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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o643.
Published online 2010 February 17. doi:  10.1107/S1600536810005702
PMCID: PMC2983659

3-(4-Fluoro­phenyl­sulfin­yl)-2,4,6,7-tetra­methyl-1-benzofuran

Abstract

In the title compound, C18H17FO2S, the 4-fluoro­phenyl ring is almost perpendicular to the benzofuran fragment [88.07 (5)°]. The crystal structure exhibits weak inter­molecular C—H(...)O hydrogen bonds and C—H(...)π inter­actions. The mol­ecules form pseudo-helices along the a axis.

Related literature

For the crystal structures of similar 2-methyl-3-phenyl­sulfinyl-1-benzofuran derivatives, see: Choi et al. (2007 [triangle], 2008a [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]).

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Object name is e-66-0o643-scheme1.jpg

Experimental

Crystal data

  • C18H17FO2S
  • M r = 316.38
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o643-efi13.jpg
  • a = 12.0034 (5) Å
  • b = 19.7455 (7) Å
  • c = 6.4918 (3) Å
  • V = 1538.64 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 169 K
  • 0.18 × 0.17 × 0.16 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.644, T max = 0.746
  • 8107 measured reflections
  • 2280 independent reflections
  • 2175 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.082
  • S = 1.06
  • 2280 reflections
  • 204 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.28 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 366 Friedel pairs
  • Flack parameter: 0.01 (12)

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 I. DOI: 10.1107/S1600536810005702/gw2077sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005702/gw2077Isup2.hkl

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

supplementary crystallographic information

Comment

Molecules containing benzofuran skeleton display significant biological activities such as antifungal (Aslam et al., 2006), antitumor and antiviral (Galal et al., 2009), antimicrobial (Khan et al., 2005) properties. These compounds are widely occurring 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-phenylsulfinyl-1-benzofuran analogues (Choi et al., 2007, 2008a,b), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.008 (2) 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 [88.07 (5)°] and is tilted slightly towards it. The crystal packing (Fig. 2) is stabilized by two intermolecular C—H···O hydrogen bonds; the first between the 4-fluorophenyl H atom and the furan O atom, with a C15—H15···O1i, and the second between the 4-fluorophenyl H atom and the oxygen of the S═O unit, with a C18—H18···O2ii, respectively (Table 1).

The title compound is crystallized in the non-centrosymmetric space group Pna21 in spite of having no asymmetric C atoms. The space group is caused by a right hand pseudo-helix along the a axis (Fig.3).

The molecular packing (Fig. 3) is further stabilized by two intermolecular C—H···π interactions; the first between the methyl H atom and the 4-fluorophenyl ring, with a C11—H11A···Cgii, the second between the methyl H atom and 4-fluorophenyl ring of an adjacent molecule, with a C12—H12A···Cgiii, respectively (Table 1; Cg is the centroid of the C13–C18 4-fluorophenyl ring.)

Experimental

77% 3-Chloroperoxybenzoic acid (291 mg, 1.3 mmol) was added in small portions to a stirred solution of 3-(4-fluorophenylsulfanyl)-2,4,6,7-tetramethyl-1-benzofuran (360 mg, 1.2 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 3h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (hexane–ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 82%, m.p. 437–438 K; Rf = 0.53 (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 ethyl acetate at room temperature.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aryl and 0.98 Å for methyl H atoms. Uiso(H) = 1.2Ueq (C) for aryl and 1.5Ueq(C) for methyl H atoms. The reported Flack parameter was obtained by TWIN/BASF procedure in SHELXL (Sheldrick, 2008).

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 interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) x - 1/2, - y + 1/2, z - 1; (ii) x + 1/2 , - y + 1/2, z; (iv) x + 1/2, - y + 1/2, z + 1; (v) x - 1/2, - y + 1/2, z.] ...
Fig. 3.
C—H···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: (ii) x + 1/2, - y + 1/2, z; (iii) x, y, z + 1; (vi) x - 1/2, - y + 1/2, z; (vii) ...

