Acta Cryst. (2010). E66, o629 [ doi:10.1107/S1600536810005581 ]
In the title compound, C17H14FIO2S, the 4-fluorophenyl ring is rotated out of the benzofuran plane, as indicated by the dihedral angle of 15.60 (6)°. The crystal structure exhibits an I
O interaction [3.052 (2) Å].
77% 3-Chloroperoxybenzoic acid (202 mg, 0.9 mmol) was added in small portions to a stirred solution of 3-ethylsulfanyl-2-(4-fluorophenyl)-5-iodo-7-methyl-1-benzofuran (330 mg, 0.8 mmol) in dichloromethane (25 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 (hexane–ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [yield 82%, m.p. 466–467 K; Rf = 0.54 (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.
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aryl, 0.97 Å for methylene, and 0.96 Å for methyl H atoms. Uiso(H) = 1.2Ueq (C) for aryl and methylene, and 1.5Ueq(C) for methyl H atoms.
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./pb2023fig1thm.gif)
| 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. |
![[Figure 2]](./pb2023fig2thm.gif)
| Fig. 2. C—I···O interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: i) - x + 1, - y + 1, - z + 2.] |
| C17H14FIO2S | Z = 2 |
| Mr = 428.24 | F(000) = 420 |
| Triclinic, P1 | Dx = 1.799 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.4681 (5) Å | Cell parameters from 6089 reflections |
| b = 10.3023 (7) Å | θ = 2.1–27.4° |
| c = 10.9761 (7) Å | µ = 2.17 mm−1 |
| α = 76.289 (1)° | T = 273 K |
| β = 89.138 (1)° | Block, colourless |
| γ = 74.802 (1)° | 0.50 × 0.25 × 0.25 mm |
| V = 790.73 (9) Å3 |
| Bruker SMART APEXII CCD diffractometer | 3386 independent reflections |
| Radiation source: Rotating Anode | 3261 reflections with I > 2σ(I) |
| Bruker HELIOS graded multilayer optics | Rint = 0.049 |
| Detector resolution: 10.0 pixels mm-1 | θmax = 27.0°, θmin = 2.8° |
| φ and ω scans | h = −9→9 |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −13→13 |
| Tmin = 0.520, Tmax = 0.582 | l = −14→13 |
| 6867 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.059 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0284P)2 + 0.4222P] where P = (Fo2 + 2Fc2)/3 |
| 3386 reflections | (Δ/σ)max < 0.001 |
| 201 parameters | Δρmax = 0.71 e Å−3 |
| 0 restraints | Δρmin = −0.81 e Å−3 |
| C17H14FIO2S | γ = 74.802 (1)° |
| Mr = 428.24 | V = 790.73 (9) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.4681 (5) Å | Mo Kα radiation |
| b = 10.3023 (7) Å | µ = 2.17 mm−1 |
