2-(4-Bromo­phen­yl)-2-oxoethyl 4-meth­oxy­benzoate

Hoong-Kun Fun; Wan-Sin Loh; B Garudachari; Arun M Isloor; M N Satyanarayan

doi:10.1107/S1600536811018988

. 2011 May 25;67(Pt 6):o1529. doi: 10.1107/S1600536811018988

2-(4-Bromophenyl)-2-oxoethyl 4-methoxybenzoate

Hoong-Kun Fun ^a,^*,^‡, Wan-Sin Loh ^a,^§, B Garudachari ^b, Arun M Isloor ^b, M N Satyanarayan ^c

PMCID: PMC3120282 PMID: 21754889

Abstract

In the title compound, C₁₆H₁₃BrO₄, the benzene rings are almost perpendicular to each other, making a dihedral angle of 84.07 (8)°. In the crystal, the molecules are linked into chains along the a axis via intermolecular C—H⋯O hydrogen bonds. A C—H⋯π interaction is also observed.

Related literature

For background to and applications of phenacyl benzoates, see: Gandhi et al. (1995 ▶); Huang et al. (1996 ▶); Litera et al. (2006 ▶); Rather & Reid (1919 ▶); Ruzicka et al. (2002 ▶); Sheehan & Umezaw (1973 ▶). For the synthesis, see: Judefind & Reid (1920 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₃BrO₄
M _r = 349.17
Triclinic,
a = 7.9700 (5) Å
b = 7.9852 (5) Å
c = 11.3185 (7) Å
α = 86.536 (1)°
β = 83.205 (1)°
γ = 89.633 (1)°
V = 713.97 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.89 mm⁻¹
T = 296 K
0.58 × 0.34 × 0.32 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.286, T _max = 0.461
10671 measured reflections
3270 independent reflections
2767 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.069
S = 1.05
3270 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.52 e Å⁻³

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 datablocks global, I. DOI: 10.1107/S1600536811018988/is2716sup1.cif

e-67-o1529-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018988/is2716Isup2.hkl

e-67-o1529-Isup2.hkl^{(160.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811018988/is2716Isup3.cml

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

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

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.48	3.386 (2)	164
C11—H11A⋯Cg1ⁱⁱ	0.93	2.81	3.6395 (18)	149

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

Acknowledgments

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of a Research Fellowship. AMI is thankful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for a ‘Young scientist’ award. GB thanks the Department of Information Technology, New Delhi, India, for financial support.

supplementary crystallographic information

Comment

Phenacyl benzoates are very useful protecting groups which can be easily removed by non-chemical reactions. The advantage of photosensitive blocking groups is that they can be removed under completely neutral and mild conditions (Sheehan & Umezaw, 1973; Ruzicka et al., 2002; Litera et al., 2006) used for identification of organic acids (Rather & Reid, 1919), synthesis of oxazoles, imidazoles (Huang et al., 1996) and benzoxazepine (Gandhi et al., 1995). Keeping this in view, we hereby report the crystal structure of 2-(4-bromophenyl)-2-oxoethyl 4-methoxybenzoate of potential commercial importance.

In the title compound (Fig. 1), the C1–C6 benzene ring [maximum deviation of 0.005 (2) Å at atom C6] is almost perpendicular with the C10–C15 benzene ring [maximum deviation of 0.014 (2) Å at atom C13] with a dihedral angle of 84.07 (8)°. Bond lengths (Allen et al., 1987) and angles are within the normal ranges.

In the crystal packing (Fig. 2), the molecules are linked into chains along the a axis via intermolecular C2—H2A···O1 hydrogen bonds (Table 1). The crystal packing is further consolidated by C—H···π interactions, involving the centroids of C1–C6 phenyl ring.

Experimental

The mixture of 4-methoxy benzoic acid (1.0 g, 0.0065 mol) sodium carbonate (0.766 g, 0.0072 mol) and 2-bromo-1-(4-bromophenyl)ethanone (2.00 g, 0.0072 mol) in dimethyl formamide (10 ml) was stirred at room temperature for 2 h. On cooling, the separated colourless needle-shaped crystals of 2-(4-bromophenyl)-2-oxoethyl 4-methoxybenzoate were collected by filtration. Compound was recrystallized from ethanol. Yield: 2.1 g (91.70%), m.p.: 429–430 K (Judefind & Reid, 1920).