5-Chloro-2-methyl-3-phenyl­sulfonyl-1-benzofuran

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

doi:10.1107/S1600536808015699

. 2008 Jun 7;64(Pt 7):o1190. doi: 10.1107/S1600536808015699

5-Chloro-2-methyl-3-phenylsulfonyl-1-benzofuran

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

PMCID: PMC2961728 PMID: 21202832

Abstract

The title compound, C₁₅H₁₁ClO₃S, was prepared by the oxidation of 5-chloro-2-methyl-3-phenylsulfanyl-1-benzofuran with 3-chloroperoxybenzoic acid. There are two symmetry-independent molecules in the asymmetric unit. The dihedral angles formed by the phenyl ring and the plane of the benzofuran system are 77.80 (8) and 78.34 (8)°. The crystal structure is stabilized by aromatic π–π stacking interactions between the furan ring and the benzene rings of neighbouring benzofuran fragments from two symmetry-independent molecules; the centroid–centroid distances within the stacks are 3.689 (4), 3.702 (4), 3.825 (4) and 3.826 (4) Å. Additionally, the stacked molecules exhibit inter- and intramolecular C—H⋯O interactions.

Related literature

For the crystal structures of similar 2-methyl-3-phenylsulfonyl-1-benzofuran derivatives, see: Choi et al. (2008a ▶,b ▶).

Experimental

Crystal data

C₁₅H₁₁ClO₃S
M _r = 306.76
Triclinic,
a = 7.4029 (7) Å
b = 9.2669 (9) Å
c = 20.889 (2) Å
α = 100.953 (2)°
β = 95.626 (2)°
γ = 104.212 (2)°
V = 1348.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 173 (2) K
0.50 × 0.50 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.795, T _max = 0.870
9232 measured reflections
4555 independent reflections
4119 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.116
S = 1.16
4555 reflections
363 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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/S1600536808015699/rk2091sup1.cif

e-64-o1190-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015699/rk2091Isup2.hkl

e-64-o1190-Isup2.hkl^{(223.1KB, 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—H15A⋯O2	0.98	2.44	3.153 (4)	130
C14—H14⋯O3ⁱ	0.95	2.51	3.429 (4)	164
C29—H29⋯O5ⁱⁱ	0.95	2.51	3.453 (4)	170
C30—H30A⋯O6	0.98	2.42	3.141 (4)	130

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

supplementary crystallographic information

Comment

This work is related to our communications on the synthesis and structure of 2-methyl-3-phenylsulfonyl-1-benzofuran analogues, viz. 5-bromo-2-methyl-3-phenylsulfonyl-1-benzofuran (Choi et al., 2008a) and 2,5-dimethyl-3-phenylsulfonyl-1-benzofuran (Choi et al., 2008b). Herein we report the crystal and molecular structure of the title compound, 5-chloro-2-methyl-3-phenylsulfonyl-1-benzofuran C₁₅H₁₁ClO₃S, (I), (Fig. 1).

The benzofuran unit is essentially planar, with a max deviation of 0.015 (2) Å for unit A, and 0.020 (2) Å for unit B, respectively, from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angles formed by the benzofuran fragment and the plane of the phenyl ring are 77.80 (8)° in unit A and 78.34 (8)° in unit B, respectively. The crystal packing (Fig. 2) is stabilized by four different π–π interactions within each stack of molecules; one between the furan ring (Cg1) and an adjacent benzene ring (Cg2ⁱ) [distance 3.702 (4) Å], a second between the furan ring (Cg1) and an adjacent benzene ring (Cg2ⁱⁱ) [distance 3.826 (4) Å], a third between the furan ring (Cg3) and an adjacent benzene ring (Cg4ⁱⁱⁱ) [distance 3.689 (4) Å], a fourth between the furan ring (Cg3) and an adjacent benzene ring (Cg4^iv) [distance 3.825 (4) Å], (Cg1, Cg2, Cg3, and Cg4 are the centroids of the O1/C8/C1/C2/C7 furan ring, the C2/C3/C4/C5/C6/C7 benzene ring, the O4/C23/C16/C17/C22 furan ring, the C17/C18/C19/C20/C21/C22 benzene ring, respectively, symmetry code as in Fig. 2). The molecular packing is further stabilized by inter- and intramolecular C—H···O hydrogen bonds (Fig. 3 and Table; symmetry codes as in Fig. 3).

Experimental

77% 3-chloroperoxybenzoic acid (471 mg, 2.1 mmol) was added in small portions to a stirred solution of 5-chloro-2-methyl-3-phenylsulfanyl-1-benzofuran (275 mg, 1.0 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 4 h at room temperature, 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–ethylacetate, 2:1 v/v) to afford the I as a colorless solid [yield 81%, m.p. 468–469 K; R_f = 0.61 (hexane–ethylacetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the I in chloroform at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.80 (s, 3H), 7.28 (d, J = 2.16 Hz, 1H), 7.33 (s, 1H), 7.51–7.55 (m, 2H), 7.58–7.61 (m, 1H), 7.88 (d, J = 2.20 Hz, 1H), 7.98–8.04 (m, 2H); EI-MS 308 [M+2], 306 [M⁺].