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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1637.
Published online 2010 June 16. doi:  10.1107/S1600536810021823
PMCID: PMC3006853

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

Abstract

In the title compound, C15H10F2O2S, the S=O and the 4-fluoro­phenyl groups are located on opposite sides of the plane of benzofuran ring system, and the 4-fluoro­phenyl ring is nearly perpendicular to the benzofuran plane with a dihedral angle of 89.93 (4)°. In the crystal structure, mol­ecules are linked by weak inter­molecular C—H(...)O hydrogen bonding and C—H(...)π inter­actions.

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-fluoro­phenyl­sulfin­yl)-2-methyl-1-benzofuran deriv­atives, see: Choi et al. (2010a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1637-scheme1.jpg

Experimental

Crystal data

  • C15H10F2O2S
  • M r = 292.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1637-efi5.jpg
  • a = 14.9369 (4) Å
  • b = 10.6284 (3) Å
  • c = 16.1532 (4) Å
  • V = 2564.41 (12) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 174 K
  • 0.40 × 0.32 × 0.28 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.898, T max = 0.927
  • 22576 measured reflections
  • 2962 independent reflections
  • 2578 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.091
  • S = 1.08
  • 2962 reflections
  • 183 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.32 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/S1600536810021823/xu2777sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021823/xu2777Isup2.hkl

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

Acknowledgments

This work was supported by a Dong-eui University grant (2010AA096).

supplementary crystallographic information

Comment

The compounds containing benzofuran skeleton exhibit diverse pharmacological properties such as antifungal (Aslam et al., 2006), antitumor and antiviral (Galal et al., 2009), antimicrobial (Khan et al., 2005) activities. These compounds widely occur 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 3-(4-fluorophenylsulfinyl)-2-methyl-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 0.012 (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 [89.93 (4)°] and is tilted slightly towards it. The crystal packing (Fig. 2) is stabilized by weak intermolecular C–H···O hydrogen bonds; the first one between the methyl H atom and the oxygen of the S═O unit, with a C9–H9B···O2i, and the second one between the 4-fluorophenyl H atom and the oxygen of the S═O unit, with a C14–H14···O2ii, respectively (Table 1). The molecular packing (Fig. 2) is further stabilized by a C–H···π interaction between the 4-fluorophenyl H atom and the furan ring of an adjacent benzofuran system, with a C15–H15···Cg ii(Table 1; Cg is the centroid of the C1/C2/C7/O1/C8 furan ring).

Experimental

77% 3-Chloroperoxybenzoic acid (291 mg, 1.3 mmol) was added in small portions to a stirred solution of 5-fluoro-3-(4-fluorophenylsulfanyl)-2-methyl-1-benzofuran (350 mg, 1.2 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 4 h, the mixture was washed with saturated sodium bicarbonate solution, 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, 1:1 v/v) to afford the title compound as a colorless solid [yield 78%, m.p. 418-419 K; Rf = 0.49 (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.
C–H···O and C–H···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) - x + 3/2, y - 1/2, z; (ii) - x ...

Crystal data

C15H10F2O2SF(000) = 1200
Mr = 292.29Dx = 1.514 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 9962 reflections
a = 14.9369 (4) Åθ = 2.4–27.6°
b = 10.6284 (3) ŵ = 0.27 mm1
c = 16.1532 (4) ÅT = 174 K
V = 2564.41 (12) Å3Block, colourless
Z = 80.40 × 0.32 × 0.28 mm

Data collection

Bruker SMART APEXII CCD diffractometer2962 independent reflections
Radiation source: rotating anode2578 reflections with I > 2σ(I)
graphite multilayerRint = 0.029
Detector resolution: 10.0 pixels mm-1θmax = 27.6°, θmin = 2.4°
[var phi] and ω scansh = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −13→11
Tmin = 0.898, Tmax = 0.927l = −18→21
22576 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.091w = 1/[σ2(Fo2) + (0.0448P)2 + 0.984P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2962 reflectionsΔρmax = 0.29 e Å3
183 parametersΔρmin = −0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0035 (5)

