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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2350.
Published online 2010 August 18. doi:  10.1107/S1600536810032502
PMCID: PMC3007851

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

Abstract

In the title compound, C15H10ClFO3S, the 4-fluoro­phenyl ring makes a dihedral angle of 75.83 (5)° with the plane of the benzofuran fragment. In the crystal, weak inter­molecular C—H(...)O hydrogen bonds link the mol­ecules into centrosymmetric dimers, which are further linked via an aromatic π–π inter­action between the benzene rings of adjacent mol­ecules [centroid–centroid distance = 3.510 (2) 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)-5-halogeno-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-o2350-scheme1.jpg

Experimental

Crystal data

  • C15H10ClFO3S
  • M r = 324.74
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2350-efi1.jpg
  • a = 7.341 (2) Å
  • b = 9.138 (2) Å
  • c = 11.347 (3) Å
  • α = 71.161 (12)°
  • β = 79.177 (11)°
  • γ = 69.108 (10)°
  • V = 670.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.46 mm−1
  • T = 173 K
  • 0.32 × 0.32 × 0.24 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.673, T max = 0.746
  • 11617 measured reflections
  • 3098 independent reflections
  • 2847 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.103
  • S = 1.08
  • 3098 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.41 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/S1600536810032502/fk2023sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032502/fk2023Isup2.hkl

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

Acknowledgments

This work was supported by Blue-Bio Industry RIC at Dongeui University as an RIC program under the Ministry of Knowledge Economy and Busan city.

supplementary crystallographic information

Comment

Many compounds containing a benzofuran skeleton show interesting pharmacological properties such as antifungal, antitumor, 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)-5-halo-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 0.013 (1) 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 75.83 (5)°. The crystal packing (Fig. 2) is stabilized by weak intermolecular C–H···O hydrogen bonds between the 4-fluorophenyl H atom and the oxygen of the O═S═O unit, with C11–H11···O3i (Table 1). The packing is further stabilized by an aromatic π–π interaction between the benzene rings of neighbouring molecules, with a Cg···Cgii distance of 3.510 (2) Å (Cg is the centroid of the C2-C7 benzene ring).

Experimental

77% 3-chloroperoxybenzoic acid (515 mg, 2.3 mmol) was added in small portions to a stirred solution of 5-chloro-3-(4-fluorophenylsulfanyl)-2-methyl-1-benzofuran (339 mg, 1.1 mmol) in dichloromethane (40 mL) at 273 K. After being stirred at room temperature for 10h, 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 (benzene) to afford the title compound as a colourless solid [yield 78%, m.p. 452-453 K; Rf = 0.54 (benzene)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in chloroform at room temperature.

Refinement

All H atoms were clearly located from Fourier difference maps and refined at idealized positions 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 small spheres of arbitrary radius.
Fig. 2.
C–H···O and π–π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+2, -z+1.]

Crystal data

C15H10ClFO3SZ = 2
Mr = 324.74F(000) = 332
Triclinic, P1Dx = 1.608 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.341 (2) ÅCell parameters from 8342 reflections
b = 9.138 (2) Åθ = 2.5–27.7°
c = 11.347 (3) ŵ = 0.46 mm1
α = 71.161 (12)°T = 173 K
β = 79.177 (11)°Block, colourless
γ = 69.108 (10)°0.32 × 0.32 × 0.24 mm
V = 670.8 (3) Å3

