5-Bromo-2-methyl-3-(4-methyl­phenyl­sulfin­yl)-1-benzofuran

Hong Dae Choi; Pil Ja Seo; Uk Lee

doi:10.1107/S160053681201389X

. 2012 Apr 4;68(Pt 5):o1298. doi: 10.1107/S160053681201389X

5-Bromo-2-methyl-3-(4-methylphenylsulfinyl)-1-benzofuran

Hong Dae Choi ^a, Pil Ja Seo ^a, Uk Lee ^b,^*

PMCID: PMC3344444 PMID: 22590206

Abstract

In the title compound, C₁₆H₁₃BrO₂S, the 4-methylphenyl ring makes a dihedral angle of 87.83 (6)° with the mean plane [mean deviation = 0.007 (1) Å] of the benzofuran fragment. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds and Br⋯O contacts [3.099 (2) Å]. The crystal structure also exhibits π–π interactions between the furan and benzene rings of neighbouring molecules [centroid–centroid distance = 3.637 (2) Å, interplanar distance = 3.317 (2) Å and slippage = 1.492 (2) Å].

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2010a ▶,b ▶). For a review of halogen bonding, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₆H₁₃BrO₂S
M _r = 349.23
Monoclinic,
a = 14.3470 (2) Å
b = 11.2122 (1) Å
c = 9.6852 (1) Å
β = 107.556 (1)°
V = 1485.41 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.91 mm⁻¹
T = 173 K
0.31 × 0.28 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.466, T _max = 0.579
14207 measured reflections
3671 independent reflections
2844 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.086
S = 1.03
3671 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201389X/xu5502sup1.cif

e-68-o1298-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201389X/xu5502Isup2.hkl

e-68-o1298-Isup2.hkl^{(180KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201389X/xu5502Isup3.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
C5—H5⋯O1ⁱ	0.95	2.49	3.420 (3)	165
C9—H9C⋯O2ⁱⁱ	0.98	2.48	3.294 (3)	141

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

supplementary crystallographic information

Comment

As a part of our ongoing study of 5-bromo-2-methyl-1-benzofuran derivatives containing 3-(4-fluorophenylsulfinyl) (Choi et al., 2010a) and 3-(4-chlorophenylsulfinyl) (Choi et al., 2010b) substituents, we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.007 (1) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle between the 4-methylphenyl ring and the mean plane of the benzofuran fragment is 87.83 (6)°. In the crystal structure (Fig. 2), molecules are linked by weak C–H···O hydrogen bonds (Table 1) and Br···O halogen-bondings between the bromine atom and the O atom of the S=O unit [Br1···O2ⁱ = 3.099 (2) Å, C4—Br1···O2ⁱ = 163.52 (8)°] (Politzer et al., 2007). The crystal packing (Fig. 3) also exhibits weak π···π interactions between the furan and benzene rings of neighbouring molecules, with a Cg1···Cg2^vii distance of 3.637 (2) Å and an interplanar distance of 3.317 (2) Å resulting in a slippage of 1.492 (2) Å (Cg1 and Cg2 are the centroids of the C1/C2/C7/O1/C8 furan ring and C2–C7 benzene ring, respectively).

Experimental

3-Chloroperoxybenzoic acid (77%, 224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-bromo-2-methyl-3-(4-methylphenylsulfanyl)-1-benzofuran (300 mg, 0.9 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 4 h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by column chromatography (hexane/ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [yield 73%, m.p. 424–425 K; R_f = 0.45 (hexane/ethyl acetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in ethyl acetate at room temperature.