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
S10.66618 (2)0.39412 (3)0.07071 (2)0.02868 (12)
F10.74089 (8)0.39246 (10)0.42659 (5)0.0468 (3)
F20.43716 (7)0.81769 (9)0.16672 (7)0.0533 (3)
O10.59409 (7)0.09156 (9)0.19275 (6)0.0308 (2)
O20.76049 (7)0.43398 (11)0.08603 (7)0.0371 (3)
C10.63924 (9)0.27918 (12)0.14445 (8)0.0257 (3)
C20.65824 (8)0.27675 (12)0.23194 (8)0.0244 (3)
C30.69806 (9)0.35842 (13)0.28866 (9)0.0287 (3)
H30.71980.43900.27300.034*
C40.70389 (10)0.31507 (14)0.36869 (9)0.0317 (3)
C50.67501 (10)0.19769 (15)0.39509 (9)0.0334 (3)
H50.68170.17350.45140.040*
C60.63635 (10)0.11614 (13)0.33859 (9)0.0318 (3)
H60.61590.03500.35440.038*
C70.62909 (8)0.15881 (12)0.25823 (8)0.0265 (3)
C80.60257 (9)0.16619 (13)0.12435 (9)0.0287 (3)
C90.57225 (10)0.11157 (15)0.04501 (10)0.0379 (4)
H9A0.50680.10580.04480.057*
H9B0.59790.02730.03840.057*
H9C0.59190.1654−0.00080.057*
C100.59618 (9)0.51953 (13)0.10727 (8)0.0275 (3)
C110.50426 (10)0.50221 (15)0.11532 (10)0.0354 (3)
H110.47860.42150.10660.043*
C120.45059 (10)0.60330 (15)0.13609 (11)0.0401 (4)
H120.38770.59340.14230.048*
C130.49058 (11)0.71859 (14)0.14756 (10)0.0364 (3)
C140.58090 (11)0.73846 (14)0.13999 (10)0.0391 (4)
H140.60610.81950.14880.047*
C150.63445 (10)0.63648 (14)0.11909 (9)0.0342 (3)
H150.69720.64710.11290.041*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.03005 (19)0.0329 (2)0.02308 (18)0.00313 (13)−0.00015 (12)0.00211 (12)
F10.0588 (6)0.0527 (6)0.0289 (5)−0.0174 (5)−0.0098 (4)−0.0059 (4)
F20.0614 (6)0.0369 (5)0.0617 (7)0.0204 (5)0.0077 (5)0.0049 (5)
O10.0328 (5)0.0259 (5)0.0338 (5)−0.0047 (4)−0.0004 (4)−0.0046 (4)
O20.0271 (5)0.0422 (6)0.0421 (6)0.0011 (4)0.0044 (4)0.0098 (5)
C10.0250 (6)0.0265 (6)0.0257 (6)0.0018 (5)−0.0009 (5)−0.0013 (5)
C20.0227 (6)0.0250 (6)0.0256 (6)0.0021 (5)0.0002 (5)−0.0009 (5)
C30.0305 (7)0.0261 (6)0.0294 (7)−0.0034 (5)−0.0007 (5)−0.0014 (5)
C40.0312 (7)0.0363 (7)0.0275 (7)−0.0027 (6)−0.0048 (5)−0.0038 (6)
C50.0342 (7)0.0388 (8)0.0273 (7)0.0008 (6)−0.0016 (6)0.0063 (6)
C60.0331 (7)0.0272 (7)0.0352 (8)−0.0009 (5)0.0024 (6)0.0053 (6)
C70.0248 (6)0.0244 (6)0.0302 (7)0.0002 (5)−0.0003 (5)−0.0031 (5)
C80.0256 (6)0.0302 (7)0.0302 (7)0.0024 (5)−0.0005 (5)−0.0039 (5)
C90.0349 (8)0.0414 (8)0.0373 (8)−0.0003 (6)−0.0064 (6)−0.0134 (6)
C100.0292 (6)0.0289 (7)0.0244 (6)0.0016 (5)−0.0027 (5)0.0035 (5)
C110.0285 (6)0.0306 (7)0.0471 (9)−0.0018 (6)−0.0034 (6)0.0011 (6)
C120.0295 (7)0.0414 (9)0.0493 (10)0.0042 (6)−0.0001 (7)0.0055 (7)
C130.0435 (8)0.0303 (7)0.0352 (8)0.0101 (6)0.0008 (6)0.0064 (6)
C140.0477 (9)0.0267 (7)0.0429 (9)−0.0032 (6)0.0018 (7)0.0028 (6)
C150.0318 (7)0.0334 (7)0.0374 (8)−0.0051 (6)0.0005 (6)0.0041 (6)

Geometric parameters (Å, °)

