2-(4-Bromo­phen­yl)-2-oxoethyl 4-bromo­benzoate

Hoong-Kun Fun; Suhana Arshad; B Garudachari; Arun M Isloor; M N Satyanarayan

doi:10.1107/S1600536811020654

. 2011 Jun 4;67(Pt 7):o1582–o1583. doi: 10.1107/S1600536811020654

2-(4-Bromophenyl)-2-oxoethyl 4-bromobenzoate

Hoong-Kun Fun ^a,^*,^‡, Suhana Arshad ^a, B Garudachari ^b, Arun M Isloor ^b, M N Satyanarayan ^c

PMCID: PMC3152043 PMID: 21836992

Abstract

The asymmetric unit of the title compound, C₁₅H₁₀Br₂O₃, consists of three crystallographically independent molecules (A, B and C). The phenyl rings in molecules A, B and C make dihedral angles of 6.1 (3), 3.2 (2) and 54.6 (2)° to each other, respectively. In the crystal, molecules are linked into two-dimensional layers parallel to the ab plane by intermolecular C—H⋯O hydrogen bonds. The crystal structure is further stabilized by C—H⋯π interactions. The studied crystal is an inversion twin, the refined ratio of the twin components being 0.128 (8):0.872 (8).

Related literature

For general background to phenacyl benzoates, see: Huang et al. (1996 ▶); Gandhi et al. (1995 ▶); Sheehan & Umezaw (1973 ▶); Ruzicka et al. (2002 ▶); Litera et al. (2006 ▶); Rather & Reid (1919 ▶). For the values of bond lengths, see: Allen et al. (1987 ▶). For stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶). For the synthetic procedure, see: Kelly & Howard (1932 ▶).

Experimental

Crystal data

C₁₅H₁₀Br₂O₃
M _r = 398.05
Monoclinic,
a = 11.0483 (3) Å
b = 5.9079 (1) Å
c = 33.8550 (8) Å
β = 108.802 (1)°
V = 2091.87 (8) Å³
Z = 6
Mo Kα radiation
μ = 5.82 mm⁻¹
T = 100 K
0.72 × 0.46 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.103, T _max = 0.809
43017 measured reflections
15850 independent reflections
11608 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.140
S = 0.98
15850 reflections
542 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.39 e Å⁻³
Δρ_min = −1.13 e Å⁻³
Absolute structure: Flack (1983 ▶), 6614 Friedel pairs
Flack parameter: 0.128 (8)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811020654/rz2603sup1.cif

e-67-o1582-sup1.cif^{(32.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020654/rz2603Isup2.hkl

e-67-o1582-Isup2.hkl^{(774.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811020654/rz2603Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2, Cg3, Cg4, Cg5, and Cg6 are the centroids of the C1A–C6A, C10A–C15A, C1B–C6B, C10B–C15B, C1C–C6C and C10C–C15C benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8A—H8AA⋯O2C	0.99	2.39	3.041 (7)	122
C8A—H8AB⋯O2B	0.99	2.36	3.157 (6)	138
C5B—H5BA⋯O3Cⁱ	0.95	2.52	3.424 (6)	159
C2C—H2CA⋯O3Aⁱⁱ	0.95	2.35	3.093 (7)	135
C15C—H15C⋯O2Cⁱⁱⁱ	0.95	2.52	3.408 (6)	155
C8C—H8CB⋯O3B^iv	0.99	2.59	3.355 (6)	134
C1B—H1BA⋯Cg1	0.95	2.85	3.567 (6)	133
C14B—H14B⋯Cg2	0.95	2.78	3.498 (5)	133
C5A—H5AA⋯Cg3ⁱⁱ	0.95	2.75	3.401 (6)	126
C12A—H12A⋯Cg4ⁱⁱ	0.95	2.70	3.394 (6)	130
C5C—H5CA⋯Cg4^v	0.95	2.94	3.691 (6)	137
C11B—H11B⋯Cg5ⁱ	0.95	2.93	3.596 (6)	128
C2A—H2AA⋯Cg6	0.95	2.83	3.425 (6)	122

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). SA thanks the Malaysian government and USM for the award of a research scholarship. AMI is thankful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India, for a ’Young Scientist’ award. BG thanks the Department of Information Technology, New Delhi, India, for financial support.

supplementary crystallographic information

Comment

Phenacyl benzoates are very useful intermediates for the synthesis of biologically active oxazoles, imidazoles (Huang et al., 1996) and benzoxazepine (Gandhi et al., 1995). Phenacyl benzoates can be easily photolysed in completely neutral and mild conditions (Sheehan & Umezaw, 1973; Ruzicka et al., 2002; Litera et al., 2006). They are also used for identification of organic acids (Rather & Reid, 1919). Keeping this in view, we hereby report the crystal structure of 2-(4-bromophenyl)-2-oxoethyl 4-bromobenzoate of potential commercial importance.

The asymmetric unit of the tittle compound (Fig. 1), consists of three crystallographically independent molecules A, B and C. The phenyl rings (C1–C6, C10–C15) in molecules A, B and C make dihedral angles of 6.1 (3), 3.2 (2) and 54.6 (2)° to each other, respectively. The bond lengths (Allen et al., 1987) and angles are within normal ranges. The crystal packing is shown in Fig. 2. The intermolecular C8A—H8AA···O2B and C8A—H8AB···O2C hydrogen bonds link molecule A with molecules B and C, respectively (Table 1). The molecules are linked into two-dimensional layers parallel to the ab plane by the intermolecular C5B—H5BA···O3C, C2C—H2CA···O3A, C15C—H15C···O2C and C8C—H8CB···O3B hydrogen bonds (Table 1). In addition, C—H···π interactions (Table 1) further stabilize the crystal structure.

Experimental

The title compound was synthesized according to the method reported in the literature (Kelly & Howard, 1932). A mixture of 4-bromo benzoic acid (1.0 g, 0.0049 mol), sodium carbonate (0.579 g, 0.0054 mol) and 2-bromo-1-(4-bromophenyl)ethanone (1.50 g, 0.0054 mol) in dimethyl formamide (10 ml) was stirred at room temperature for 2 h. On cooling, the separated colourless block shaped crystals of 2-(4-bromophenyl)-2-oxoethyl 4-bromobenzoate were collected by filtration. The compound was recrystallized from ethanol. Yield: 1.80 g, 91.37%. M.p.: 407–408 K.