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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1297.
Published online 2010 May 8. doi:  10.1107/S1600536810016181
PMCID: PMC2979595

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

Abstract

In the title compound, C15H10BrFO2S, the O atom and the 4-fluoro­phenyl group of the 4-fluoro­phenyl­sulfinyl substituent are located on opposite sides of the plane through the benzofuran fragment; the 4-fluoro­phenyl ring is approximately perpendicular to this plane [dihedral angle = 89.38 (6)°]. In the crystal, mol­ecules are linked by a Br(...)Br contact [3.4816 (5) Å], and weak inter­molecular C—S(...)π [3.499 (2) Å] and C—F(...)π [3.535 (2) Å] inter­actions.

Related literature

For the crystal structures of similar derivatives, see: Choi et al. (2010a [triangle],b [triangle]). For the biological 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]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1297-scheme1.jpg

Experimental

Crystal data

  • C15H10BrFO2S
  • M r = 353.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1297-efi3.jpg
  • a = 11.4704 (4) Å
  • b = 6.1776 (2) Å
  • c = 19.6420 (7) Å
  • β = 98.432 (2)°
  • V = 1376.78 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.15 mm−1
  • T = 173 K
  • 0.32 × 0.26 × 0.21 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.453, T max = 0.746
  • 11827 measured reflections
  • 3148 independent reflections
  • 2655 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.072
  • S = 1.05
  • 3148 reflections
  • 182 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.53 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810016181/ng2767sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016181/ng2767Isup2.hkl

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

supplementary crystallographic information

Comment

The compounds containing benzofuran skeleton show potent biological activities such as antifungal (Aslam et al.., 2006), antitumor and antiviral (Galal et al.., 2009), antimicrobial (Khan et al.., 2005) properties. These compounds occur widely in nature (Akgul & Anil, 2003; Soekamto et al.. 2003). As a part of our ongoing studies of the effect of side chain substituents on the solid state structures of 2-methyl-3-(4-fluorophenylsulfinyl)-1-benzofuran analogues (Choi et al.., 2010a,b), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.007 (1) Å from the least-squares plane defined by the nine constituent atoms. The 4-fluorophenyl ring is almost perpendicular to the plane of the benzofuran fragment [89.38 (6)°] and is tilted slightly towards it. The crystal packing (Fig. 2) is stabilized by a Br···Br interaction at 3.4816 (5) Å. The molecular packing (Fig. 2) is further stabilized by a weak intermolecular C–S···π interaction between the sulfur and the 4-fluorophenyl ring of an adjacent molecule, with a C1–S···Cg1ii [3.499 (2) Å] (Cg1 is the centroid of the C10-C15 4-fluorophenyl ring), and by a weak intermolecular C–F···π interaction between the fluorine and the benzene ring of a neighbouring benzofuran system, with C13–F···Cg2iii [3.535 (2) Å] (Cg2 is the centroid of the C2-C7 benzene ring).

Experimental

77% 3-Chloroperoxybenzoic acid (224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-bromo-3-(4-fluorophenylsulfanyl)-2-methyl-1-benzofuran (303 mg, 0.9 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 4h, 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 (silica gel, hexane-ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 78%, m.p. 401-402 K; Rf = 0.64 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in benzene at room temperature.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C–H = 0.93 Å for aryl and 0.96 Å for methyl H atoms. Uiso(H) = 1.2Ueq(C) for aryl and 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.
Br···Br, C–S···π and C–F···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: ...