S1—O21.492 (1)C6—C71.379 (2)
S1—C11.753 (1)C6—H60.9500
S1—C101.794 (1)C8—C91.478 (2)
F1—C41.363 (2)C9—H9A0.9800
F2—C131.357 (2)C9—H9B0.9800
O1—C81.366 (2)C9—H9C0.9800
O1—C71.379 (2)C10—C151.381 (2)
C1—C81.359 (2)C10—C111.391 (2)
C1—C21.442 (2)C11—C121.382 (2)
C2—C71.393 (2)C11—H110.9500
C2—C31.395 (2)C12—C131.376 (2)
C3—C41.375 (2)C12—H120.9500
C3—H30.9500C13—C141.371 (2)
C4—C51.387 (2)C14—C151.389 (2)
C5—C61.385 (2)C14—H140.9500
C5—H50.9500C15—H150.9500
O2—S1—C1107.57 (6)C1—C8—C9132.66 (14)
O2—S1—C10106.55 (7)O1—C8—C9116.41 (13)
C1—S1—C1099.22 (6)C8—C9—H9A109.5
C8—O1—C7106.51 (10)C8—C9—H9B109.5
C8—C1—C2107.32 (12)H9A—C9—H9B109.5
C8—C1—S1123.09 (10)C8—C9—H9C109.5
C2—C1—S1129.30 (10)H9A—C9—H9C109.5
C7—C2—C3119.53 (12)H9B—C9—H9C109.5
C7—C2—C1104.67 (11)C15—C10—C11120.97 (13)
C3—C2—C1135.77 (13)C15—C10—S1118.22 (11)
C4—C3—C2115.84 (13)C11—C10—S1120.50 (11)
C4—C3—H3122.1C12—C11—C10119.48 (14)
C2—C3—H3122.1C12—C11—H11120.3
F1—C4—C3117.95 (13)C10—C11—H11120.3
F1—C4—C5117.26 (13)C13—C12—C11118.25 (14)
C3—C4—C5124.79 (13)C13—C12—H12120.9
C6—C5—C4119.34 (13)C11—C12—H12120.9
C6—C5—H5120.3F2—C13—C14118.64 (14)
C4—C5—H5120.3F2—C13—C12117.82 (14)
C7—C6—C5116.56 (13)C14—C13—C12123.53 (14)
C7—C6—H6121.7C13—C14—C15117.92 (14)
C5—C6—H6121.7C13—C14—H14121.0
C6—C7—O1125.52 (12)C15—C14—H14121.0
C6—C7—C2123.92 (13)C10—C15—C14119.84 (14)
O1—C7—C2110.55 (12)C10—C15—H15120.1
C1—C8—O1110.93 (12)C14—C15—H15120.1
O2—S1—C1—C8−129.33 (12)C1—C2—C7—O1−0.14 (14)
C10—S1—C1—C8119.93 (12)C2—C1—C8—O11.61 (15)
O2—S1—C1—C243.56 (14)S1—C1—C8—O1175.85 (9)
C10—S1—C1—C2−67.18 (13)C2—C1—C8—C9−177.80 (14)
C8—C1—C2—C7−0.87 (14)S1—C1—C8—C9−3.6 (2)
S1—C1—C2—C7−174.64 (10)C7—O1—C8—C1−1.69 (15)
C8—C1—C2—C3176.94 (15)C7—O1—C8—C9177.83 (12)
S1—C1—C2—C33.2 (2)O2—S1—C10—C1517.87 (13)
C7—C2—C3—C4−1.17 (19)C1—S1—C10—C15129.42 (12)
C1—C2—C3—C4−178.74 (14)O2—S1—C10—C11−168.52 (11)
C2—C3—C4—F1−178.89 (12)C1—S1—C10—C11−56.97 (13)
C2—C3—C4—C51.3 (2)C15—C10—C11—C12−0.5 (2)
F1—C4—C5—C6179.52 (13)S1—C10—C11—C12−173.95 (12)
C3—C4—C5—C6−0.7 (2)C10—C11—C12—C130.4 (2)
C4—C5—C6—C7−0.1 (2)C11—C12—C13—F2179.03 (14)
C5—C6—C7—O1178.89 (12)C11—C12—C13—C14−0.4 (3)
C5—C6—C7—C20.2 (2)F2—C13—C14—C15−179.02 (14)
C8—O1—C7—C6−177.78 (13)C12—C13—C14—C150.4 (2)
C8—O1—C7—C21.10 (14)C11—C10—C15—C140.5 (2)
C3—C2—C7—C60.5 (2)S1—C10—C15—C14174.11 (12)
C1—C2—C7—C6178.75 (13)C13—C14—C15—C10−0.5 (2)
C3—C2—C7—O1−178.39 (11)

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the furan ring.
D—H···AD—HH···AD···AD—H···A
C9—H9B···O2i0.982.453.200 (2)133
C14—H14···O2ii0.952.553.270 (2)133
C15—H15···Cgii0.952.983.828 (2)149

Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+3/2, y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2777).

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). APEX2SADABS 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, o1297. [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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