2-Bromo-1,3-bis­(4-chloro­phen­yl)prop-2-en-1-one

William T A Harrison; Q N M Hakim Al-Arique; B Narayana; H S Yathirajan; B K Sarojini

doi:10.1107/S160053680903815X

. 2009 Oct 3;65(Pt 11):o2648. doi: 10.1107/S160053680903815X

2-Bromo-1,3-bis(4-chlorophenyl)prop-2-en-1-one

William T A Harrison ^a,^*, Q N M Hakim Al-Arique ^b, B Narayana ^c, H S Yathirajan ^b, B K Sarojini ^d

PMCID: PMC2971337 PMID: 21578262

Abstract

In the title compound, C₁₅H₉BrCl₂O, the two benzene rings are twisted from each other with a dihedral angle of 47.33 (8)°. The crystal structure is stabilized by aromatic π–π interactions between the benzene rings of neighbouring molecules [centroid–centroid distance = 3.680 (2) Å], and by weak intermolecular C—H⋯O and C—H⋯Cl interactions. Additionally, the crystal structure exhibits a short intramolecular C—H⋯Br contact (H⋯Br = 2.69 Å).

Related literature

For background on chalcones as possible nonlinear optical materials, see: Harrison et al. (2006 ▶). For related structures with the same backbone and different substituents on the aromatic rings, see: Butcher et al. (2006 ▶, 2007 ▶); Dhanasekaran et al. (2007a ▶,b ▶); Fun et al. (2008 ▶).

Experimental

Crystal data

C₁₅H₉BrCl₂O
M _r = 356.03
Monoclinic,
a = 7.7416 (3) Å
b = 9.7981 (4) Å
c = 9.6717 (3) Å
β = 109.075 (2)°
V = 693.34 (5) Å³
Z = 2
Mo Kα radiation
μ = 3.34 mm⁻¹
T = 120 K
0.18 × 0.16 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.585, T _max = 0.824
12526 measured reflections
3129 independent reflections
2873 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.079
S = 1.04
3129 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −0.46 e Å⁻³
Absolute structure: Flack (1983 ▶), 1434 Friedel pairs
Flack parameter: 0.044 (9)

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶), SCALEPACK and SORTAV (Blessing, 1995 ▶); 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/S160053680903815X/lx2111sup1.cif

e-65-o2648-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903815X/lx2111Isup2.hkl

e-65-o2648-Isup2.hkl^{(153.5KB, hkl)}

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

Table 1. Selected torsion angles (°).

C6—C7—C8—C9	32.6 (5)
O1—C7—C8—Br1	31.2 (5)
C7—C8—C9—C10	174.4 (4)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.95	2.47	3.411 (5)	171
C11—H11⋯Cl1ⁱⁱ	0.95	2.81	3.619 (4)	143
C15—H15⋯Br1	0.95	2.69	3.377 (4)	129

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

Acknowledgments

We thank the EPSRC UK National Crystallography Service (University of Southampton) for the data collection.

supplementary crystallographic information

Comment

As part of our ongoing investigations of chalcone derivatives as possible non-linear optical materials (Harrison et al., 2006), we now report the synthesis and structure of the noncentrosymmetric title compound, (I), (Fig 1.).

The molecule adopts a twisted conformation with the dihedral angle between ring A (C1-C6) and ring B (C10-C15) being 47.33 (8)°. Some of the atoms bonded to the benzene rings deviate significantly from their attached ring planes: Cl1 and C7 deviate by 0.106 (5) and 0.140 (6)Å respectively from the mean plane of C1-C6 and Cl2 and C9 deviate by 0.028 (5) and 0.063 (6)Å from the mean plane of C10-C15. The dihedral angles between atoms C7/C8/C9 and ring planes A and B are 55.9 (2) and 20.1 (3)°, respectively. The strongly twisted conformation (Table 1) may arise, in part, to relieve the short intramolecular H1···H9 contact of 2.35 Å. A short intramolecular C–H···Br contact occurs (Table 1).

The crystal packing for (I) is influenced by weak intermolecular C–H···O and C–H···Cl interactions (Table 2), resulting in a noncentrosymmetric structure. The C–H···O links lead to chains propagating in [010], which appear to be reinforced by aromatic π–π stacking between the A and B rings [centroid-centroid separation = 3.680 (2) Å; inter-plane angle = 10.82 (19)°]. The weaker C–H···Cl interaction also generates [010] chains and together, the non-classical bonds lead to (100) sheets.

Experimental

2,3-Dibromo-1,3-[bis(4-chlorophenyl)]-2-propan-1-one (4.32 g, 0.01 mol) was mixed with triethylamine (5 ml, 0.05 mol) in toluene (100 ml). The mixture was stirred well for 24 hrs and the precipitated ethylenehydrobromide was filtered off and the solvent was removed under reduced pressure. The resulting solid mass obtained on cooling was collected by filtration. The compound was dried and recrystallized four times with ethanol to yield colourless blocks of (I). Yield: 60%; m. p.: 325-328 K; analysis for C₁₅H₉BrCl₂O: found (calculated): C: 18.01 (18.02); H: 9.15 (9.07).