| c = 10.9761 (7) Å | T = 273 K |
| α = 76.289 (1)° | 0.50 × 0.25 × 0.25 mm |
| β = 89.138 (1)° |
| Bruker SMART APEXII CCD diffractometer | 3386 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3261 reflections with I > 2σ(I) |
| Tmin = 0.520, Tmax = 0.582 | Rint = 0.049 |
| 6867 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
| wR(F2) = 0.059 | Δρmax = 0.71 e Å−3 |
| S = 1.06 | Δρmin = −0.81 e Å−3 |
| 3386 reflections | Absolute structure: ? |
| 201 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| I | 0.542549 (19) | 0.247310 (13) | 1.062688 (11) | 0.02504 (6) | |
| F | −0.0461 (2) | 0.7492 (2) | −0.01911 (13) | 0.0441 (4) | |
| O1 | 0.2937 (2) | 0.37876 (15) | 0.50304 (13) | 0.0214 (3) | |
| O2 | 0.3809 (2) | 0.75140 (17) | 0.66534 (15) | 0.0284 (3) | |
| C1 | 0.2629 (3) | 0.5691 (2) | 0.57785 (18) | 0.0204 (4) | |
| C2 | 0.3398 (3) | 0.4484 (2) | 0.67903 (19) | 0.0201 (4) | |
| C3 | 0.3934 (3) | 0.4255 (2) | 0.80613 (18) | 0.0215 (4) | |
| H3 | 0.3824 | 0.4982 | 0.8447 | 0.026* | |
| C4 | 0.4640 (3) | 0.2880 (2) | 0.87108 (18) | 0.0215 (4) | |
| C5 | 0.4839 (3) | 0.1760 (2) | 0.8147 (2) | 0.0243 (4) | |
| H5 | 0.5346 | 0.0861 | 0.8620 | 0.029* | |
| C6 | 0.4289 (3) | 0.1976 (2) | 0.68911 (19) | 0.0217 (4) | |
| C7 | 0.3574 (3) | 0.3354 (2) | 0.62726 (18) | 0.0205 (4) | |
| C8 | 0.2388 (3) | 0.5210 (2) | 0.47433 (19) | 0.0205 (4) | |
| C9 | 0.1667 (3) | 0.5850 (2) | 0.34449 (19) | 0.0219 (4) | |
| C10 | 0.0601 (3) | 0.7217 (3) | 0.3068 (2) | 0.0284 (5) | |
| H10 | 0.0353 | 0.7757 | 0.3652 | 0.034* | |
| C11 | −0.0100 (3) | 0.7790 (3) | 0.1840 (2) | 0.0313 (5) | |
| H11 | −0.0791 | 0.8710 | 0.1587 | 0.038* | |
| C12 | 0.0261 (3) | 0.6952 (3) | 0.1005 (2) | 0.0298 (5) | |
| C13 | 0.1322 (3) | 0.5599 (3) | 0.1329 (2) | 0.0303 (5) | |
| H13 | 0.1545 | 0.5065 | 0.0740 | 0.036* | |
| C14 | 0.2052 (3) | 0.5048 (2) | 0.2553 (2) | 0.0259 (4) | |
| H14 | 0.2799 | 0.4142 | 0.2785 | 0.031* | |
| C15 | 0.4396 (4) | 0.0826 (2) | 0.6251 (2) | 0.0295 (5) | |
| H15A | 0.3163 | 0.0779 | 0.6072 | 0.044* | |
| H15B | 0.5075 | −0.0038 | 0.6791 | 0.044* | |
| H15C | 0.5018 | 0.0999 | 0.5482 | 0.044* | |
| C16 | 0.0218 (3) | 0.7605 (2) | 0.6731 (2) | 0.0279 (4) | |
| H16A | −0.0783 | 0.7464 | 0.6269 | 0.034* | |
| H16B | 0.0467 | 0.6908 | 0.7520 | 0.034* | |
| C17 | −0.0346 (4) | 0.9043 (3) | 0.6981 (2) | 0.0383 (6) | |
| H17A | 0.0664 | 0.9186 | 0.7417 | 0.057* | |
