5-Bromo-3-(3-fluoro­phenyl­sulfin­yl)-2-methyl-1-benzofuran

Hong Dae Choi; Pil Ja Seo; Uk Lee

doi:10.1107/S1600536812032394

. 2012 Jul 18;68(Pt 8):o2491. doi: 10.1107/S1600536812032394

5-Bromo-3-(3-fluorophenylsulfinyl)-2-methyl-1-benzofuran

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

PMCID: PMC3414946 PMID: 22904933

Abstract

In the title compound, C₁₅H₁₀BrFO₂S, the 3-fluorophenyl ring makes a dihedral angle of 85.0 (1)° with the mean plane [r.m.s. deviation = 0.008 (2) Å] of the benzofuran fragment. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds and a Br⋯O contact [3.200 (3) Å]. The crystal structure also exhibits slipped π–π interactions between the benzene and furan rings of neighbouring molecules [centroid–centroid distance = 3.619 (4) Å and slippage of 1.389 (4) Å]. In the 3-fluorophenyl ring, the F atom is disordered over two positions with site-occupancy factors of 0.583 (5) and 0.417 (5).

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2010a ▶,b ▶, 2012 ▶). For a review of halogen bonding, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₅H₁₀BrFO₂S
M _r = 353.20
Monoclinic,
a = 13.0488 (4) Å
b = 11.1874 (3) Å
c = 9.9295 (3) Å
β = 105.709 (2)°
V = 1395.39 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.10 mm⁻¹
T = 173 K
0.25 × 0.24 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.494, T _max = 0.746
13225 measured reflections
3460 independent reflections
2392 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.115
S = 1.03
3460 reflections
192 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −1.10 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/S1600536812032394/kp2435sup1.cif

e-68-o2491-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032394/kp2435Isup2.hkl

e-68-o2491-Isup2.hkl^{(169.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812032394/kp2435Isup3.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	2.50	3.429 (4)	167
C9—H9A⋯O2ⁱⁱ	0.98	2.44	3.269 (4)	142

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

Acknowledgments

This work was supported by the Blue-Bio Industry Regional Innovation Center (RIC08-06-07) at Dongeui University as an RIC program under the Ministry of Knowledge Economy and Busan city.

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), 3-(4-chlorophenylsulfinyl) (Choi et al., 2010b), and 3-(4-methylphenylsulfinyl) (Choi et al., 2012) substituents, we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is planar with a mean deviation of 0.008 (2) Å from the least-squares plane defined by the nine constituent atoms. In the 3-fluorophenyl ring, the F atom is disordered over two positions with site-occupancy factors, from refinement of 0.583 (5)(part A) and 0.417 (5)(part B). The dihedral angle between the 3-fluorophenyl ring and the mean plane of the benzofuran ring is 85.0 (1)°. In the crystal structure (Fig. 2), molecules are connected by weak C–H···O hydrogen bonds (Table 1), and a Br···O interaction between the bromine and the oxygen of the S═O unit [Br···O2ⁱ = 3.200 (3) Å, C4—BrI···O2ⁱ = 159.51 (11)°] (Politzer et al., 2007). The crystal packing (Fig. 3) also exhibits slipped π–π interactions between the benzene and furan rings of neighbouring molecules, with a Cg1···Cg2^iv distance of 3.619 (4) Å and an interplanar distance of 3.342 (4) Å resulting in a slippage of 1.389 (4) Å (Cg1 and Cg2 are the centroids of the C2-C7 benzene ring and the C1/C2/C7/O1/C8 furan ring, respectively).

Experimental

3-Chloroperoxybenzoic acid (77%, 224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-bromo-3-(3-fluorophenylsulfanyl)-2-methyl-1-benzofurann (303 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 colourless solid [yield 74%, m.p. 393–394 K; R_f = 0.58 (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 acetone at room temperature.