Crystal data

C18H17FO2SF(000) = 664
Mr = 316.38Dx = 1.366 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 4518 reflections
a = 12.0034 (5) Åθ = 2.7–27.4°
b = 19.7455 (7) ŵ = 0.23 mm1
c = 6.4918 (3) ÅT = 169 K
V = 1538.64 (11) Å3Block, colourless
Z = 40.18 × 0.17 × 0.16 mm

Data collection

Bruker SMART APEXII CCD diffractometer2280 independent reflections
Radiation source: Rotating Anode2175 reflections with I > 2σ(I)
Bruker HELIOS graded multilayer opticsRint = 0.024
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 2.0°
[var phi] and ω scansh = −13→15
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −25→25
Tmin = 0.644, Tmax = 0.746l = −4→8
8107 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)] = 0.032H-atom parameters constrained
wR(F2) = 0.082w = 1/[σ2(Fo2) + (0.0551P)2 + 0.1527P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2280 reflectionsΔρmax = 0.25 e Å3
204 parametersΔρmin = −0.28 e Å3
1 restraintAbsolute structure: Flack (1983), 366 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (12)

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
S0.38790 (4)0.25971 (2)0.83129 (12)0.02606 (12)
F0.48409 (13)0.07177 (8)0.1553 (3)0.0599 (5)
O10.66099 (10)0.36300 (7)0.9163 (2)0.0258 (3)
O20.28018 (11)0.29365 (7)0.7817 (3)0.0352 (4)
C10.49909 (14)0.31749 (9)0.8113 (3)0.0235 (4)
C20.52977 (15)0.36899 (9)0.6611 (3)0.0232 (4)
C30.48697 (16)0.39560 (10)0.4772 (3)0.0273 (4)
C40.54918 (17)0.44634 (9)0.3828 (3)0.0307 (4)
H40.52140.46550.25870.037*
C50.65120 (17)0.47098 (9)0.4609 (4)0.0306 (4)
C60.69347 (16)0.44561 (9)0.6454 (4)0.0265 (4)
C70.62992 (15)0.39505 (9)0.7356 (3)0.0241 (4)
C80.57968 (16)0.31611 (9)0.9575 (3)0.0246 (4)
C90.38031 (17)0.37126 (12)0.3799 (3)0.0315 (5)
H9A0.35370.40510.28120.047*
H9B0.32390.36440.48710.047*
H9C0.39390.32840.30810.047*
C100.71324 (19)0.52419 (10)0.3411 (5)0.0419 (5)
H10A0.70750.56780.41260.063*
H10B0.68090.52820.20310.063*
H10C0.79180.51120.32970.063*
C110.80130 (18)0.46820 (11)0.7418 (4)0.0362 (5)
H11A0.86220.43950.69200.054*
H11B0.79590.46430.89200.054*