| H17B | −0.1411 | 0.9124 | 0.7486 | 0.057* | |
| H17C | −0.0646 | 0.9727 | 0.6198 | 0.057* | |
| S1 | 0.22856 (8) | 0.74390 (5) | 0.58266 (4) | 0.02169 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I | 0.03433 (10) | 0.02416 (9) | 0.01561 (8) | −0.00848 (6) | −0.00381 (5) | −0.00178 (5) |
| F | 0.0453 (9) | 0.0628 (11) | 0.0171 (6) | −0.0101 (8) | −0.0098 (6) | −0.0001 (6) |
| O1 | 0.0293 (7) | 0.0200 (7) | 0.0156 (6) | −0.0069 (6) | −0.0013 (5) | −0.0048 (5) |
| O2 | 0.0352 (9) | 0.0272 (8) | 0.0266 (8) | −0.0114 (7) | −0.0022 (6) | −0.0101 (6) |
| C1 | 0.0250 (10) | 0.0188 (9) | 0.0174 (9) | −0.0055 (8) | −0.0002 (7) | −0.0046 (7) |
| C2 | 0.0234 (10) | 0.0188 (9) | 0.0181 (9) | −0.0056 (7) | 0.0007 (7) | −0.0046 (7) |
| C3 | 0.0294 (10) | 0.0200 (9) | 0.0166 (9) | −0.0077 (8) | −0.0010 (7) | −0.0057 (7) |
| C4 | 0.0274 (10) | 0.0222 (10) | 0.0152 (8) | −0.0077 (8) | −0.0017 (7) | −0.0035 (7) |
| C5 | 0.0302 (11) | 0.0197 (10) | 0.0219 (10) | −0.0064 (8) | −0.0010 (8) | −0.0029 (8) |
| C6 | 0.0276 (10) | 0.0193 (10) | 0.0200 (9) | −0.0077 (8) | 0.0017 (8) | −0.0065 (7) |
| C7 | 0.0244 (10) | 0.0231 (10) | 0.0158 (9) | −0.0089 (8) | 0.0006 (7) | −0.0052 (7) |
| C8 | 0.0230 (10) | 0.0196 (9) | 0.0194 (9) | −0.0066 (8) | 0.0009 (7) | −0.0042 (7) |
| C9 | 0.0245 (10) | 0.0268 (10) | 0.0161 (9) | −0.0107 (8) | 0.0004 (7) | −0.0044 (8) |
| C10 | 0.0329 (12) | 0.0287 (11) | 0.0216 (10) | −0.0056 (9) | −0.0029 (8) | −0.0052 (8) |
| C11 | 0.0320 (12) | 0.0311 (12) | 0.0249 (11) | −0.0049 (10) | −0.0045 (9) | 0.0011 (9) |
| C12 | 0.0272 (11) | 0.0448 (14) | 0.0164 (9) | −0.0126 (10) | −0.0034 (8) | −0.0019 (9) |
| C13 | 0.0338 (12) | 0.0415 (13) | 0.0197 (10) | −0.0137 (10) | 0.0013 (8) | −0.0111 (9) |
| C14 | 0.0276 (11) | 0.0303 (11) | 0.0211 (10) | −0.0085 (9) | −0.0005 (8) | −0.0078 (8) |
| C15 | 0.0445 (13) | 0.0200 (10) | 0.0263 (10) | −0.0089 (9) | 0.0002 (9) | −0.0092 (8) |
| C16 | 0.0291 (11) | 0.0263 (11) | 0.0258 (10) | −0.0035 (9) | 0.0021 (8) | −0.0055 (8) |
| C17 | 0.0466 (15) | 0.0275 (12) | 0.0331 (12) | 0.0036 (11) | 0.0038 (11) | −0.0076 (10) |
| S1 | 0.0315 (3) | 0.0166 (2) | 0.0164 (2) | −0.00631 (19) | −0.00063 (18) | −0.00285 (17) |
| I—C4 | 2.106 (2) | C9—C14 | 1.405 (3) |
| I—O2i | 3.052 (2) | C10—C11 | 1.387 (3) |
| F—C12 | 1.357 (2) | C10—H10 | 0.9300 |
| O1—C8 | 1.373 (2) | C11—C12 | 1.380 (4) |
| O1—C7 | 1.380 (2) | C11—H11 | 0.9300 |
| O2—S1 | 1.495 (2) | C12—C13 | 1.376 (4) |
