Propyl 2-(5-iodo-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate

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

doi:10.1107/S1600536808042359

. 2008 Dec 17;65(Pt 1):o151. doi: 10.1107/S1600536808042359

Propyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate

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

PMCID: PMC2968065 PMID: 21581609

Abstract

In the title compound, C₁₄H₁₅IO₄S, the O atom and the methyl group of the methylsulfinyl substituent lie on opposite sides of the plane of the benzofuran ring system. The crystal structure is stabilized by intermolecular C—H⋯π interactions between an H atom of the propyl methylene group closest to the carboxylate O atom and the benzene ring of a neighbouring molecule, and between an H atom of the outer propyl methylene group and the furan ring of a neighbouring molecule, respectively. Additionally, the crystal structure exhibits intermolecular C—H⋯O hydrogen bonds.

Related literature

For the synthesis and crystal structures of similar alkyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate derivatives. see: Choi et al. (2007 ▶, 2008 ▶).

Experimental

Crystal data

C₁₄H₁₅IO₄S
M _r = 406.22
Triclinic,
a = 8.5468 (4) Å
b = 10.0329 (5) Å
c = 10.3239 (5) Å
α = 72.442 (1)°
β = 81.345 (1)°
γ = 65.088 (1)°
V = 765.21 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.24 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T _min = 0.583, T _max = 0.787
6182 measured reflections
2982 independent reflections
2778 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.069
S = 1.18
2982 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.56 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/S1600536808042359/sj2566sup1.cif

e-65-0o151-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042359/sj2566Isup2.hkl

e-65-0o151-Isup2.hkl^{(146.3KB, 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
C11—H11B⋯Cg1ⁱ	0.97	3.12	3.814 (4)	130
C12—H12B⋯Cg2ⁱⁱ	0.97	2.99	3.929 (3)	162
C3—H3⋯O4ⁱⁱⁱ	0.93	2.60	3.468 (4)	157
C9—H9B⋯O4^iv	0.97	2.40	3.356 (4)	167

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg1 and Cg2 are the centroids of the C2–C7 benzene ring and the C1/C2/C7/O1/C8 furan ring, respectively.

supplementary crystallographic information

Comment

This work is related to our previous communications on the synthesis and structure of alkyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate analogues, viz. ethyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007) and isopropyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2008). Here we report the crystal structure of the title compound, propyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.012 (2) Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by intermolecular C—H···π interactions within each stack of molecules; one between the hydrogen of 11–methylene group and the benzene ring of the benzofuran unit, with a C11—H11B···Cg1ⁱ separation of 3.12 Å, and a second between the hydrogen of 12-methylene group and the furan ring of the benzofuran unit, with a C12—H12B···Cg2ⁱ with a separation of 2.99 Å (Table 1 and Fig. 2; Cg1 and Cg2 are the centroids of the C2–C7 benzene ring and the C1/C2/C7/O1/C8 furan ring, respectively, symmetry code as in Fig. 2). In addition, intermolecular C—H···O hydrogen bonds in the structure are observed (Table 1).

Experimental

77% 3-chloroperoxybenzoic acid (173 mg, 0.77 mmol) was added in small portions to a stirred solution of propyl 2-(5-iodo-3-methylsulfanyl-1-benzofuran-2-yl)acetate (273 mg, 0.7 mmol) in dichloromethane (30 ml) at 273 K. After stirring for 3 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-ethyl acetate, 1:2 v/v) to afford the title compound as a colorless solid [yield 80%, m.p. 412-413 K; R_f = 0.58 (hexane-ethyl acetate, 1;2 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in acetone at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 0.93 (t, J = 7.36 Hz, 3H), 1.64-1.72 (m, 2H), 3.07 (s, 3H), 4.02 (s, 2H), 4.11 (t, J = 6.60 Hz, 2H), 7.29 (d, J = 8.76 Hz, 1H), 7.66 (dd, J = 8.80 Hz and J = 1.84 Hz, 1H), 8.28 (d, J = 1.48 Hz, 1H); EI-MS 406 [M⁺].