5-Bromo-2-(4-fluoro­phen­yl)-7-methyl-3-methyl­sulfinyl-1-benzofuran

Hong Dae Choi; Pil Ja Seo; Byeng Wha Son; Uk Lee

doi:10.1107/S160053680905418X

. 2009 Dec 19;66(Pt 1):o215. doi: 10.1107/S160053680905418X

5-Bromo-2-(4-fluorophenyl)-7-methyl-3-methylsulfinyl-1-benzofuran

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

PMCID: PMC2980175 PMID: 21580099

Abstract

In the title compound, C₁₆H₁₂BrFO₂S, the O atom and the methyl group of the methylsulfinyl substituent are located on opposite sides of the plane through the benzofuran fragment. The 4-fluorophenyl ring is rotated out of the benzofuran plane, as indicated by the dihedral angle of 16.17 (5)°. The crystal structure exhibits an intermolecular C—H⋯O hydrogen bond and a Br⋯O halogen interaction [3.112 (2) Å].

Related literature

For the crystal structures of similar 2-(4-fluorophenyl)-5-halo-3-methylsulfinyl-1-benzofuran derivatives, see: Choi et al. (2009a ▶,b ▶, 2010 ▶). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 ▶); Twyman & Allsop (1999 ▶). For natural products with benzofuran rings, see: Akgul & Anil (2003 ▶); Soekamto et al. (2003 ▶). For a review of halogen interactions, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₆H₁₂BrFO₂S
M _r = 367.23
Triclinic,
a = 7.5313 (6) Å
b = 9.8089 (7) Å
c = 10.9117 (8) Å
α = 106.567 (1)°
β = 92.634 (1)°
γ = 109.526 (1)°
V = 719.23 (9) Å³
Z = 2
Mo Kα radiation
μ = 3.01 mm⁻¹
T = 173 K
0.60 × 0.40 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.586, T _max = 0.746
6248 measured reflections
3083 independent reflections
2802 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.060
S = 1.05
3083 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.39 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 datablocks global, I. DOI: 10.1107/S160053680905418X/kp2245sup1.cif

e-66-0o215-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680905418X/kp2245Isup2.hkl

e-66-0o215-Isup2.hkl^{(151.2KB, 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
C15—H15C⋯O2ⁱ	0.96	2.58	3.294 (2)	131

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Molecules of benzofuran ring skeleton have attracted considerable interest, on account of their pharmacological activity (Howlett et al., 1999; Twyman & Allsop, 1999) and their occurrence as natural products (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our continuing studies on the effect of side chain substituents on the solid state structures of 2-(4-fluorophenyl)-5-halo-3-methylsulfinyl-1-benzofuran analogues (Choi et al., 2009a, b, 2010), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.014 (1) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle formed by the plane of the benzofuran and the 4-fluorophenyl ring is 16.17 (5)°. The crystal packing (Fig. 2) is stabilized by an intermolecular C—H···O hydrogen bond between the methyl H atom and the oxygen of the S═O unit, with a C15—H15C···O2ⁱ (Table 1and Fig. 2). The contact C-Br···O involving the the oxygen atom of the S═O unit [Br···O2ⁱⁱ = 3.112 (1) Å; C—Br···O2ⁱⁱ = 173.44 (7)°] is significantly shorter than the sum of van der Waals radia (3.40 Å) (Politzer et al., 2007).

Experimental

77% 3-Chloroperoxybenzoic acid (247 mg, 1.1 mmol) was added in small portions to a stirred solution of 5-bromo-2-(4-fluorophenyl)-7-methyl-3-methylsulfanyl-1-benzofuran (351 mg, 1.0 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 3 h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (hexane–ethyl acetate, 1:1 v/v) to afford the title compound as a colourless solid [yield 85%, m.p. 477–478 K; R_f = 0.71 (hexane–ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in tetrahydrofuran at room temperature.