| C1—C8 | 1.374 (3) | C13—C14 | 1.387 (3) |
| C1—C2 | 1.449 (3) | C13—H13 | 0.9300 |
| C1—S1 | 1.765 (2) | C14—H14 | 0.9300 |
| C2—C7 | 1.389 (3) | C15—H15A | 0.9600 |
| C2—C3 | 1.405 (3) | C15—H15B | 0.9600 |
| C3—C4 | 1.391 (3) | C15—H15C | 0.9600 |
| C3—H3 | 0.9300 | C16—C17 | 1.520 (3) |
| C4—C5 | 1.407 (3) | C16—S1 | 1.815 (2) |
| C5—C6 | 1.394 (3) | C16—H16A | 0.9700 |
| C5—H5 | 0.9300 | C16—H16B | 0.9700 |
| C6—C7 | 1.385 (3) | C17—H17A | 0.9600 |
| C6—C15 | 1.499 (3) | C17—H17B | 0.9600 |
| C8—C9 | 1.465 (3) | C17—H17C | 0.9600 |
| C9—C10 | 1.391 (3) | ||
| C4—I—O2i | 168.75 (7) | C12—C11—H11 | 121.1 |
| C8—O1—C7 | 106.96 (15) | C10—C11—H11 | 121.1 |
| C8—C1—C2 | 106.76 (18) | F—C12—C13 | 118.6 (2) |
| C8—C1—S1 | 126.56 (16) | F—C12—C11 | 118.3 (2) |
| C2—C1—S1 | 126.41 (15) | C13—C12—C11 | 123.0 (2) |
| C7—C2—C3 | 119.10 (19) | C12—C13—C14 | 118.5 (2) |
| C7—C2—C1 | 105.34 (17) | C12—C13—H13 | 120.7 |
| C3—C2—C1 | 135.56 (19) | C14—C13—H13 | 120.7 |
| C4—C3—C2 | 116.33 (18) | C13—C14—C9 | 120.4 (2) |
| C4—C3—H3 | 121.8 | C13—C14—H14 | 119.8 |
| C2—C3—H3 | 121.8 | C9—C14—H14 | 119.8 |
| C3—C4—C5 | 123.00 (18) | C6—C15—H15A | 109.5 |
| C3—C4—I | 117.95 (15) | C6—C15—H15B | 109.5 |
| C5—C4—I | 119.06 (15) | H15A—C15—H15B | 109.5 |
| C6—C5—C4 | 121.11 (19) | C6—C15—H15C | 109.5 |
| C6—C5—H5 | 119.4 | H15A—C15—H15C | 109.5 |
| C4—C5—H5 | 119.4 | H15B—C15—H15C | 109.5 |
| C7—C6—C5 | 114.58 (18) | C17—C16—S1 | 109.14 (18) |
| C7—C6—C15 | 121.77 (18) | C17—C16—H16A | 109.9 |
| C5—C6—C15 | 123.63 (19) | S1—C16—H16A | 109.9 |
| O1—C7—C6 | 123.70 (18) | C17—C16—H16B | 109.9 |
| O1—C7—C2 | 110.45 (18) | S1—C16—H16B | 109.9 |
| C6—C7—C2 | 125.85 (18) | H16A—C16—H16B | 108.3 |
| O1—C8—C1 | 110.48 (17) | C16—C17—H17A | 109.5 |
| O1—C8—C9 | 114.21 (17) | C16—C17—H17B | 109.5 |
| C1—C8—C9 | 135.31 (19) | H17A—C17—H17B | 109.5 |
| C10—C9—C14 | 118.92 (19) | C16—C17—H17C | 109.5 |
| C10—C9—C8 | 122.32 (19) | H17A—C17—H17C | 109.5 |
| C14—C9—C8 | 118.8 (2) | H17B—C17—H17C | 109.5 |
| C11—C10—C9 | 121.3 (2) | O2—S1—C1 | 107.96 (10) |
| C11—C10—H10 | 119.4 | O2—S1—C16 | 106.52 (10) |
| C9—C10—H10 | 119.4 | C1—S1—C16 | 97.83 (11) |
| C12—C11—C10 | 117.9 (2) | ||
| C8—C1—C2—C7 | 0.4 (2) | C2—C1—C8—O1 | 0.4 (2) |
| S1—C1—C2—C7 | −173.92 (16) | S1—C1—C8—O1 | 174.74 (15) |
| C8—C1—C2—C3 | −179.2 (2) | C2—C1—C8—C9 | 179.1 (2) |
| S1—C1—C2—C3 | 6.5 (4) | S1—C1—C8—C9 | −6.6 (4) |
| C7—C2—C3—C4 | 0.9 (3) | O1—C8—C9—C10 | 162.3 (2) |
