5-Chloro-3-ethyl­sulfinyl-7-methyl-2-(4-methyl­phen­yl)-1-benzo­furan

Hong Dae Choi; Pil Ja Seo; Uk Lee

doi:10.1107/S1600536814005601

. 2014 Mar 19;70(Pt 4):o458. doi: 10.1107/S1600536814005601

5-Chloro-3-ethylsulfinyl-7-methyl-2-(4-methylphenyl)-1-benzofuran

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

PMCID: PMC3998548 PMID: 24826157

Abstract

In the title compound, C₁₈H₁₇ClO₂S, the dihedral angle between the mean planes of the benzofuran ring system and the methylphenyl ring is 14.50 (4)°. The centroid–centroid distances between the benzene and the methylphenyl rings are 3.827 (2) and 3.741 (2) Å, while the centroid–centroid distance between the furan and methylphenyl rings is 3.843 (2) Å. These distances indicate π–π interactions; on the other hand, the interplanar angles between the benzene and methylphenyl rings, and between the furan and methylphenyl rings are 13.89 (4) and 15.53 (4)°, respectively. In the crystal, the molecules stack along the a-axis direction.

Related literature

For background information about related compounds and their crystal structures, see Choi et al. (2010a ▶,b ▶). For π–π stacking in metal complexes with aromatic nitrogen ligands, see: Janiak (2000 ▶).

Experimental

Crystal data

C₁₈H₁₇ClO₂S
M _r = 332.83
Triclinic,
a = 7.3638 (5) Å
b = 10.2524 (6) Å
c = 11.8335 (7) Å
α = 68.949 (3)°
β = 89.362 (3)°
γ = 71.460 (3)°
V = 785.11 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 173 K
0.46 × 0.37 × 0.33 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.691, T _max = 0.746
13937 measured reflections
3759 independent reflections
3348 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.100
S = 1.06
3759 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 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/S1600536814005601/fb2296sup1.cif

e-70-0o458-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814005601/fb2296Isup2.hkl

e-70-0o458-Isup2.hkl^{(184.3KB, hkl)}

Click here for additional data file.^{(6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814005601/fb2296Isup3.cml

CCDC reference: 991267

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

supplementary crystallographic information

1. Comment

As a part of our ongoing study of 5-chloro-3-ethylsulfinyl-7-methyl-1-benzofuran derivatives which contain 4-fluorophenyl and 4 iodophenyl substituents in the 2-position (Choi et al. (2010a,b) for the F and I-compound, respectively), we report the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with the mean deviation from the least-squares plane defined by the nine constituent atoms which equals to 0.016 (1) Å. The 4-methylphenyl ring is also essentially planar, with the mean deviation of 0.004 (1) Å from the least-squares plane defined by the six core-ring atoms. The dihedral angle between the benzofuran ring system and the core of the 4-methylphenyl rings is 14.50 (4)°.

Let the centroid names Cg1, Cg2 and Cg3 be assigned to the benzene ring (C2–C7), the furan ring (C1/C2/C7/O1/C8) and the core of 4-methylphenyl ring (C10–C15), respectively: The centroid–centroid separations of Cg1···Cg3ⁱ, Cg1···Cg3ⁱⁱ and Cg2···Cg3ⁱ are 3.827 (2), 3.741 (2) and 3.843 (2) Å, respectively. (The symmetry codes are: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y + 1, -z + 1.)

The interplanar angles between the benzene and the core of 4-methylphenyl ring and between the furan and the core of 4-methylphenyl ring equal to 13.89 (4) and 15.53 (4)°, respectively. These angles are quite large for the rings being in π-electron···π-electron interactions as it follows from the study by Janiak (2000) who investigated π–π stacking in metal complexes with aromatic nitrogen ligands. According to Fig. 8 of Janiak's study, the interplanar angles between the rings that are involved in π-electron···π-electron interactions are less than 10° in overwhelming majority of cases.

2. Experimental

3-Chloroperoxybenzoic acid (77%, 224 mg, 1.0 mmol) was added in small portions to the stirred solution of 5-chloro-3-ethylsulfanyl-7-methyl-2-(4-methylphenyl)-1-benzofuran (285 mg, 0.9 mmol) in dichloromethane (30 ml) at 273 K. The mixture was washed with saturated sodium hydrogen carbonate solution after having been stirred at room temperature for 4h. 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, 1:1v/v) to afford the title compound as a colourless solid [yield 71%, m.p. 392–393 K; R_f = 0.56 (hexane–ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of the 5% solution of the title compound in acetone at room temperature. The average crystal size was approximately 1.1 × 1.3 × 0.8 mm. (The measured crystal was cut from a large one.) The crystals are soluble in polar solvents.