H11C0.81600.51540.70430.054*
C120.59977 (17)0.27324 (11)1.1404 (4)0.0297 (4)
H12A0.53540.24361.16300.045*
H12B0.61090.30211.26150.045*
H12C0.66640.24551.11790.045*
C130.42124 (15)0.20619 (9)0.6169 (3)0.0248 (4)
C140.33994 (16)0.19268 (9)0.4725 (4)0.0274 (4)
H140.26970.21460.48120.033*
C150.36070 (16)0.14697 (9)0.3142 (4)0.0311 (4)
H150.30590.13750.21270.037*
C160.46320 (18)0.11590 (10)0.3093 (4)0.0370 (5)
C170.54509 (18)0.12796 (11)0.4537 (4)0.0387 (5)
H170.61450.10500.44600.046*
C180.52465 (16)0.17380 (10)0.6092 (4)0.0309 (4)
H180.58000.18320.70970.037*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0189 (2)0.0315 (2)0.0278 (2)−0.00380 (16)0.0001 (2)0.0014 (2)
F0.0513 (8)0.0624 (9)0.0659 (11)0.0177 (7)−0.0131 (9)−0.0339 (9)
O10.0215 (7)0.0287 (6)0.0273 (7)−0.0043 (5)−0.0026 (6)0.0005 (6)
O20.0195 (7)0.0421 (8)0.0440 (10)0.0022 (6)0.0003 (6)−0.0035 (7)
C10.0197 (8)0.0252 (8)0.0255 (9)−0.0019 (6)0.0007 (8)−0.0010 (8)
C20.0212 (8)0.0233 (8)0.0252 (9)0.0028 (7)0.0013 (7)−0.0002 (8)
C30.0268 (9)0.0274 (9)0.0276 (10)0.0066 (7)−0.0018 (8)−0.0002 (8)
C40.0328 (10)0.0297 (9)0.0294 (11)0.0072 (8)0.0002 (8)0.0044 (8)
C50.0326 (10)0.0221 (8)0.0372 (11)0.0048 (8)0.0075 (10)0.0043 (9)
C60.0257 (9)0.0216 (8)0.0322 (10)0.0009 (7)0.0042 (9)−0.0023 (8)
C70.0223 (9)0.0241 (8)0.0258 (9)0.0019 (6)0.0010 (8)−0.0015 (8)
C80.0211 (9)0.0263 (9)0.0263 (9)−0.0023 (7)0.0005 (8)−0.0026 (7)
C90.0289 (10)0.0375 (10)0.0282 (12)0.0049 (8)−0.0065 (8)0.0007 (8)
C100.0422 (11)0.0345 (10)0.0490 (13)0.0003 (9)0.0082 (13)0.0131 (12)
C110.0327 (11)0.0328 (10)0.0431 (12)−0.0084 (8)0.0013 (10)−0.0025 (10)
C120.0259 (10)0.0351 (10)0.0279 (10)−0.0026 (8)−0.0022 (9)0.0053 (8)
C130.0205 (9)0.0235 (8)0.0303 (9)−0.0031 (7)−0.0028 (8)0.0019 (8)
C140.0212 (9)0.0268 (8)0.0342 (10)−0.0014 (7)−0.0054 (8)0.0023 (8)
C150.0275 (9)0.0294 (9)0.0364 (12)−0.0023 (7)−0.0083 (10)−0.0017 (10)
C160.0374 (11)0.0314 (9)0.0421 (13)0.0042 (8)−0.0050 (11)−0.0079 (10)
C170.0277 (11)0.0358 (11)0.0525 (14)0.0074 (8)−0.0074 (11)−0.0071 (11)
C180.0228 (9)0.0297 (9)0.0403 (11)0.0010 (8)−0.0071 (9)0.0002 (9)