| C1—C2—C3—C4 | −179.6 (2) | C1—C8—C9—C10 | −16.3 (4) |
| C2—C3—C4—C5 | 0.6 (3) | O1—C8—C9—C14 | −17.0 (3) |
| C2—C3—C4—I | −179.02 (15) | C1—C8—C9—C14 | 164.4 (2) |
| C3—C4—C5—C6 | −1.5 (4) | C14—C9—C10—C11 | 0.7 (4) |
| I—C4—C5—C6 | 178.17 (17) | C8—C9—C10—C11 | −178.6 (2) |
| C4—C5—C6—C7 | 0.7 (3) | C9—C10—C11—C12 | 1.3 (4) |
| C4—C5—C6—C15 | −177.5 (2) | C10—C11—C12—F | 178.2 (2) |
| C8—O1—C7—C6 | −178.4 (2) | C10—C11—C12—C13 | −2.0 (4) |
| C8—O1—C7—C2 | 1.4 (2) | F—C12—C13—C14 | −179.7 (2) |
| C5—C6—C7—O1 | −179.43 (19) | C11—C12—C13—C14 | 0.5 (4) |
| C15—C6—C7—O1 | −1.2 (3) | C12—C13—C14—C9 | 1.7 (4) |
| C5—C6—C7—C2 | 0.9 (3) | C10—C9—C14—C13 | −2.3 (3) |
| C15—C6—C7—C2 | 179.1 (2) | C8—C9—C14—C13 | 177.1 (2) |
| C3—C2—C7—O1 | 178.56 (18) | C8—C1—S1—O2 | −139.72 (19) |
| C1—C2—C7—O1 | −1.1 (2) | C2—C1—S1—O2 | 33.5 (2) |
| C3—C2—C7—C6 | −1.7 (3) | C8—C1—S1—C16 | 110.0 (2) |
| C1—C2—C7—C6 | 178.6 (2) | C2—C1—S1—C16 | −76.8 (2) |
| C7—O1—C8—C1 | −1.1 (2) | C17—C16—S1—O2 | 65.53 (18) |
| C7—O1—C8—C9 | 179.96 (18) | C17—C16—S1—C1 | 176.96 (16) |
| Symmetry codes: (i) −x+1, −y+1, −z+2. |
Akgul, Y. Y. & Anil, H. (2003). Phytochemistry, 63, 939–943.
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). SADABS. APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010a). Acta Cryst. E66, o323.
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst. E66, o402.
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.
Khan, M. W., Alam, M. J., Rashid, M. A. & Chowdhury, R. (2005). Bioorg. Med. Chem. 13, 4796–4805.
Politzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model. 13, 305–311.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Soekamto, N. H., Achmad, S. A., Ghisalberti, E. L., Hakim, E. H. & Syah, Y. M. (2003). Phytochemistry, 64, 831–834.
Compounds containing benzofuran skeleton show diverse pharmacological activities such as antifungal (Aslam et al., 2006), antitumor and antiviral (Galal et al., 2009), antimicrobial (Khan et al., 2005) properties. 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-ethylsulfinyl-2-(4-fluorophenyl)-5-halo-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 (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 15.60 (6)°. The crystal packing (Fig. 2) is stabilized by an I···O halogen bond between the iodine and the oxygen of the S═O unit [C4—I···O2i = 3.052 (2) Å; C4—I···O2i = 168.75 (7)°] (Politzer et al., 2007).