2-(4-Iodo­phen­yl)-5,7-dimethyl-3-methyl­sulfinyl-1-benzofuran

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

doi:10.1107/S1600536808014104

. 2008 May 17;64(Pt 6):o1088. doi: 10.1107/S1600536808014104

2-(4-Iodophenyl)-5,7-dimethyl-3-methylsulfinyl-1-benzofuran

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

PMCID: PMC2961519 PMID: 21202603

Abstract

The title compound, C₁₇H₁₅IO₂S, was prepared by the oxidation of 2-(4-iodophenyl)-5,7-dimethyl-3-methylsulfanyl-1-benzofuran using 3-chloroperoxybenzoic acid. The 4-iodophenyl ring makes a dihedral angle of 26.0 (1)° with the plane of the benzofuran fragment, and the O atom and the methyl group of the methylsulfinyl substituent lie on opposite sides of this plane. The crystal structure is stabilized by inter- and intramolecular C—H⋯O hydrogen bonds, and by an I⋯O halogen bond with an I⋯O distance of 3.145 (2) Å and a nearly linear C—I⋯O angle of 164.01 (9)°.

Related literature

For the crystal structures of similar 2-aryl-3-methylsulfinyl-1-benzofuran compounds, see: Choi et al. (2007a ▶,b ▶). For a review of halogen bonding, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₇H₁₅IO₂S
M _r = 410.25
Triclinic,
a = 8.6320 (9) Å
b = 8.917 (1) Å
c = 11.638 (1) Å
α = 94.580 (2)°
β = 100.949 (2)°
γ = 113.725 (2)°
V = 792.90 (14) Å³
Z = 2
Mo Kα radiation
μ = 2.15 mm⁻¹
T = 293 (2) K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.594, T _max = 0.647
6882 measured reflections
3408 independent reflections
3214 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.080
S = 1.22
3408 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.66 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 I, global. DOI: 10.1107/S1600536808014104/zl2115sup1.cif

e-64-o1088-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014104/zl2115Isup2.hkl

e-64-o1088-Isup2.hkl^{(167.1KB, 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
C16—H16B⋯O1	0.96	2.55	2.975 (4)	107
C16—H16A⋯O2ⁱ	0.96	2.39	3.288 (4)	156
C17—H17B⋯O1ⁱⁱ	0.96	2.51	3.422 (4)	159

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

Acknowledgments

This work was supported by a grant from Dongeui University (2008 A A098).

supplementary crystallographic information

Comment

As a part of our ongoing studies on the synthesis and structure of 2-aryl-3-methylsulfinyl-1-benzofuran analogues, the crystal structure of 2-(4-bromophenyl)-5-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007a) and 2-(4-bromophenyl)-5,7-dimethyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b) have been described in the literature. Here we report the crystal structure of the title compound, 2-(4-iodophenyl)-5,7-dimethyl-3-methylsulfinyl-1-benzofuran (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.01 Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by three different C—H···O hydrogen bonds; one between a methyl H atom and the furan O atom, i.e. C16—H16B···O1, and a second between a methyl H atom and the oxygen of a neighbouring S═O unit, i.e. C16—H16A···O2ⁱ, and a third between a methyl H atom of the methylsulfinyl substituent and the furan O atom of neighbouring molecules, i.e. C17—H17B···O1ⁱⁱ, (Fig. 2 and Table 1; symmetry code as in Fig. 2). Further stabilization of the structure comes from a weak I···O halogen bond (Fig. 2) (Politzer et al., 2007) between the iodine atom and the oxygen of a neighbouring S═O unit, with an I···O2ⁱⁱⁱ distance of 3.145 (2) Å (Symmetry code as in Fig. 2).

Experimental

77% 3-chloroperoxybenzoic acid (359 mg, 1.60 mmol) was added in small portions to a stirred solution of 2-(4-iodophenyl)-5,7-dimethyl-3-methylsulfanyl-1-benzofuran (591 mg, 1.50 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 2 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 (ethyl acetate) to afford the title compound as a colorless solid [yield 80%, m.p. 450–451 K; R_f = 0.57 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in tetrahydrofuran at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.44 (s, 3H), 2.53 (s, 3H), 3.10 (s, 3H), 7.03 (s, 1H), 7.59 (d, J = 8.44 Hz, 2H), 7.80 (s, 1H), 7.84 (d, J = 8.44 Hz, 2H); EI—MS 410 [M⁺].