Crystal structure of 3-(2-bromo­phenyl­sulfon­yl)-2,5,7-trimethyl-1-benzo­furan

Hong Dae Choi; Uk Lee

doi:10.1107/S1600536814021850

. 2014 Oct 8;70(Pt 11):o1152. doi: 10.1107/S1600536814021850

Crystal structure of 3-(2-bromophenylsulfonyl)-2,5,7-trimethyl-1-benzofuran

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

PMCID: PMC4257325 PMID: 25484796

Abstract

In the title compound, C₁₇H₁₅BrO₃S, the dihedral angle between the planes of the benzofuran ring system [r.m.s. deviation = 0.016 (2) Å] and the 2-bromophenyl ring is 82.93 (6)°. In the crystal, molecules are linked via pairs of C—H⋯π hydrogen bonds and π–π interactions between the benzene and furan rings of neighbouring molecules [centroid–centroid distance = 3.881 (2) Å] into inversion-related dimers along the b-axis direction. These dimers are further linked by short Br⋯O [3.185 (2) Å] contacts.

Keywords: crystal structure, benzofuran, 2-bromophenyl, C—H⋯π hydrogen bonds, π–π interactions, Br⋯O contact

Related literature

For a related structure and background to benzofuran derivatives, see: Choi & Lee (2014 ▶). For further synthetic details, see: Choi et al. (1999 ▶). For a review of halogen bonding, see: Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₇H₁₅BrO₃S
M _r = 379.26
Monoclinic,
a = 7.8969 (2) Å
b = 8.1489 (2) Å
c = 24.3146 (6) Å
β = 96.210 (1)°
V = 1555.49 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.79 mm⁻¹
T = 173 K
0.31 × 0.27 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.479, T _max = 0.713
27395 measured reflections
3867 independent reflections
3130 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.080
S = 1.03
3867 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.34 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/S1600536814021850/mw2127sup1.cif

e-70-o1152-sup1.cif^{(832.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814021850/mw2127Isup2.hkl

e-70-o1152-Isup2.hkl^{(189.6KB, hkl)}

Click here for additional data file.^{(5.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814021850/mw2127Isup3.cml

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

. DOI: 10.1107/S1600536814021850/mw2127fig1.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.^{(1.3MB, tif)}

x y z x y z x y z x y z . DOI: 10.1107/S1600536814021850/mw2127fig2.tif

A view of the C—H⋯π, π–π and Br⋯O 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 + 1, − z + 1; (ii) − x + Inline graphic , y − , − z + ; (iii) − x, − y + 1, − z + 1; (iv) − x + , y + , − z + .]

CCDC reference: 1027593

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C2C7 benzene ring.

DHA	DH	HA	D A	DHA
C9H9C Cg1ⁱ	0.98	2.84	3.608(2)	136

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

S1. Comment

As a part of our continuing program for benzofuran derivatives (Choi & Lee, 2014), 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 0.016 (2) Å from the least-squares plane defined by the nine constituent atoms. The 2-bromophenyl ring is essentially planar, with a mean deviation of 0.004 (2) Å from the least-squares plane defined by the six constituent atoms. The dihedral angle formed by the benzofuran ring and the 2-bromophenyl ring is 82.93 (6)°. In the crystal structure (Fig. 2), molecules are linked via two different pairs of C—H···π hydrogen bonds (Table 1, Cg1 is the centroid of the C2–C7 benzene ring) and π–π interactions between the benzene and furan rings of neighbouring molecules, with a Cg1···Cg2ⁱⁱⁱ distance of 3.881 (2) Å and an interplanar distance of 3.562 (2) Å resulting in a slippage of 1.541 (2) Å (Cg2 is the centroid of the C1/C2/C7/O1/C8 furan ring), into inversion-related dimers along the b-axis direction. These dimers are further linked by halogen-bondings (Politzer et al. 2007) between the bromine and the O atom of the O═S═O unit [Br1..O3ⁱⁱ = 3.185 (2) Å, C17—Br1···O3ⁱⁱ = 164.49 (7)°, symmetry code: (ii) - x + 1/2, y - 1/2, - z + 3/2].

S2. Experimental

The starting material 3-(2-bromophenylsulfanyl)-2,5,7-trimethyl-1-benzofuran was prepared by a literature method (Choi et al., 1999). 3-Chloroperoxybenzoic acid (77%, 403 mg, 1.8 mmol) was added in small portions to a stirred solution of 3-(2-bromophenylsulfanyl)-2,5,7-trimethyl-1-benzofuran (278 mg, 0.8 mmol) in dichloromethane (30 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, 4:1 v/v) to afford the title compound as a colorless solid [yield 72% (218 mg); m.p. 453–454 K; R_f = 0.51 (hexane-ethyl acetate, 4:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound (21 mg) in acetone (15 ml) at room temperature.