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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2049.
Published online 2010 July 17. doi:  10.1107/S1600536810027741
PMCID: PMC3007450

5-Bromo-3-(4-fluoro­phenyl­sulfon­yl)-2-methyl-1-benzofuran

Abstract

In the title compound, C15H10BrFO3S, the 4-fluoro­phenyl ring makes a dihedral angle of 76.51 (6)° with the plane of the benzofuran fragment. In the crystal, mol­ecules are linked by weak non-classical inter­molecular C—H(...)O hydrogen bonds and an aromatic π–π inter­action between the benzene rings of neighbouring mol­ecules [centroid–centroid distance = 3.540 (3) Å].

Related literature

For the pharmacological activity of benzofuran compounds, see: Aslam et al. (2006 [triangle]); Galal et al. (2009 [triangle]); Khan et al. (2005 [triangle]). For natural products with benzofuran rings, see: Akgul & Anil (2003 [triangle]); Soekamto et al. (2003 [triangle]). For the structures of related 3-(4-fluoro­phenyl­sulfon­yl)-2-methyl-1-benzofuran derivatives, see: Choi et al. (2010a [triangle],b [triangle],c [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2049-scheme1.jpg

Experimental

Crystal data

  • C15H10BrFO3S
  • M r = 369.20
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2049-efi1.jpg
  • a = 7.4519 (3) Å
  • b = 9.2313 (4) Å
  • c = 11.4570 (5) Å
  • α = 70.652 (2)°
  • β = 78.495 (2)°
  • γ = 68.371 (2)°
  • V = 688.57 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 3.15 mm−1
  • T = 174 K
  • 0.35 × 0.33 × 0.31 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.405, T max = 0.439
  • 11771 measured reflections
  • 3137 independent reflections
  • 2741 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.082
  • S = 1.08
  • 3137 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.58 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810027741/rk2220sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027741/rk2220Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Many compounds containing a benzofuran moiety show diverse pharmacological properties such as antifungal, antitumor and antiviral, and antimicrobial activities (Aslam et al., 2006, Galal et al., 2009, Khan et al., 2005). These compounds widely occur in nature (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our study of the substituent effect on the solid state structures of 3-(4-fluorophenylsulfonyl)-2-methyl-1-benzofuran analogues (Choi et al., 2010a,b,c), we report the molecular structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.013 (2)Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle formed by the benzofuran plane and the 4-fluorophenyl ring is 76.51 (6)°. The molecular packing (Fig. 2) is stabilized by a weak intermolecular non-classical C—H···O hydrogen bond between the 4-fluorophenyl H atom and the oxygen of the O═S═O unit, with a C15—H15···O3i (Table 1). The crystal packing (Fig. 2) is further stabilized by an aromatic π–π interaction between the benzene rings of neighbouring molecules, with a Cg···Cgii distance of 3.540 (3)Å (Cg is the centroid of the C2–C7 benzene ring).

Experimental

The 77% 3-chloroperoxybenzoic acid (493 mg, 2.2 mmol) was added in small portions to a stirred solution of 5-bromo-3-(4-fluorophenylsulfanyl)-2-methyl-1-benzofuran (337 mg, 1.0 mmol) in dichloromethane (40 mL) at 273 K. After being stirred at room temperature for 10 h, the mixture was washed with saturated sodium bicarbonate solution 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 colourless solid [yield 74%, m.p. 459–460 K; Rf=0.68 (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.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95Å for aryl and 0.98Å for methyl H atoms. The Uiso(H) = 1.2Ueq(C) for aryl H atoms and Uiso(H) = 1.5Ueq(C) for methyl H atoms.

Figures

Fig. 1.
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 a small spheres of arbitrary radius.
Fig. 2.
Presentation of non-classical C—H···O and π–π interactions (dashed lines) in the crystal structure of the title compound. Cg denotes the ring centroid. Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) ...

