5-Iodo-2-phenyl-3-phenyl­sulfinyl-1-benzofuran

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

doi:10.1107/S1600536809024556

. 2009 Jul 11;65(Pt 8):o1809. doi: 10.1107/S1600536809024556

5-Iodo-2-phenyl-3-phenylsulfinyl-1-benzofuran

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

PMCID: PMC2977478 PMID: 21583512

Abstract

In the title compound, C₂₀H₁₃IO₂S, the O atom and the phenyl group of the phenylsulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment; the phenyl ring is almost perpendicular to this plane [83.84 (5)°]. The phenyl ring in the 2-position is rotated out of the benzofuran plane, making a dihedral angle of 40.47 (5)°. The crystal structure is stabilized by non-classical intermolecular C—H⋯O interactions, and by an I⋯O halogen bond of 3.124 (1) Å [C—I⋯O = 165.84 (5)°].

Related literature

For the crystal structures of similar 5-iodo-1-benzofuran derivatives, see: Choi et al. (2007a ▶,b ▶). For a review of halogen interactions, see: Politzer et al. (2007 ▶). The Cambridge Structural Database (version 5.28; Allen et al., 2002 ▶) has 39 compounds with C–I⋯O=S contact distances less than or equal to 3.3 Å.

Experimental

Crystal data

C₂₀H₁₃IO₂S
M _r = 444.26
Triclinic,
a = 9.3544 (4) Å
b = 9.7565 (5) Å
c = 10.2808 (5) Å
α = 113.381 (1)°
β = 92.640 (1)°
γ = 98.047 (1)°
V = 847.42 (7) Å³
Z = 2
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 273 K
0.40 × 0.40 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1999 ▶) T _min = 0.467, T _max = 0.665
7217 measured reflections
3616 independent reflections
3503 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.017
wR(F ²) = 0.044
S = 1.07
3616 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.39 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 global, I. DOI: 10.1107/S1600536809024556/ng2605sup1.cif

e-65-o1809-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024556/ng2605Isup2.hkl

e-65-o1809-Isup2.hkl^{(177.3KB, 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
C10—H10⋯O2ⁱ	0.93	2.53	3.438 (2)	165
C19—H19⋯O1ⁱⁱ	0.93	2.59	3.483 (2)	162
C20—H20⋯O2ⁱⁱⁱ	0.93	2.53	3.412 (2)	159

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

supplementary crystallographic information

Comment

This work is related to our communications on the synthesis and structures of 5-iodo-1-benzofuran analogues, viz. 5-iodo-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 5-iodo-2-methyl-3-phenylsulfinyl-1-benzofuran (Choi et al., 2007b). We present the crystal structure of the title compound (I), 5-iodo-2-phenyl-3-phenylsulfinyl-1-benzofuran (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 dihedral angle in (I) formed by the planes of the benzofuran and 2-phenyl rings is 40.47 (5)°, and the phenyl ring (C15-C20) with 83.84 (5)° lies toward the benzofuran plane. The crystal packing (Fig. 2) is stabilized by non-classical intermolecular C–H···O interactions; the first between an H atom of the 2-phenyl ring and the oxygen of the S═O unit, with a C10–H10···O2ⁱ, the second between a phenyl H atom of the phenylsulfinyl substituent and the furan O atom, with a C19–H19···O1ⁱⁱ, the third between a phenyl H atom of the phenylsulfinyl substituent and the oxygen of the S═O unit, with a C20–H20···O2ⁱⁱⁱ, respectively (Table 1 and Fig. 2; symmetry code as in Fig. 2). The molecular packing (Fig. 2) is further stabilized by an I···O halogen bond (Politzer et al., 2007) between the iodine atom and the oxygen of neighbouring S═O unit, with an I···O^iv (Symmetry code as in Fig. 2). The observed I···O separation of 3.124 (1) Å and the nearly linear C–I···O angle of 165.84 (5)° are typical for such halogen bonds. A search of Cambridge Structural Database (version 5.28; Allen, 2002) revealed 39 compounds with C–I···O═S contact distances equal to or less than 3.3 Å.

Experimental

The 77% 3-chloroperoxybenzoic acid (123 mg, 0.55 mmol) was added in small portions to a stirred solution of 5-iodo-2-phenyl-3-phenylsulfanyl-1-benzofuran (214 mg, 0.5 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 3h, 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, 2:1 v/v) to afford the title compound as a colorless solid [yield 76%, m.p. 423-424 K; R_f = 0.74 (hexane-ethyl acetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in acetone at room temperature.