Crystal structure of 5-chloro-2,4,6-trimethyl-3-(4-methyl­phenyl­sulfin­yl)-1-benzo­furan

Hong Dae Choi; Uk Lee

doi:10.1107/S160053681402385X

. 2014 Nov 5;70(Pt 12):o1233–o1234. doi: 10.1107/S160053681402385X

Crystal structure of 5-chloro-2,4,6-trimethyl-3-(4-methylphenylsulfinyl)-1-benzofuran

Hong Dae Choi ^a, Uk Lee ^b,^*

PMCID: PMC4257403 PMID: 25553017

Abstract

In the title compound, C₁₈H₁₇ClO₂S, the dihedral angle between the planes of the benzofuran ring [r.m.s. deviation = 0.013 (1) Å] and the 4-methylphenyl ring is 87.37 (5)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds and π–π interactions between the furan and benzene rings of neighbouring molecules [centroid–centroid distance = 3.525 (2) Å]. In addition, an S⋯S [3.6584 (9) Å] contact is observed.

Keywords: crystal structure, benzofuran, 4-methylphenyl, C—H⋯O and C—H⋯π hydrogen bonds, π–π and S⋯S interactions

Related literature

For the pharmacological properties of benzofuran compounds, see: Aslam et al. (2009 ▶); Galal et al. (2009 ▶); Howlett et al. (1999 ▶); Wahab Khan et al. (2005 ▶); Ono et al. (2002 ▶). For natural products with a benzofuran ring, see: Akgul & Anil (2003 ▶); Soekamto et al. (2003 ▶). For the synthesis of the starting material 5-chloro-2,4,6-trimethyl-3-(4-methylphenylsulfanyl)-1-benzofuran, see: Choi et al. (1999 ▶). For a related structure, see: Choi et al. (2012 ▶).

Experimental

Crystal data

C₁₈H₁₇ClO₂S
M _r = 332.83
Triclinic,
a = 8.7938 (2) Å
b = 9.1775 (3) Å
c = 10.7298 (3) Å
α = 86.571 (1)°
β = 69.157 (1)°
γ = 81.093 (2)°
V = 799.51 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 173 K
0.60 × 0.56 × 0.08 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.807, T _max = 0.971
14763 measured reflections
3988 independent reflections
3502 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.124
S = 1.05
3988 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681402385X/nk2227sup1.cif

e-70-o1233-sup1.cif^{(443.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402385X/nk2227Isup2.hkl

e-70-o1233-Isup2.hkl^{(195.4KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supporting information file. DOI: 10.1107/S160053681402385X/nk2227Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S160053681402385X/nk2227fig1.tif

The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

Click here for additional data file.^{(1.6MB, tif)}

x y z x y z x y z x y z x y z x y z . DOI: 10.1107/S160053681402385X/nk2227fig2.tif

A view of the C—H⋯O, π–π and S⋯S interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) x + 1, y, z; (ii) − x + 1, − y + 2, − z + 1; (iii) − x + 1, − y + 1, − z + 1; (iv) − x, − y + 2, − z + 1; (v) x − 1, y, z; (vi) x, y − 1, z.]

CCDC reference: 1031568

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C6H6O2ⁱ	0.95	2.30	3.180(2)	154
C17H17O1ⁱⁱ	0.95	2.56	3.434(2)	153

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

Acknowledgments

The X-ray centre of the Gyeongsang National University is acknowledged for providing access to the single-crystal diffractometer.

supplementary crystallographic information

S1. Comment

Substituted benzofurans show interesting pharmacological properties such as antibacterial and antifungal, antitumor and antiviral, antimicrobial activities (Aslam et al. 2009, Galal et al., 2009, Wahab Khan et al., 2005), and potential inhibitor of β-amyloid aggregation (Howlett et al., 1999, Ono et al., 2002). These benzofuran compounds occur in a great number of natural products. (Akgul & Anil, 2003, Soekamto et al., 2003). As a part of our ongoing project of 3-arylsulfinyl-5-chloro-2-methyl-1-benzofuran derivatives containing 4-bromophenylsulfinyl substituent in 3-position (Choi et al., 2012), we report herein on the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.013 (1) Å from the least-squares plane defined by the nine constituent atoms. The 4-methylphenyl ring is essentially planar, with a mean deviation of 0.003 (1) Å from the least-squares plane defined by the six constituent atoms. The dihedral angle formed by the benzofuran ring and the 4-methylphenyl ring is 87.37 (5)°. In the crystal structure (Fig. 2), molecules are linked by C—H···O hydrogen bonds (Table 1) and π–π interactions between the furan and benzene rings of neighbouring molecules, with a Cg1···Cg2ⁱⁱⁱ distance of 3.525 (2) Å and an interplanar distance of 3.479 (2) Å resulting in a slippage of 0.568 (2) Å (Cg1 and Cg2 are the centroids of the C1/C2/C7/O1/C8 furan ring and the C2–C7 benzene ring, respectively). In the crystal (Fig. 2), an S1···S1^iv [3.6584 (9) Å] contact are observed.

S2. Experimental

The starting material 5-chloro-2,4,6-trimethyl-3-(4-methylphenylsulfanyl)-1-benzofuran was prepared by literature method (Choi et al. 1999). 3-Chloroperoxybenzoic acid (77%, 224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-chloro-2,4,6-trimethyl-3-(4-methylphenylsulfanyl)-1-benzofuran (285 mg, 0.9 mmol) in dichloromethane (25 mL) at 273 K. After being stirred at room temperature for 8h, the mixture was washed with saturated sodium bicarbonate solution (2 X 10 mL) and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by column chromatography (hexane–ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [yield 68% (226 mg); m.p. 466–467 K; R_f = 0.43 (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 (23 mg) in acetone (15 mL) at room temperature.