Crystal data

C15H10BrFO2SF(000) = 704
Mr = 353.20Dx = 1.704 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4955 reflections
a = 11.4704 (4) Åθ = 2.6–27.5°
b = 6.1776 (2) ŵ = 3.15 mm1
c = 19.6420 (7) ÅT = 173 K
β = 98.432 (2)°Block, colourless
V = 1376.78 (8) Å30.32 × 0.26 × 0.21 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer3148 independent reflections
Radiation source: rotating anode2655 reflections with I > 2σ(I)
graphite multilayerRint = 0.028
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.8°
[var phi] and ω scansh = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −8→7
Tmin = 0.453, Tmax = 0.746l = −25→25
11827 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)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.072H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0338P)2 + 0.5303P] where P = (Fo2 + 2Fc2)/3
3148 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = −0.53 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br0.50266 (2)0.78650 (4)0.558051 (12)0.04487 (9)
S0.93498 (4)0.16534 (9)0.60352 (3)0.03310 (13)
F0.72642 (13)0.0128 (3)0.31650 (7)0.0625 (4)
O10.69236 (13)0.0086 (2)0.71739 (7)0.0367 (3)
O20.97008 (13)0.3979 (3)0.60830 (8)0.0431 (4)
C10.80963 (16)0.1358 (3)0.64457 (9)0.0291 (4)
C20.70597 (16)0.2719 (3)0.63776 (9)0.0273 (4)
C30.66711 (16)0.4522 (3)0.59916 (10)0.0296 (4)
H30.71130.51280.56800.035*
C40.55947 (17)0.5382 (3)0.60907 (9)0.0308 (4)
C50.49100 (17)0.4492 (4)0.65478 (10)0.0343 (5)
H50.41880.51140.65940.041*
C60.52929 (19)0.2691 (4)0.69335 (10)0.0367 (5)
H60.48450.20760.72410.044*
C70.63708 (18)0.1851 (3)0.68398 (9)0.0299 (4)
C80.79788 (18)−0.0166 (3)0.69259 (10)0.0329 (4)
C90.8737 (2)−0.1974 (4)0.72202 (12)0.0460 (6)
H9A0.9422−0.20580.69930.069*
H9B0.8305−0.33070.71550.069*
H9C0.8975−0.17300.77030.069*
C100.86555 (15)0.1228 (3)0.51655 (10)0.0284 (4)
C110.81711 (18)−0.0770 (4)0.49734 (11)0.0370 (5)
H110.8172−0.18630.52990.044*
C120.7688 (2)−0.1142 (4)0.42988 (12)0.0436 (5)
H120.7342−0.24660.41640.052*
C130.77312 (18)0.0497 (4)0.38319 (11)0.0400 (5)
C140.82316 (19)0.2465 (4)0.40008 (11)0.0391 (5)
H140.82570.35290.36680.047*
C150.87026 (17)0.2836 (3)0.46836 (11)0.0332 (4)
H150.90480.41620.48150.040*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.04284 (15)0.03939 (15)0.05249 (15)0.01201 (10)0.00742 (10)0.00670 (10)
S0.0217 (2)0.0377 (3)0.0401 (3)−0.0009 (2)0.00528 (19)0.0033 (2)
F0.0624 (9)0.0825 (12)0.0413 (7)−0.0034 (8)0.0035 (6)−0.0134 (7)
O10.0403 (8)0.0406 (9)0.0311 (7)0.0008 (7)0.0112 (6)0.0085 (6)
O20.0390 (8)0.0431 (9)0.0478 (9)−0.0181 (7)0.0088 (7)−0.0041 (7)
C10.0260 (9)0.0304 (10)0.0309 (9)−0.0018 (8)0.0041 (7)0.0009 (8)
C20.0252 (9)0.0294 (10)0.0275 (9)−0.0034 (8)0.0045 (7)−0.0024 (8)
C30.0276 (9)0.0298 (11)0.0323 (9)−0.0024 (8)0.0076 (7)0.0019 (8)
C40.0312 (10)0.0300 (11)0.0304 (9)0.0005 (8)0.0023 (8)−0.0037 (8)
C50.0270 (10)0.0450 (13)0.0319 (10)0.0022 (9)0.0076 (8)−0.0072 (9)
C60.0355 (11)0.0477 (14)0.0296 (10)−0.0023 (10)0.0136 (8)0.0015 (9)
C70.0339 (10)0.0317 (11)0.0248 (9)−0.0024 (9)0.0063 (7)0.0001 (8)
C80.0336 (11)0.0345 (11)0.0299 (9)0.0004 (9)0.0027 (8)0.0014 (8)
C90.0523 (14)0.0442 (14)0.0402 (12)0.0076 (11)0.0027 (10)0.0124 (10)
C100.0198 (8)0.0293 (10)0.0384 (10)0.0022 (8)0.0116 (7)0.0008 (8)
C110.0366 (11)0.0294 (11)0.0472 (12)−0.0027 (9)0.0137 (9)0.0025 (9)
C120.0407 (12)0.0369 (13)0.0549 (13)−0.0071 (10)0.0131 (10)−0.0131 (11)
C130.0329 (11)0.0516 (15)0.0368 (11)0.0042 (10)0.0095 (9)−0.0071 (10)
C140.0342 (11)0.0430 (13)0.0419 (11)0.0045 (10)0.0118 (9)0.0077 (10)
C150.0259 (9)0.0294 (11)0.0459 (11)−0.0003 (8)0.0100 (8)0.0020 (9)

Geometric parameters (Å, °)

