5-(4-Bromo­phen­yl)-2-(3,4-methyl­ene­dioxy­phen­yl)-3-methyl­sulfanyl-1-benzofuran

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

doi:10.1107/S1600536809038148

. 2009 Sep 26;65(Pt 10):o2530. doi: 10.1107/S1600536809038148

5-(4-Bromophenyl)-2-(3,4-methylenedioxyphenyl)-3-methylsulfanyl-1-benzofuran

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

PMCID: PMC2970320 PMID: 21577975

Abstract

The title compound, C₂₂H₁₅BrO₃S, crystallizes with four molecules in the asymmetric unit. The 4-bromophenyl rings are rotated out of the benzofuran planes, with dihedral angles for the four molecules of 20.8 (2), 17.8 (2), 23.5 (4) and 23.9 (4)°. The dihedral angles between the 3,4-methylenedioxyphenyl ring and the benzofuran plane are 13.5 (2), 7.1 (2), 18.6 (3) and 14.2 (3)° in the four molecules. The crystal structure is stabilized by weak nonclassical intermolecular C—H⋯O hydrogen bonds. The crystal structure also exhibits intermolecular aromatic π–π interactions between the benzene and furan rings and between the 4-bromophenyl and 3,4-methylenedioxyphenyl rings from molecules of the same type; the centroid–centroid distances are 3.92 (1) and 3.79 (1), 3.91 (1), 3.77 (1) and 3.77 (1), and 3.79 (1) and 3.75 (1)Å in the four molecules.

Related literature

For the crystal structures of similar 3-methylsulfanyl-2-phenyl-1-benzofuran derivatives, see: Choi, Seo et al. (2006 ▶); Choi, Woo et al. (2006 ▶). For natural products of benzofuran ring systems, see: Akgul & Anil (2003 ▶); von Reuss & König (2004 ▶).

Experimental

Crystal data

C₂₂H₁₅BrO₃S
M _r = 439.31
Triclinic,
a = 12.3757 (8) Å
b = 16.067 (1) Å
c = 19.587 (1) Å
α = 84.078 (1)°
β = 88.6573 (9)°
γ = 68.0552 (9)°
V = 3592.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 2.43 mm⁻¹
T = 173 K
0.24 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.594, T _max = 0.760
26887 measured reflections
12562 independent reflections
6573 reflections with I > 2σ(I)
R _int = 0.094

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.150
S = 1.06
12562 reflections
973 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.73 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/S1600536809038148/pb2008sup1.cif

e-65-o2530-sup1.cif^{(50.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038148/pb2008Isup2.hkl

e-65-o2530-Isup2.hkl^{(614.1KB, 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
C12—H12A⋯O4	0.99	2.58	3.50 (1)	154
C21—H21⋯O6ⁱ	0.95	2.51	3.37 (1)	150
C57—H57A⋯O10ⁱⁱ	0.99	2.50	3.32 (1)	141
C65—H65⋯O11ⁱⁱⁱ	0.95	2.58	3.47 (1)	156
C79—H79B⋯O7^iv	0.99	2.56	3.26 (1)	128

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

supplementary crystallographic information

Comment

Molecules containing benzofuran skeleton constitute a major group of naturally-occurring compounds that are of considerable interest because of their biological activities (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 3-methylsulfanyl-2-phenyl-1-benzofuran analogues (Choi, Seo et al., 2006; Choi, Woo et al., 2006), we report the crystal structure of the title compound, which has four unique molecules in the asymmetric unit (further marked as A, B, C and D) (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.018 (6) Å for A, 0.011 (6) Å for B, 0.010 (6) Å for C and 0.022 (6) Å for D, respectively, from the least-squares plane defined by the nine constituent atoms. The 4-bromophenyl rings are rotated out of the benzofuran planes, with dihedral angles of 20.8 (2), 6.7 (2), 23.5 (4) and 23.9 (4)° in the molecules A, B, C and D, respectively. The dihedral angles between the 3,4-methylenedioxyphenyl ring and the benzofuran plane are 13.5 (2), 7.1 (2), 18.6 (3) and 14.2 (3)° for the molecules A, B, C and D, respectively.