Data collection

Bruker SMART APEXII CCD diffractometer3098 independent reflections
Radiation source: rotating anode2847 reflections with I > 2σ(I)
graphite multilayerRint = 0.031
Detector resolution: 10.0 pixels mm-1θmax = 27.7°, θmin = 1.9°
[var phi] and ω scansh = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −11→11
Tmin = 0.673, Tmax = 0.746l = −14→14
11617 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)] = 0.035Hydrogen site location: difference Fourier map
wR(F2) = 0.103H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0581P)2 + 0.2203P] where P = (Fo2 + 2Fc2)/3
3098 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.41 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
Cl0.24730 (7)0.91535 (6)0.18345 (4)0.04478 (15)
S0.53086 (5)0.60366 (4)0.70560 (3)0.02358 (12)
O10.22044 (16)1.06562 (13)0.64622 (10)0.0287 (2)
O20.64062 (16)0.58741 (14)0.80400 (10)0.0305 (3)
O30.63148 (17)0.54999 (13)0.59840 (10)0.0316 (3)
C10.3925 (2)0.80676 (17)0.65127 (13)0.0239 (3)
C20.3246 (2)0.88838 (17)0.52755 (13)0.0233 (3)
C30.3365 (2)0.84457 (19)0.41916 (14)0.0269 (3)
H30.40570.73940.41350.032*
C40.2404 (2)0.9649 (2)0.32022 (14)0.0295 (3)
C50.1371 (2)1.1238 (2)0.32493 (15)0.0321 (3)
H50.07561.20060.25570.038*
C60.1260 (2)1.16749 (19)0.43212 (16)0.0306 (3)
H60.05851.27310.43740.037*
C70.2195 (2)1.04713 (18)0.53112 (14)0.0252 (3)
C80.3252 (2)0.91825 (18)0.71784 (14)0.0266 (3)
C90.3365 (3)0.9110 (2)0.84855 (15)0.0357 (4)
H9A0.41350.80340.89140.053*
H9B0.20710.93650.88980.053*
H9C0.39630.98860.84920.053*
C100.3594 (2)0.50045 (17)0.77249 (13)0.0239 (3)
C110.2586 (2)0.46848 (18)0.69636 (14)0.0278 (3)
H110.28140.50150.60990.033*
C120.1243 (2)0.3871 (2)0.75089 (17)0.0338 (4)
H120.05330.36590.70220.041*
C130.0986 (3)0.3385 (2)0.87841 (17)0.0355 (4)
C140.1979 (3)0.3677 (2)0.95508 (16)0.0395 (4)
H140.17690.33181.04150.047*
C150.3287 (3)0.4512 (2)0.90095 (15)0.0331 (3)
H150.39630.47450.95050.040*
F−0.03024 (18)0.25795 (15)0.93220 (12)0.0533 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0493 (3)0.0579 (3)0.0263 (2)−0.0134 (2)−0.01042 (18)−0.01054 (19)
S0.02279 (19)0.02453 (19)0.02076 (19)−0.00504 (14)−0.00356 (14)−0.00462 (13)
O10.0298 (6)0.0254 (5)0.0308 (6)−0.0077 (4)−0.0021 (4)−0.0093 (4)
O20.0275 (5)0.0352 (6)0.0283 (6)−0.0104 (5)−0.0088 (4)−0.0041 (5)
O30.0311 (6)0.0313 (6)0.0261 (5)−0.0037 (5)0.0011 (4)−0.0088 (4)
C10.0231 (7)0.0255 (7)0.0221 (7)−0.0078 (5)−0.0023 (5)−0.0047 (5)
C20.0197 (6)0.0244 (7)0.0236 (7)−0.0080 (5)−0.0014 (5)−0.0030 (5)
C30.0251 (7)0.0292 (7)0.0239 (7)−0.0071 (6)−0.0021 (6)−0.0059 (6)
C40.0268 (7)0.0377 (8)0.0225 (7)−0.0129 (6)−0.0023 (6)−0.0036 (6)
C50.0255 (7)0.0339 (8)0.0297 (8)−0.0105 (6)−0.0060 (6)0.0038 (6)
C60.0254 (7)0.0234 (7)0.0372 (8)−0.0072 (6)−0.0028 (6)−0.0011 (6)
C70.0221 (7)0.0257 (7)0.0276 (7)−0.0100 (6)−0.0005 (5)−0.0053 (6)
C80.0240 (7)0.0278 (7)0.0280 (7)−0.0095 (6)−0.0013 (6)−0.0070 (6)
C90.0400 (9)0.0395 (9)0.0296 (8)−0.0107 (7)−0.0023 (7)−0.0150 (7)
C100.0254 (7)0.0210 (6)0.0233 (7)−0.0046 (5)−0.0044 (5)−0.0053 (5)
C110.0281 (7)0.0280 (7)0.0269 (7)−0.0040 (6)−0.0053 (6)−0.0108 (6)
C120.0331 (8)0.0308 (8)0.0426 (9)−0.0080 (6)−0.0100 (7)−0.0156 (7)
C130.0322 (8)0.0283 (8)0.0461 (10)−0.0143 (7)−0.0036 (7)−0.0050 (7)
C140.0460 (10)0.0450 (10)0.0271 (8)−0.0225 (8)−0.0039 (7)−0.0002 (7)
C150.0391 (9)0.0396 (9)0.0246 (7)−0.0186 (7)−0.0068 (6)−0.0052 (6)
F0.0511 (7)0.0503 (7)0.0638 (8)−0.0340 (6)−0.0040 (6)−0.0032 (6)