Br—C41.895 (2)C6—C71.378 (3)
Br—Bri3.4816 (5)C6—H60.9300
S—O21.4910 (17)C8—C91.480 (3)
S—C11.7581 (19)C9—H9A0.9600
S—C101.795 (2)C9—H9B0.9600
F—C131.360 (2)C9—H9C0.9600
O1—C81.378 (2)C10—C151.379 (3)
O1—C71.378 (2)C10—C111.383 (3)
C1—C81.353 (3)C11—C121.379 (3)
C1—C21.446 (3)C11—H110.9300
C2—C31.384 (3)C12—C131.372 (3)
C2—C71.395 (3)C12—H120.9300
C3—C41.384 (3)C13—C141.365 (3)
C3—H30.9300C14—C151.389 (3)
C4—C51.390 (3)C14—H140.9300
C5—C61.381 (3)C15—H150.9300
C5—H50.9300
C4—Br—Bri158.65 (6)C1—C8—C9133.19 (19)
O2—S—C1107.60 (10)O1—C8—C9116.30 (18)
O2—S—C10106.21 (9)C8—C9—H9A109.5
C1—S—C1098.20 (8)C8—C9—H9B109.5
C8—O1—C7106.71 (15)H9A—C9—H9B109.5
C8—C1—C2107.72 (17)C8—C9—H9C109.5
C8—C1—S124.30 (16)H9A—C9—H9C109.5
C2—C1—S127.87 (15)H9B—C9—H9C109.5
C3—C2—C7119.89 (18)C15—C10—C11120.69 (19)
C3—C2—C1135.47 (17)C15—C10—S119.42 (16)
C7—C2—C1104.63 (17)C11—C10—S119.65 (16)
C2—C3—C4117.02 (17)C12—C11—C10120.0 (2)
C2—C3—H3121.5C12—C11—H11120.0
C4—C3—H3121.5C10—C11—H11120.0
C3—C4—C5122.64 (19)C13—C12—C11118.1 (2)
C3—C4—Br118.76 (14)C13—C12—H12121.0
C5—C4—Br118.60 (15)C11—C12—H12121.0
C6—C5—C4120.57 (19)F—C13—C14118.4 (2)
C6—C5—H5119.7F—C13—C12118.2 (2)
C4—C5—H5119.7C14—C13—C12123.4 (2)
C7—C6—C5116.72 (18)C13—C14—C15118.1 (2)
C7—C6—H6121.6C13—C14—H14120.9
C5—C6—H6121.6C15—C14—H14120.9
C6—C7—O1126.41 (17)C10—C15—C14119.7 (2)
C6—C7—C2123.16 (19)C10—C15—H15120.2
O1—C7—C2110.43 (17)C14—C15—H15120.2
C1—C8—O1110.50 (17)
O2—S—C1—C8−130.32 (18)C1—C2—C7—O10.0 (2)
C10—S—C1—C8119.71 (19)C2—C1—C8—O10.7 (2)
O2—S—C1—C245.3 (2)S—C1—C8—O1177.08 (14)
C10—S—C1—C2−64.66 (19)C2—C1—C8—C9−179.4 (2)
C8—C1—C2—C3178.8 (2)S—C1—C8—C9−3.1 (4)
S—C1—C2—C32.6 (3)C7—O1—C8—C1−0.7 (2)
C8—C1—C2—C7−0.4 (2)C7—O1—C8—C9179.43 (18)
S—C1—C2—C7−176.65 (15)O2—S—C10—C159.31 (17)
C7—C2—C3—C40.1 (3)C1—S—C10—C15120.42 (16)
C1—C2—C3—C4−179.1 (2)O2—S—C10—C11−176.30 (15)
C2—C3—C4—C5−0.8 (3)C1—S—C10—C11−65.20 (17)
C2—C3—C4—Br179.50 (14)C15—C10—C11—C12−2.5 (3)
C3—C4—C5—C60.7 (3)S—C10—C11—C12−176.83 (16)
Br—C4—C5—C6−179.57 (16)C10—C11—C12—C131.5 (3)
C4—C5—C6—C70.0 (3)C11—C12—C13—F179.44 (18)
C5—C6—C7—O1179.32 (19)C11—C12—C13—C140.3 (3)
C5—C6—C7—C2−0.7 (3)F—C13—C14—C15179.71 (18)
C8—O1—C7—C6−179.6 (2)C12—C13—C14—C15−1.1 (3)
C8—O1—C7—C20.4 (2)C11—C10—C15—C141.7 (3)
C3—C2—C7—C60.6 (3)S—C10—C15—C14175.98 (15)
C1—C2—C7—C6180.00 (19)C13—C14—C15—C100.1 (3)
C3—C2—C7—O1−179.40 (17)

Symmetry codes: (i) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2767).

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, o543. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst. E66, o564. [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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