Crystal data

C15H10BrFO3SZ = 2
Mr = 369.20F(000) = 368
Triclinic, P1Dx = 1.781 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4519 (3) ÅCell parameters from 7545 reflections
b = 9.2313 (4) Åθ = 2.5–27.5°
c = 11.4570 (5) ŵ = 3.15 mm1
α = 70.652 (2)°T = 174 K
β = 78.495 (2)°Block, colourless
γ = 68.371 (2)°0.35 × 0.33 × 0.31 mm
V = 688.57 (5) Å3

Data collection

Bruker SMART APEXII CCD diffractometer3137 independent reflections
Radiation source: rotating anode2741 reflections with I > 2σ(I)
graphite multilayerRint = 0.040
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.9°
[var phi]– and ω–scansh = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −11→11
Tmin = 0.405, Tmax = 0.439l = −14→14
11771 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0442P)2 + 0.0824P] where P = (Fo2 + 2Fc2)/3
3137 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.58 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br0.75115 (3)0.08439 (3)0.82425 (2)0.04195 (10)
S0.46680 (7)0.39556 (6)0.29542 (5)0.02422 (12)
F1.0254 (2)0.73795 (18)0.06607 (16)0.0525 (4)
O10.7799 (2)−0.06606 (16)0.35232 (13)0.0283 (3)
O20.3581 (2)0.41371 (18)0.19806 (14)0.0315 (3)
O30.3671 (2)0.44837 (18)0.40280 (14)0.0331 (3)
C10.6054 (3)0.1915 (2)0.34920 (18)0.0244 (4)
C20.6740 (3)0.1097 (2)0.47105 (18)0.0229 (4)
C30.6615 (3)0.1518 (2)0.57888 (18)0.0258 (4)
H30.58970.25830.58520.031*
C40.7587 (3)0.0310 (3)0.67691 (19)0.0273 (4)
C50.8637 (3)−0.1268 (3)0.6709 (2)0.0304 (5)
H50.9269−0.20570.74070.037*
C60.8759 (3)−0.1687 (2)0.5639 (2)0.0293 (5)
H60.9468−0.27540.55770.035*
C70.7807 (3)−0.0488 (2)0.46705 (19)0.0249 (4)
C80.6742 (3)0.0817 (2)0.28167 (19)0.0262 (4)
C90.6637 (3)0.0903 (3)0.1523 (2)0.0356 (5)
H9A0.57770.19780.11090.053*
H9B0.61280.00670.15160.053*
H9C0.79360.07220.10830.053*
C100.6374 (3)0.4971 (2)0.22804 (19)0.0240 (4)
C110.6702 (3)0.5460 (3)0.0994 (2)0.0305 (5)
H110.60340.52260.04910.037*
C120.8000 (3)0.6283 (3)0.0455 (2)0.0373 (5)
H120.82270.6642−0.04230.045*
C130.8962 (3)0.6577 (3)0.1208 (2)0.0354 (5)
C140.8684 (3)0.6105 (3)0.2478 (2)0.0343 (5)
H140.93870.63240.29690.041*
C150.7348 (3)0.5297 (2)0.3030 (2)0.0283 (4)
H150.71030.49710.39080.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.04901 (16)0.04935 (17)0.02543 (14)−0.00911 (12)−0.01044 (10)−0.01172 (11)
S0.0240 (2)0.0251 (3)0.0201 (2)−0.00436 (19)−0.00352 (19)−0.0053 (2)
F0.0530 (9)0.0482 (9)0.0613 (10)−0.0315 (7)−0.0082 (7)−0.0033 (8)
O10.0304 (7)0.0261 (7)0.0282 (8)−0.0070 (6)−0.0013 (6)−0.0107 (6)
O20.0301 (7)0.0349 (8)0.0286 (8)−0.0102 (6)−0.0104 (6)−0.0038 (7)
O30.0335 (8)0.0316 (8)0.0249 (8)−0.0015 (6)0.0021 (6)−0.0091 (7)
C10.0239 (9)0.0257 (10)0.0216 (10)−0.0067 (8)−0.0014 (8)−0.0060 (8)
C20.0202 (8)0.0238 (10)0.0231 (10)−0.0077 (7)−0.0004 (7)−0.0050 (8)
C30.0264 (9)0.0249 (10)0.0232 (10)−0.0062 (8)−0.0019 (8)−0.0058 (8)
C40.0239 (9)0.0341 (11)0.0226 (10)−0.0098 (8)−0.0026 (8)−0.0060 (9)
C50.0269 (10)0.0305 (11)0.0276 (11)−0.0086 (8)−0.0053 (8)0.0006 (9)
C60.0242 (9)0.0231 (10)0.0344 (12)−0.0048 (8)−0.0012 (9)−0.0044 (9)
C70.0240 (9)0.0260 (10)0.0256 (10)−0.0102 (8)0.0003 (8)−0.0076 (8)
C80.0254 (9)0.0277 (10)0.0241 (10)−0.0078 (8)−0.0022 (8)−0.0064 (8)
C90.0418 (12)0.0394 (13)0.0278 (12)−0.0100 (10)−0.0040 (10)−0.0154 (10)
C100.0256 (9)0.0202 (9)0.0245 (10)−0.0037 (7)−0.0048 (8)−0.0069 (8)
C110.0368 (11)0.0335 (11)0.0242 (10)−0.0135 (9)−0.0076 (9)−0.0070 (9)
C120.0432 (13)0.0379 (13)0.0295 (12)−0.0179 (10)−0.0021 (10)−0.0036 (10)
C130.0363 (11)0.0255 (11)0.0456 (14)−0.0126 (9)−0.0061 (10)−0.0072 (10)
C140.0358 (11)0.0271 (11)0.0459 (14)−0.0074 (9)−0.0137 (10)−0.0153 (10)
C150.0323 (10)0.0248 (10)0.0253 (10)−0.0005 (8)−0.0084 (8)−0.0105 (9)