Geometric parameters (Å, °)

S—O21.4915 (14)C9—H9C0.9800
S—C11.7606 (18)C10—H10A0.9800
S—C131.793 (2)C10—H10B0.9800
F—C161.350 (3)C10—H10C0.9800
O1—C81.372 (2)C11—H11A0.9800
O1—C71.384 (2)C11—H11B0.9800
C1—C81.356 (3)C11—H11C0.9800
C1—C21.456 (3)C12—H12A0.9800
C2—C71.394 (3)C12—H12B0.9800
C2—C31.402 (3)C12—H12C0.9800
C3—C41.392 (3)C13—C141.379 (3)
C3—C91.506 (3)C13—C181.397 (3)
C4—C51.412 (3)C14—C151.390 (3)
C4—H40.9500C14—H140.9500
C5—C61.394 (3)C15—C161.375 (3)
C5—C101.504 (3)C15—H150.9500
C6—C71.386 (3)C16—C171.379 (3)
C6—C111.505 (3)C17—C181.378 (3)
C8—C121.478 (3)C17—H170.9500
C9—H9A0.9800C18—H180.9500
C9—H9B0.9800
O2—S—C1110.49 (9)C5—C10—H10B109.5
O2—S—C13106.91 (10)H10A—C10—H10B109.5
C1—S—C1398.95 (9)C5—C10—H10C109.5
C8—O1—C7106.41 (15)H10A—C10—H10C109.5
C8—C1—C2107.61 (16)H10B—C10—H10C109.5
C8—C1—S118.44 (15)C6—C11—H11A109.5
C2—C1—S133.91 (15)C6—C11—H11B109.5
C7—C2—C3118.25 (18)H11A—C11—H11B109.5
C7—C2—C1104.08 (16)C6—C11—H11C109.5
C3—C2—C1137.67 (18)H11A—C11—H11C109.5
C4—C3—C2116.62 (18)H11B—C11—H11C109.5
C4—C3—C9120.07 (19)C8—C12—H12A109.5
C2—C3—C9123.30 (18)C8—C12—H12B109.5
C3—C4—C5123.73 (19)H12A—C12—H12B109.5
C3—C4—H4118.1C8—C12—H12C109.5
C5—C4—H4118.1H12A—C12—H12C109.5
C6—C5—C4120.03 (18)H12B—C12—H12C109.5
C6—C5—C10121.0 (2)C14—C13—C18121.06 (19)
C4—C5—C10119.0 (2)C14—C13—S118.92 (15)
C7—C6—C5114.95 (18)C18—C13—S119.72 (16)
C7—C6—C11120.7 (2)C13—C14—C15120.07 (18)
C5—C6—C11124.32 (19)C13—C14—H14120.0
O1—C7—C6122.64 (18)C15—C14—H14120.0
O1—C7—C2110.96 (16)C16—C15—C14117.8 (2)
C6—C7—C2126.40 (19)C16—C15—H15121.1
C1—C8—O1110.94 (17)C14—C15—H15121.1
C1—C8—C12133.67 (17)F—C16—C15118.1 (2)
O1—C8—C12115.30 (17)F—C16—C17118.86 (19)
C3—C9—H9A109.5C15—C16—C17123.0 (2)
C3—C9—H9B109.5C18—C17—C16118.98 (19)
H9A—C9—H9B109.5C18—C17—H17120.5
C3—C9—H9C109.5C16—C17—H17120.5
H9A—C9—H9C109.5C17—C18—C13119.01 (19)
H9B—C9—H9C109.5C17—C18—H18120.5
C5—C10—H10A109.5C13—C18—H18120.5
O2—S—C1—C8137.99 (16)C11—C6—C7—C2−179.11 (19)
C13—S—C1—C8−110.10 (17)C3—C2—C7—O1−179.38 (16)
O2—S—C1—C2−44.4 (2)C1—C2—C7—O10.3 (2)
C13—S—C1—C267.5 (2)C3—C2—C7—C6−0.1 (3)
C8—C1—C2—C7−0.4 (2)C1—C2—C7—C6179.60 (18)
S—C1—C2—C7−178.16 (16)C2—C1—C8—O10.3 (2)
C8—C1—C2—C3179.2 (2)S—C1—C8—O1178.51 (13)
S—C1—C2—C31.4 (4)C2—C1—C8—C12−176.0 (2)
C7—C2—C3—C40.3 (3)S—C1—C8—C122.2 (3)
C1—C2—C3—C4−179.3 (2)C7—O1—C8—C1−0.1 (2)
C7—C2—C3—C9179.36 (18)C7—O1—C8—C12176.90 (17)
C1—C2—C3—C9−0.2 (4)O2—S—C13—C14−13.62 (19)
C2—C3—C4—C50.6 (3)C1—S—C13—C14−128.35 (17)
C9—C3—C4—C5−178.50 (19)O2—S—C13—C18172.58 (16)
C3—C4—C5—C6−1.7 (3)C1—S—C13—C1857.85 (18)
C3—C4—C5—C10177.73 (19)C18—C13—C14—C15−1.0 (3)
C4—C5—C6—C71.7 (3)S—C13—C14—C15−174.70 (16)
C10—C5—C6—C7−177.71 (18)C13—C14—C15—C160.7 (3)
C4—C5—C6—C11179.86 (19)C14—C15—C16—F−179.6 (2)
C10—C5—C6—C110.4 (3)C14—C15—C16—C170.2 (4)
C8—O1—C7—C6−179.43 (18)F—C16—C17—C18179.0 (2)
C8—O1—C7—C2−0.12 (19)C15—C16—C17—C18−0.8 (4)
C5—C6—C7—O1178.31 (17)C16—C17—C18—C130.6 (4)
C11—C6—C7—O10.1 (3)C14—C13—C18—C170.3 (3)
C5—C6—C7—C2−0.9 (3)S—C13—C18—C17173.99 (18)

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C13–C18 ring.
D—H···AD—HH···AD···AD—H···A
C15—H15···O1i0.952.593.529 (3)169
C18—H18···O2ii0.952.493.328 (2)147
C11—H11A···Cgii0.982.663.553 (3)152
C12—H12A···Cgiii0.982.783.590 (3)141

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GW2077).

References

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  • Khan, M. W., Alam, M. J., Rashid, M. A. & Chowdhury, R. (2005). Bioorg. Med. Chem 13, 4796–4805. [PubMed]
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