Methyl 2-[5-(4-hydroxy­phen­yl)-3-methyl­sulfanyl-1-benzofuran-2-yl]acetate

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

doi:10.1107/S1600536809037763

. 2009 Sep 26;65(Pt 10):o2529. doi: 10.1107/S1600536809037763

Methyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate

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

PMCID: PMC2970204 PMID: 21577974

Abstract

In the title compound, C₁₈H₁₆O₄S, the 4-hydroxyphenyl ring is rotated out of the benzofuran plane, making a dihedral angle of 34.52 (6)°. The methyl group of the methylsulfanyl substituent is almost perpendicular to the plane of the benzofuran fragment [100.90 (8)°] and is slightly tilted towards it. The crystal structure is stabilized by intermolecular O—H⋯O hydrogen bonds, and by intermolecular C—H⋯π interactions between a methyl H atom of the methylsulfanyl substituent and the 4-hydroxyphenyl ring.

Related literature

For the crystal structures of similar alkyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate derivatives, see: Choi et al. (2006 ▶, 2009 ▶). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 ▶); Twyman & Allsop (1999 ▶). For natural products involving a benzofuran ring, see: Akgul & Anil (2003 ▶); von Reuss & König (2004 ▶).

Experimental

Crystal data

C₁₈H₁₆O₄S
M _r = 328.37
Monoclinic,
a = 13.6661 (6) Å
b = 7.6643 (3) Å
c = 15.6344 (7) Å
β = 95.4731 (6)°
V = 1630.10 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 173 K
0.45 × 0.25 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.940, T _max = 0.961
13917 measured reflections
3703 independent reflections
2894 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.097
S = 1.08
3703 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 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/S1600536809037763/si2201sup1.cif

e-65-o2529-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037763/si2201Isup2.hkl

e-65-o2529-Isup2.hkl^{(181.6KB, 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
O4—H4⋯O3ⁱ	0.81 (3)	1.97 (3)	2.7826 (18)	177 (2)
C18—H18C⋯Cgⁱⁱ	0.96	2.88	3.762 (2)	153

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Symmetry codes: (i) Inline graphic ; (ii) . Cg is the centroid of the C12–C17 phenyl ring.

supplementary crystallographic information

Comment

Benzofuran ring systems have received considerable interest in view of their pharmacological properties (Howlett et al., 1999; Twyman & Allsop, 1999), and these compounds are occurring in natural products (Akgul & Anil, 2003; von Reuss & König, 2004). As a part of our ongoing studies of the effect of side chain substituents on the solid state structures of alkyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate analogues (Choi et al., 2006, 2009), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.005 (1) Å from the least-squares plane defined by the nine constituent atoms. The 4-hydroxyphenyl ring is rotated out of the benzofuran plane, making a dihedral angle of 34.52 (6)°. The methyl group of the methylsulfanyl substituent is tilted towards the plane of the benzofuran unit [100.90 (8)°]. The molecular packing (Fig. 2) is stabilized by intermolecular O—H···O hydrogen bonds between the hydroxy H atom and the oxygen of the C═O unit, with a O4—H4···O3ⁱ (Table 1). The crystal packing (Fig. 2) is further stabilized by intermolecular C—H···π interactions between the methyl H atom of the methylsulfanyl substituent and the 4-hydroxyphenyl ring, with a C18—H18C···Cgⁱⁱ (Table 1; Cg is the centroid of the C12–C17 phenyl ring).

Experimental

2-[5-(4-Hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid (471 mg, 1.5 mmol) was added to a solution of concentrated sulfuric acid (3 drops) in methanol (20 ml), and the mixture was refluxed for 6h, then cooled. The solvent was evaporated and the residue was poured into water. The mixture was extracted with dichloromethane, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by column chromatography (benzene–acetone, 9 : 1 v/v) to afford the title compound as a colorless solid [yield 88%, m.p. 446–447 K; R_f = 0.49 (benzene–acetone, 9 : 1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in benzene at room temperature.