5-Bromo-2,7-dimethyl-3-(3-methyl­phenyl­sulfon­yl)-1-benzo­furan

Hong Dae Choi; Pil Ja Seo; Uk Lee

doi:10.1107/S1600536814008149

. 2014 Apr 16;70(Pt 5):o567. doi: 10.1107/S1600536814008149

5-Bromo-2,7-dimethyl-3-(3-methylphenylsulfonyl)-1-benzofuran

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

PMCID: PMC4011232 PMID: 24860372

Abstract

In the title compound, C₁₇H₁₅BrO₃S, the dihedral angle between the mean planes of the benzofuran and 3-methylphenyl rings is 77.37 (5)°. In the crystal, molecules are linked via pairs of Br⋯O [Br⋯O = 3.335 (2) Å] contacts into inversion dimers. These dimers are further linked by C—H⋯O hydrogen bonds and π–π interactions between the benzene and furan rings of neighbouring molecules [centroid–centroid separation = 3.884 (3) Å] into supramolecular chains running along the a-axis direction.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2011 ▶, 2012 ▶, 2013 ▶). For a review of halogen bonding, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₇H₁₅BrO₃S
M _r = 379.26
Monoclinic,
a = 8.8813 (3) Å
b = 6.5976 (2) Å
c = 26.5044 (8) Å
β = 97.635 (1)°
V = 1539.26 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.82 mm⁻¹
T = 296 K
0.50 × 0.46 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.379, T _max = 0.746
26392 measured reflections
3831 independent reflections
3188 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.081
S = 1.07
3831 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.45 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814008149/bh2497sup1.cif

e-70-0o567-sup1.cif^{(24KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008149/bh2497Isup2.hkl

e-70-0o567-Isup2.hkl^{(187.8KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814008149/bh2497Isup3.cml

CCDC reference: 996711

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O2ⁱ	0.96	2.54	3.338 (3)	141
C17—H17C⋯O3ⁱⁱ	0.96	2.41	3.357 (3)	170

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

supplementary crystallographic information

1. Introduction

2. Experimental

2.1. Synthesis and crystallization

3-Chloroperoxybenzoic acid (77%, 448 mg, 2.0 mmol) was added in small portions to a stirred solution of 5-bromo-2,7-dimethyl-3-(3-methylphenylsulfanyl)-1-benzofuran (312 mg, 0.9 mmol) in dichloromethane (40 mL) at 273 K. After being stirred at room temperature for 8 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, 4:1 v/v) to afford the title compound as a colorless solid [yield 68%, m.p. 438–439 K; R_f = 0.51 (hexane–ethyl acetate, 4:1 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.

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aryl and 0.98 Å for methyl H atoms, respectively. U_iso (H) = 1.2U_eq (C) for aryl and 1.5U_eq (C) for methyl H atoms. The positions of methyl hydrogens were optimized using the SHELXL-97's command AFIX 137 (Sheldrick, 2008).

3. Results and discussion

As a part of our ongoing study of 5-bromo-2,7-dimethyl-1-benzofuran derivatives containing cyclohexylsulfonyl (Choi et al., 2011), 4-fluorophenylsulfonyl (Choi et al., 2012) and 4-methylphenylsulfinyl (Choi et al., 2013) substituents in the 3-position, we report here on the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran ring system is essentially planar, with a mean deviation of 0.010 (2) Å from the least-squares plane defined by the nine constituent atoms. The 3-methylphenyl ring is essentially planar, with a mean deviation of 0.004 (1) Å from the least-squares plane defined by the six constituent atoms. The dihedral angle formed by the benzofuran ring system and the 3-methylphenyl ring is 77.37 (5)°. In the crystal structure (Fig. 2), molecules are linked by pairs of Br···O halogen-bondings (Politzer et al. 2007) between the bromine and the O atom of the O═S═O unit [Br1···O2ⁱⁱⁱ = 3.335 (2) Å, C4—Br1···O2ⁱⁱⁱ = 168.67 (6)°, symmetry code: (iii) -x+1, -y+2, -z+1]. These dimers are further linked by C—H···O hydrogen bonds (Table 1), and by π···π interactions between the benzene and furan rings of neighbouring molecules, with a Cg1···Cg2^iv distance of 3.884 (3) Å and an interplanar distance of 3.440 (3) Å resulting in a slippage of 1.804 (3) Å (Cg1 and Cg2 are the centroids of the C2–C7 benzene ring and the C1/C2/C7/O1/C8 furan ring, respectively), forming supramolecular chains running along the a–axis direction.