Geometric parameters (Å, °)

Br—C41.894 (2)C6—C71.371 (3)
S—O21.4369 (15)C6—H60.9500
S—O31.4385 (14)C8—C91.474 (3)
S—C11.745 (2)C9—H9A0.9800
S—C101.760 (2)C9—H9B0.9800
F—C131.359 (3)C9—H9C0.9800
O1—C81.366 (2)C10—C111.390 (3)
O1—C71.377 (2)C10—C151.391 (3)
C1—C81.367 (3)C11—C121.374 (3)
C1—C21.443 (3)C11—H110.9500
C2—C31.390 (3)C12—C131.370 (3)
C2—C71.396 (3)C12—H120.9500
C3—C41.389 (3)C13—C141.370 (3)
C3—H30.9500C14—C151.390 (3)
C4—C51.394 (3)C14—H140.9500
C5—C61.380 (3)C15—H150.9500
C5—H50.9500
O2—S—O3119.74 (9)O1—C8—C1110.28 (18)
O2—S—C1108.91 (9)O1—C8—C9115.36 (17)
O3—S—C1106.96 (9)C1—C8—C9134.3 (2)
O2—S—C10107.49 (9)C8—C9—H9A109.5
O3—S—C10107.99 (10)C8—C9—H9B109.5
C1—S—C10104.78 (9)H9A—C9—H9B109.5
C8—O1—C7107.04 (14)C8—C9—H9C109.5
C8—C1—C2107.63 (17)H9A—C9—H9C109.5
C8—C1—S125.95 (17)H9B—C9—H9C109.5
C2—C1—S126.38 (15)C11—C10—C15120.92 (19)
C3—C2—C7119.08 (18)C11—C10—S118.93 (16)
C3—C2—C1136.46 (18)C15—C10—S120.14 (16)
C7—C2—C1104.44 (17)C12—C11—C10119.6 (2)
C4—C3—C2116.97 (18)C12—C11—H11120.2
C4—C3—H3121.5C10—C11—H11120.2
C2—C3—H3121.5C13—C12—C11118.7 (2)
C3—C4—C5122.9 (2)C13—C12—H12120.7
C3—C4—Br118.43 (15)C11—C12—H12120.7
C5—C4—Br118.66 (16)F—C13—C14118.7 (2)
C6—C5—C4120.1 (2)F—C13—C12118.0 (2)
C6—C5—H5119.9C14—C13—C12123.4 (2)
C4—C5—H5119.9C13—C14—C15118.3 (2)
C7—C6—C5116.77 (18)C13—C14—H14120.9
C7—C6—H6121.6C15—C14—H14120.9
C5—C6—H6121.6C14—C15—C10119.2 (2)
C6—C7—O1125.27 (18)C14—C15—H15120.4
C6—C7—C2124.12 (19)C10—C15—H15120.4
O1—C7—C2110.59 (17)
O2—S—C1—C828.0 (2)C1—C2—C7—O10.0 (2)
O3—S—C1—C8158.69 (18)C7—O1—C8—C1−1.0 (2)
C10—S—C1—C8−86.8 (2)C7—O1—C8—C9177.27 (18)
O2—S—C1—C2−154.43 (17)C2—C1—C8—O10.9 (2)
O3—S—C1—C2−23.7 (2)S—C1—C8—O1178.94 (14)
C10—S—C1—C290.80 (19)C2—C1—C8—C9−176.8 (2)
C8—C1—C2—C3177.7 (2)S—C1—C8—C91.2 (4)
S—C1—C2—C3−0.3 (3)O2—S—C10—C11−12.64 (18)
C8—C1—C2—C7−0.6 (2)O3—S—C10—C11−143.12 (15)
