2,3-Dibromo-3-(4-chloro­phen­yl)-1-(4-nitro­thio­phen-2-yl)propan-1-one

Hoong-Kun Fun; Suhana Arshad; Shobhitha Shetty; Balakrishna Kalluraya; M Babu

doi:10.1107/S1600536812034551

. 2012 Aug 11;68(Pt 9):o2681. doi: 10.1107/S1600536812034551

2,3-Dibromo-3-(4-chlorophenyl)-1-(4-nitrothiophen-2-yl)propan-1-one

Hoong-Kun Fun ^a,^*,^‡, Suhana Arshad ^a, Shobhitha Shetty ^b, Balakrishna Kalluraya ^b, M Babu ^b

PMCID: PMC3435703 PMID: 22969574

Abstract

The title compound, C₁₃H₈Br₂ClNO₃S, exhibits whole-molecule disorder over two orientations in a 0.805 (6):0.195 (6) ratio. The dihedral angles between the thiophene ring [maximum deviations = 0.017 (4) and 0.033 (9) Å for the major and minor components, respectively] and the chloro-substituted phenyl ring are 32.1 (5) (major component) and 26.3 (18)° (minor component). In the crystal, C—H⋯Cl and C—H⋯O hydrogen bonds link the molecules into sheets lying parallel to the bc plane. Aromatic π–π stacking interactions [centroid–centroid distance = 3.550 (7) Å] are also observed.

Related literature

For background to nitrothiophene derivatives, see: Holla et al. (1986 ▶); Kalluraya et al. (1994 ▶); Kalluraya & Shetty (1997 ▶); Rai et al. (2008 ▶). For related structures, see: Fun et al. (2010 ▶, 2011 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₃H₈Br₂ClNO₃S
M _r = 453.53
Monoclinic,
a = 28.5425 (17) Å
b = 9.5470 (5) Å
c = 11.4047 (7) Å
β = 103.224 (2)°
V = 3025.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 5.68 mm⁻¹
T = 100 K
0.31 × 0.24 × 0.11 mm

Data collection

Bruker SMART APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.269, T _max = 0.564
33329 measured reflections
5031 independent reflections
4272 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.112
S = 1.11
5031 reflections
275 parameters
504 restraints
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.75 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 datablock(s) global, I. DOI: 10.1107/S1600536812034551/hb6917sup1.cif

e-68-o2681-sup1.cif^{(31.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034551/hb6917Isup2.hkl

e-68-o2681-Isup2.hkl^{(246.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812034551/hb6917Isup3.cml

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
C7—H7BA⋯Cl1ⁱ	1.00	2.82	3.441 (4)	121
C11—H11B⋯O1ⁱⁱ	0.95	2.49	3.435 (6)	175

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). SA also thanks the Malaysian Government and USM for the Academic Staff Training Scheme (ASTS) award.

supplementary crystallographic information

Comment

Nitrothiophene and its derivatives possess a wide variety of pharmacological activity. The presence of a nitro group at the 4-position of the molecule conferred antibacterial activity (Holla et al., 1986). A large number of nitrothiophene derivatives are reported to exhibit a variety of biological activity such as antibacterial, antifungal etc. (Kalluraya et al., 1994; Kalluraya & Shetty, 1997). Dibromopropanones were obtained by the bromination of 1-aryl-3-(4-nitro-2-thienyl)-2-propen-1-ones. Acid-catalysed condensation of acetophenones with 4-nitrothiophenediacetate in acetic acid yielded the required 1-aryl-3-(4-nitro-2-thienyl)-2-propen-1-ones known as chalcones (Rai et al., 2008).

The molecular structure is shown in Fig. 1. Bond lengths and angles are within normal ranges and comparable to the related structures (Fun et al., 2010; Fun et al., 2011). The whole molecule of the title compound is disordered over two positions with a refined site-occupancies ratio of 0.805 (6): 0.195 (6). For the major disorder component, the thiophene ring (S1/C10–C13) is approximately planar with maximum deviation of 0.017 (4) Å at atom C10 and forms a dihedral angle of 32.1 (5)° with the chloro-substituted phenyl ring (C1–C6). Meanwhile, for the minor disorder component, the approximately planar thiophene ring [S1X/C10X–C13X, with maximum deviation of 0.033 (9) Å at atom S1X] makes a dihedral angle of 26.3 (18)° with the chloro-substituted phenyl ring (C1X–C6X).

In the crystal (Fig. 2), C7—H7BA···Cl1 and C11—H11A···O1 hydrogen bonds (Table 1) link the molecules into a two-dimensional network parallel to the bc-plane. π–π interaction of Cg1···Cg1 = 3.550 (7) Å (symmetry code: 1/2 - x, -1/2 - y,-z) consolidate the crystal structure [Cg1 is the centroid of the major component of the thiophene ring (S1/C10–C13)].

Experimental

3-(4-Chlorophenyl)-1-(4-nitrothiophen-2-yl)prop-2-en-1-one (0.01 mol) was dissolved in glacial acetic acid (25 ml) by gentle warming. A solution of bromine in glacial acetic acid (30% w/v) was added to it with constant stirring until the yellow color of the bromine persisted. The reaction mixture was kept aside at room temperature for overnight. Crystals of dibromopropanone that separated out were collected by filtration and washed with petroleum ether and dried. They were then recrystallized from glacial acetic acid. Colourless blocks were obtained from 1:2 mixtures of DMF and ethanol solution by slow evaporation.