Geometric parameters (Å, °)

Cl—C41.7388 (17)C6—H60.9300
S—O31.4336 (11)C8—C91.480 (2)
S—O21.4365 (11)C9—H9A0.9600
S—C11.7344 (15)C9—H9B0.9600
S—C101.7534 (16)C9—H9C0.9600
O1—C81.3619 (18)C10—C151.380 (2)
O1—C71.3716 (19)C10—C111.392 (2)
C1—C81.360 (2)C11—C121.380 (2)
C1—C21.448 (2)C11—H110.9300
C2—C71.389 (2)C12—C131.367 (3)
C2—C31.390 (2)C12—H120.9300
C3—C41.383 (2)C13—F1.341 (2)
C3—H30.9300C13—C141.373 (3)
C4—C51.392 (2)C14—C151.371 (2)
C5—C61.378 (2)C14—H140.9300
C5—H50.9300C15—H150.9300
C6—C71.377 (2)
O3—S—O2119.62 (7)C1—C8—O1110.49 (13)
O3—S—C1107.05 (7)C1—C8—C9134.07 (15)
O2—S—C1108.80 (7)O1—C8—C9115.40 (13)
O3—S—C10107.97 (7)C8—C9—H9A109.5
O2—S—C10107.47 (7)C8—C9—H9B109.5
C1—S—C10105.01 (7)H9A—C9—H9B109.5
C8—O1—C7107.07 (11)C8—C9—H9C109.5
C8—C1—C2107.35 (13)H9A—C9—H9C109.5
C8—C1—S126.21 (12)H9B—C9—H9C109.5
C2—C1—S126.43 (11)C15—C10—C11121.27 (15)
C7—C2—C3119.30 (14)C15—C10—S118.69 (12)
C7—C2—C1104.34 (13)C11—C10—S120.04 (12)
C3—C2—C1136.33 (14)C12—C11—C10119.11 (15)
C4—C3—C2116.80 (14)C12—C11—H11120.4
C4—C3—H3121.6C10—C11—H11120.4
C2—C3—H3121.6C13—C12—C11118.22 (15)
C3—C4—C5123.19 (15)C13—C12—H12120.9
C3—C4—Cl118.60 (13)C11—C12—H12120.9
C5—C4—Cl118.21 (12)F—C13—C12118.62 (16)
C6—C5—C4120.04 (15)F—C13—C14117.88 (16)
C6—C5—H5120.0C12—C13—C14123.50 (16)
C4—C5—H5120.0C15—C14—C13118.32 (16)
C7—C6—C5116.73 (14)C15—C14—H14120.8
C7—C6—H6121.6C13—C14—H14120.8
C5—C6—H6121.6C14—C15—C10119.55 (15)
O1—C7—C6125.32 (14)C14—C15—H15120.2
O1—C7—C2110.74 (13)C10—C15—H15120.2
C6—C7—C2123.93 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11···O3i0.932.483.335 (2)153.

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FK2023).

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, o1909. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst. E66, o2049. [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]
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  • 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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