconnected by π–π interactions between the salicylaldehyde and aniline units, the shortest interplanar distance being 3.317 (3) Å. These pairs and their translation equivalents are further linked by C—H⋯F hydrogen bonds, forming a one-dimensional infinite chain. In addition, there is an intramolecular O—H⋯N hydrogen bond connecting the OH group and the imine N atom.

Related literature

For related literature, see: Collinson & Fenton (1996 ▶); Garnovski & Vasil Chenko (2002 ▶); Kannan & Ramesh (2006 ▶); Karvembu et al. (2003 ▶); Kumar & Ramesh (2004 ▶); Nakajima et al. (1998 ▶); Prabhakaran et al. (2004 ▶); Ramesh & Maheswaran (2003 ▶); Sivagamasundari & Ramesh (2007 ▶).

Experimental

Crystal data

C₁₃H₈BrClFNO
M _r = 328.56
Triclinic,
a = 8.2274 (3) Å
b = 8.6566 (3) Å
c = 10.8880 (4) Å
α = 69.545 (2)°
β = 70.820 (2)°
γ = 62.341 (2)°
V = 630.48 (4) Å³
Z = 2
Mo Kα radiation
μ = 3.47 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEX2 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.451, T _max = 0.573 (expected range = 0.393–0.500)
16111 measured reflections
3975 independent reflections
2533 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.138
S = 0.99
3975 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017443/im2067sup1.cif

e-64-o1333-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017443/im2067Isup2.hkl

e-64-o1333-Isup2.hkl^{(190.8KB, 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
C11—H11⋯F1ⁱ	0.93	2.45	3.349 (4)	162
O1—H1⋯N1	0.82	1.86	2.577 (3)	146

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Sophisticated Analytical Instruments Facility, Indian Institute of Technology Madras, Chennai, for the X-ray data collection.

supplementary crystallographic information

Comment

Monobasic bidentate Schiff base ligands exemplified by the title compound exhibiting both N and O donor sites play an important role in the synthesis of metal complexes and represent an important class of chelating ligands (Sivagamasundari et al., 2007; Prabhakaran et al., 2004). Among the prodigious number and variety of Schiff bases, salicylaldimines have been studied widely because of their synthetic proclivity and structural diversity (Collinson et al., 1996; Garnovski et al., 2002). In recent years, there has been considerable interest in the chemistry of transition metal complexes of Schiff bases. This is due to the fact that Schiff bases offer opportunities for inducing substrate chirality, tuning metal centered electronic properties, enhancing solubility and stability of either homogeneous or heterogeneous catalysts and producing antibacterial agents (Karvembu et al., 2003; Nakajima et al., 1998; Kumar et al., 2004; Ramesh et al., 2003; Kannan et al., 2006). With the above view, in our ongoing research, we have chosen the title compound as a specific and representative ligand to synthesize ruthenium complexes. The title compound and its complexes will be screened against the bacterei E. coli, S.aureous, P.mirabilis and P.vulgaris.

The title compound, C₉H₈BrClFNO, crystallizes in the triclinic space group P1 with one molecule in the asymmetric unit. Figure 1 shows the ORTEP representation of the molecule with thermal ellipsoids at the 50% probability level. The packing of the molecules in the unit cell showing the inter molecular interactions is depicted in Figure 2. The molecule and its inversion analogue are linked to each other by Π-Π interactions between the salicylaldehyde moiety and the aniline moiety with the shortest interplanar distance of 3.317 (3) Å (1 - x, 1 - y, 1 - z). The molecules are further connected by C11—H11···F1 hydrogen bonds (2.452 Å, 161.89°, 1 + x, -1 + y, 1 + z) forming an one- dimensional infinite chain. The packing is further stabilized by Van der Waals interactions. In addition, an intramolecular hydrogen bonding O1—H1···N1 (2.577 (3) Å, 145.9°) linking the OH group of the former salicyleldehyde and the imine N atom. The dihedral angle between the salicylaldehyde and aniline moieties is 8.8 (2)°.

Experimental

The monobasic bidentate Schiff base ligand, 2-bromo-4-chloro-6-[(4' -fluorophenylimino)-methyl]-phenol, was synthesized by the condensation of 3-bromo-5-chloro-2-hydroxybenzaldehyde (0.1 mmol) with 4-fluoroaniline (0.1 mmol) in a 1:1 molar ratio in MeOH (25 cm³). The solution was heated under reflux for 3 h with continuous stirring and then concentrated to 5 cm³. On cooling the pale orange crystalline product precipitated, was filtered off, washed with ice cold EtOH and dried. The product was recrystallized from EtOH. The purity of the compound was checked by TLC.