S—C1—C2—C7−178.53 (15)C1—S—C10—C11103.12 (17)
C7—C2—C3—C40.3 (3)O2—S—C10—C15166.35 (15)
C1—C2—C3—C4−177.8 (2)O3—S—C10—C1535.87 (18)
C2—C3—C4—C5−0.6 (3)C1—S—C10—C15−77.89 (17)
C2—C3—C4—Br178.41 (14)C15—C10—C11—C12−0.3 (3)
C3—C4—C5—C60.6 (3)S—C10—C11—C12178.67 (17)
Br—C4—C5—C6−178.47 (15)C10—C11—C12—C131.0 (3)
C4—C5—C6—C7−0.1 (3)C11—C12—C13—F179.4 (2)
C5—C6—C7—O1178.37 (18)C11—C12—C13—C14−0.6 (4)
C5—C6—C7—C2−0.2 (3)F—C13—C14—C15179.46 (19)
C8—O1—C7—C6−178.15 (19)C12—C13—C14—C15−0.5 (3)
C8—O1—C7—C20.6 (2)C13—C14—C15—C101.2 (3)
C3—C2—C7—C60.1 (3)C11—C10—C15—C14−0.8 (3)
C1—C2—C7—C6178.73 (19)S—C10—C15—C14−179.79 (15)
C3—C2—C7—O1−178.63 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15···O3i0.952.493.362 (3)152
C11—H11···O2ii0.952.673.345 (3)128

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2220).

References

  • Akgul, Y. Y. & Anil, H. (2003). Phytochemistry, 63, 939–943. [PubMed]
  • Aslam, S. N., Stevenson, P. C., Phythian, S. J., Veitch, N. C. & Hall, D. R. (2006). Tetrahedron, 62, 4214–4226.
  • Brandenburg, K. (1998). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2009). APEX2, SADABS and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010a). Acta Cryst. E66, o1067. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst. E66, o1813. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010c). Acta Cryst. E66, o1909. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Galal, S. A., Abd El-All, A. S., Abdallah, M. M. & El-Diwani, H. I. (2009). Bioorg. Med. Chem. Lett 19, 2420–2428. [PubMed]
  • Khan, M. W., Alam, M. J., Rashid, M. A. & Chowdhury, R. (2005). Bioorg. Med. Chem 13, 4796–4805. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Soekamto, N. H., Achmad, S. A., Ghisalberti, E. L., Hakim, E. H. & Syah, Y. M. (2003). Phytochemistry, 64, 831–834. [PubMed]

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