(2E)-3-(1,3-Benzodioxol-5-yl)-1-(3-bromo-2-thien­yl)prop-2-en-1-one

William T A Harrison; C S Chidan Kumar; H S Yathirajan; B V Ashalatha; B Narayana

doi:10.1107/S1600536810035129

. 2010 Sep 4;66(Pt 10):o2477. doi: 10.1107/S1600536810035129

(2E)-3-(1,3-Benzodioxol-5-yl)-1-(3-bromo-2-thienyl)prop-2-en-1-one

William T A Harrison ^a,^*, C S Chidan Kumar ^b, H S Yathirajan ^b, B V Ashalatha ^c, B Narayana ^c

PMCID: PMC2983118 PMID: 21587478

Abstract

In the title molecule, C₁₄H₉BrO₃S, the the prop-2-en-1-one (enone) fragment is close to planar [C—C—C—O = 2.5 (7)°] and it subtends dihedral angles of 12.5 (3) and 5.3 (4)° with respect to the thiophene and benzene rings, respectively. The dihedral angle between the aromatic ring systems is 12.60 (18)°. Two C—H⋯O interactions help to consolidate the non-centrosymmetic crystal packing, which features undulating (100) sheets incorporating C(11) and C(12) chain motifs.

Related literature

For related structures, see: Butcher et al. (2007 ▶); Harrison et al. (2006 ▶, 2007 ▶); Yathirajan et al. (2006a ▶,b ▶,c ▶). For background to chalcone derivatives as non-linear optical materials, see: Sarojini et al. (2006 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₉BrO₃S
M _r = 337.18
Monoclinic,
a = 4.0013 (3) Å
b = 11.0211 (9) Å
c = 14.6931 (11) Å
β = 95.781 (2)°
V = 644.65 (9) Å³
Z = 2
Mo Kα radiation
μ = 3.35 mm⁻¹
T = 291 K
0.48 × 0.16 × 0.09 mm

Data collection

Bruker SMART1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.296, T _max = 0.753
4452 measured reflections
2684 independent reflections
2180 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.091
S = 0.94
2684 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Absolute structure: Flack (1983 ▶), 1127 Friedel pairs
Flack parameter: 0.057 (11)

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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 I, global. DOI: 10.1107/S1600536810035129/su2204sup1.cif

e-66-o2477-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035129/su2204Isup2.hkl

e-66-o2477-Isup2.hkl^{(131.8KB, 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
C1—H1⋯O2ⁱ	0.93	2.51	3.420 (6)	167
C14—H14A⋯O1ⁱⁱ	0.97	2.44	3.400 (6)	171

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

Acknowledgments

CSC thanks the Department of Studies in Chemistry, University of Mysore, for the provision of research facilities.

supplementary crystallographic information

Comment

The title compound (Fig. 1), was prepared as part of our ongoing synthetic and structural studies of molecules containing thienyl and aromatic rings linked by an enone bridge as possible non-linear optical materials (Sarojini et al., 2006). The crystal structures of (2E)-1-(3-bromo-2-thienyl)-3-(4,5-dimethoxy-2-nitrophenyl)prop-2-en-1-one (Yathirajan et al., 2006a), (2E)-1-(3-bromo-2-thienyl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one (Yathirajan et al., 2006b), (2E)-1-(3-bromo-2-thienyl)-3-(4-methoxy-2,3,6-trimethylphenyl)prop-2-en-1-one (Yathirajan et al., 2006c), (2E)-1-(3-bromo-2-thienyl)-3-(4-methoxyphenyl)prop-2-en-1-one (Harrison et al., 2006), 1-(3-bromo-2-thienyl)-3-(6-methoxy-2-naphthyl)prop-2-en-1-one (Butcher et al., 2007), (2E)-1-(3-bromo-2-thienyl)-3-(4-nitrophenyl)prop-2-en-1-one (Harrison et al., 2007) have been reported previously.

The C4—C3—Br1 angle in the title molecule of 127.0 (3)° is significantly larger than angle C2—C3—Br1 [118.3 (3)°], perhaps due to steric repulsion between atoms Br1 and H6 (H···Br = 2.75 Å), as also seen in a related structure (Harrison et al., 2007). Br1 is displaced from the C1—C4/S1 ring mean plane by 0.047 (6) Å.

The enone fragment is close to planar [O1—C5—C6—C7 = 2.5 (7)°] and it subtends dihedral angles of 12.5 (3)° and 5.3 (4)°, respectively, with respect to the adjacent thienyl (C1—C4/S1) and benzene (C8—C13) rings. The O and S atoms are in a syn conformation [S1—C4—C5—O1 = 11.0 (5)°]. The dihedral angle between the thienyl and benzene ring systems is 12.60 (18)°. The five-membered C11/C12/C14/O2/O3 ring is almost planar (r.m.s. deviation = 0.003 Å) and it subtends a dihedral angle of 0.6 (3)° with ring C8–C13, i.e. the rings are statistically co-planar.

In the crystal of the title compound, two weak C—H···O interactions occur (Table 1). The bond involving atom H1 leads to C(12) chains propagating in [001], and that involving atom H14A to zigzag C(11) chains in [010]. Taken together, (100) sheets (Fig. 2) arise, in which unusual R⁴₄(31) loops are apparent.

Experimental

To 1-(3-Bromo-2-thienyl)ethanone (2.0 g, 0.01 mol) and 1,3-benzodioxole-5-carbaldehyde (1.5 g, 0.01 mol) in 25 ml of methanol, 5 ml of 10% KOH solution was slowly added with stirring at 278 K, and the stirring was continued for 4 h at RT. The solid separated was filtered out and washed with cold methanol. Recrystallization from methanol yielded the pure compound in 90% yield. Pale yellow bar-like crystals of the title compound were obtained by slow evaporation of a solution in acetone (m.p.: 419–421 K).