The molecular packing (Fig. 2) is stabilized by weak non-classical C–H···O hydrogen bonds; the first between the methylene H atom and the furan O atom, with a C12–H12A···O4, the second between the 4-bromophenyl H atom and the oxygen of the methylenedioxy group, with a C21–H21···O6ⁱ, the third between the methylene H atom and the furan O atom, with a C57–H57A···O10ⁱⁱ, the fourth between the 4-bromophenyl H atom and the oxygen of the methylenedioxy group, with a C65–H65···O11ⁱⁱⁱ, the fifth between the methylene H atom and the furan O atom, with a C79–H79B···O7^iv, respectively (Table 1).

The crystal packing (Fig. 3) exhibits aromatic π–π interactions between the benzene/the furan rings and the 4-bromophenyl/the 3,4-methylenedioxyphenyl rings from two A molecules [Cg1···Cg2^v = 3.92 (1) Å, Cg3···Cg4^v = 3.79 (1) Å] (Cg1, Cg2, Cg3 and Cg4 are the centroids of the C2-C7 benzene ring, the C1/C2/C7/O1/C8 furan ring, the C16-C21 phenyl ring and the C9/C10/C11/C13/C14/C15 phenyl ring, respectively). The crystal packing (Fig. 3) also exhibits aromatic π–π interactions between the benzene/the furan rings and the 4-bromophenyl/the 3,4-methylenedioxyphenyl rings from two B molecules [Cg5···Cg6^vi = 4.22 (1) Å, Cg7···Cg8^vi = 3.91 (1) Å] (Cg5, Cg6, Cg7 and Cg8 are the centroids of the C24-C29 benzene ring, the C23/C24/C29/O4/C30 furan ring, the C38-C43 phenyl ring and the C31/C32/C33/C34/C36/C37 phenyl ring, respectively). The crystal packing (Fig. 4) exhibits aromatic π–π interactions between the benzene/the furan rings and the 4-bromophenyl/the 3,4-methylenedioxyphenyl rings from two C molecules [Cg9···Cg10^vii = 3.77 (1) Å, Cg11···Cg12^vii = 3.77 (1) Å] (Cg9, Cg10, Cg11 and Cg12 are the centroids of the C46-C51 benzene ring, the C45/C46/C51/O7/C52 furan ring, the C60-C65 phenyl ring and the C53/C54/C55/C56/C58/C59 phenyl ring, respectively). The crystal packing (Fig. 4) exhibits aromatic π–π interactions between the benzene/the furan rings and the 4-bromophenyl/the 3,4-methylenedioxyphenyl rings from two D molecules [Cg13···Cg14^viii = 3.79 (1) Å, Cg15···Cg16^viii = 3.75 (1) Å] (Cg13, Cg14, Cg15 and Cg16 are the centroids of the C68-C73 benzene ring, the C67/C68/C73/O10/C74 furan ring, the C82-C87 phenyl ring and the C75/C76/C77/C78/C80/C81 phenyl ring, respectively).

Experimental

Zinc chloride (409 mg, 3.0 mmol) was added to a stirred solution of 4'-bromo-[1,1'-biphenyl]-4-ol (747 mg, 3.0 mmol) and 2-chloro-2-methylsulfanyl-(3',4'-methylenedioxy)acetophenone (733 mg, 3.0 mmol) in dichloromethane (40 ml) at room temperature, and stirring was continued at the same temperature for 40 min. The reaction was quenched by the addition of water and the organic layer separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (carbon tetrachloride) to afford the title compound as a colorless solid [yield 62%, m.p. 456-457 K; R_f = 0.35 (carbon tetrachloride)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in tetrahydrofuran at room temperature. Spectroscopic analysis: ¹H NMR ( CDCl₃, 400 MHz) δ 2.38 (s, 3H), 6.04 (s, 2H), 6.94 (d, J = 8.6 Hz, 1H), 7.49 (d, J = 1.96 Hz, 1H), 7.50-7.54 (m, 3H), 7.56-7.59 (m, 2H), 7.81 (d, J = 1.56 Hz, 1H), 7.84-7.87 (m, 2H); ¹³C NMR (CDCl₃, 100 MHz) δ 18.4, 101.4, 107.5, 107.9, 108.5, 111.4, 117.9, 121.2, 121.9, 124.1, 124.2, 129.1, 131.8, 131.9, 135.6, 140.4, 147.8, 148.4, 153.1, 156.1; EI-MS 438 [M⁺], 440 [M+2]