2-Bromo-1-(3-nitro­phen­yl)ethanone

Jerry P Jasinski; Ray J Butcher; A S Praveen; H S Yathirajan; B Narayana

doi:10.1107/S1600536810049585

. 2010 Dec 4;67(Pt 1):o29–o30. doi: 10.1107/S1600536810049585

2-Bromo-1-(3-nitrophenyl)ethanone

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, A S Praveen ^c, H S Yathirajan ^c, B Narayana ^d

PMCID: PMC3050415 PMID: 21522741

Abstract

In the title compound, C₈H₆BrNO₃, there are two molecules, A and B, in the asymmetric unit. The nitro and ethanone groups lie close to the plane of the benzene ring and the bromine atom is twisted slightly: the dihedral angles between the mean planes of the nitro and ethanone groups and the benzene ring are 4.6 (4) (A) and 2.8 (3) (B), and 0.8 (8) (A) and 5.5 (8)° (B), respectively. An extensive array of weak C—H⋯O hydrogen bonds, π–π ring stacking [centroid–centroid distances = 3.710 (5) and 3.677 (5) Å] and short non-hydrogen Br⋯O and O⋯Br intermolecular interactions [3.16 (6)and 3.06 (8) Å] contribute to the crystal stability, forming a supermolecular three-dimensional network structure along 110. These interactions give rise to a variety of cyclic graph-set motifs and form interconnected sheets in the three-dimensional structure.

Related literature

For the use of α-haloketones in the synthesis of pharmaceuticals, see: Erian et al. (2003 ▶). For related structures, see: Gupta & Prasad (1971 ▶); Sim (1986 ▶); Sutherland & Hoy (1968 ▶, 1969 ▶); Sutherland et al. (1974 ▶); Yathirajan et al. (2007 ▶); Young et al. (1968 ▶). For cyclic graph-set motifs, see: Etter (1990 ▶). For reference bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₈H₆BrNO₃
M _r = 244.05
Triclinic,
a = 8.8259 (7) Å
b = 8.8651 (8) Å
c = 11.6775 (8) Å
α = 74.691 (7)°
β = 75.174 (7)°
γ = 78.681 (7)°
V = 843.76 (12) Å³
Z = 4
Cu Kα radiation
μ = 6.45 mm⁻¹
T = 123 K
0.75 × 0.62 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.066, T _max = 0.389
4708 measured reflections
3215 independent reflections
3023 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.090
wR(F ²) = 0.248
S = 1.12
3215 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 2.39 e Å⁻³
Δρ_min = −1.83 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶)); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049585/sj5067sup1.cif

e-67-00o29-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049585/sj5067Isup2.hkl

e-67-00o29-Isup2.hkl^{(157.7KB, 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
C4A—H4AA⋯O1Bⁱ	0.95	2.49	3.314 (10)	145
C5A—H5AA⋯Br2ⁱⁱ	0.95	3.04	3.849 (8)	144
C5A—H5AA⋯O2Bⁱ	0.95	2.55	3.409 (11)	150
C6A—H6AA⋯O3Bⁱⁱ	0.95	2.38	3.320 (10)	171
C4B—H4BA⋯O1Aⁱⁱⁱ	0.95	2.56	3.420 (9)	150
C6B—H6BA⋯O3A	0.95	2.35	3.278 (10)	165

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

Acknowledgments

ASP thanks the University of Mysore (UOM) for research facilities and HSY thanks UOM for sabbatical leave. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

α-Haloketones have been attracting increasing attention in view of their high reactivity as building blocks for the preparation of compounds of various classes due to their selective transformations with different reagents. The α-haloketones can be particularly promising synthons in combinatorial synthesis of functionalized carbo- and heterocyclic compounds used in the design of novel highly effective pharmaceuticals with a broad spectrum of bioresponses (Erian et al., 2003). Crystal structures of some acetyl biphenyl derivatives viz., 4-acetyl-2'-fluorobiphenyl (Young et al., 1968), 4-acetyl-2'-chlorobiphenyl (Sutherland & Hoy, 1968), 4-acetyl-3'-bromobiphenyl (Sutherland & Hoy, 1969), 4-acetyl-2'-nitrobiphenyl (Sutherland et al., 1974), α-bromoacetophenone (Gupta & Prasad, 1971), 2-Bromo-4'-phenylacetophenone (Sim, 1986 ) and methyl 4-(bromomethyl)benzoate (Yathirajan et al.2007) have been reported. In view of the importance of the α-haloketones, the title compound, (I), has been prepared and its crystal structure is reported.

In the title compound, C₈H₆BrNO₃, two molecules crystallize in the asymmetric unit (Fig. 2). The nitro and ethanone groups are planar with the benzene ring and the bromine atom is twisted slightly (Torsion angles C1A/C7A/C8A/Br1 = -177.5 (5)° and C1B/C7B/C8B/Br2 = 168.6 (5)°. Bond distances and angles are in normal ranges (Allen et al., 1987). An extensive array of weak C—H···O and C—H···Br hydrogen bonds (Table 1), π–π ring stacking (Table 2) and short non-hydrogen, Br···O and O···Br, intermolecular interactions (Table 3) contribute to crystal stability forming a supermolecular 3-dimensional network structure along 110 (Fig. 3). These interactions give rise to a variety of cyclic graph-set motifs (R₃¹(3), R₂²(7), R₂²(8), R₃³(12), R₃³(18)), Fig. 3, (Etter, 1990) and form interconnected sheets in the three-dimensional structure.

Experimental

To a stirred solution of 1-(3-nitrophenyl)ethanone (1 g, 6.05 mmol) in chloroform (10 ml), bromine (0.97 g, 6.05 mmol) was added at 0–5°C (Fig. 1). The reaction mixture was stirred at room temperature for 2 h, poured into ice cold water and layers were separated. The organic layer was washed with water (1 x 10 ml), 10% aq.sodium bicarbonate solution (1 x 10 ml) and brine (1 x 10 ml), dried over Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography in silca gel (230–400 mesh) using 0–10% petroleum ether and ethyl acetate as the elutant. Single crystals were grown from THF by the slow evaporation method with a yield of 96% (m.p.365–367 K).