Acta Cryst. (2009). E65, o2609 [ doi:10.1107/S1600536809039324 ]
In the title compound, C20H13BrO2S, the O atom and the phenyl group of the phenylsulfinyl substituent are located on opposite sides of the plane of the benzofuran system. The S-bound phenyl ring is almost perpendicular to this plane [80.35 (8)°]. The phenyl ring in the 2-position is twisted with respect to the benzofuran plane, making a dihedral angle of 16.0 (1)°.
77% 3-Chloroperoxybenzoic acid (224 mg, 1.0 mmol) was added in small portions to a stirred solution of 5-bromo-2-phenyl-3-phenylsulfanyl-1-benzofuran (343 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 in vacuum. The residue was purified by column chromatography (hexane-ethyl acetate, 2 : 1 v/v) to afford the title compound as a colorless solid [yield 73%, m.p. 417-418 K; Rf = 0.56 (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 benzene at room temperature.
All H atoms were fixed geometrically and treated as riding with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C)
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2491fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radii. |
| C20H13BrO2S | Z = 2 |
| Mr = 397.27 | F(000) = 400 |
| Triclinic, P1 | Dx = 1.586 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.2670 (1) Å | Cell parameters from 5885 reflections |
| b = 9.5233 (2) Å | θ = 2.4–26.0° |
| c = 11.8663 (2) Å | µ = 2.61 mm−1 |
| α = 72.187 (1)° | T = 293 K |
| β = 80.772 (1)° | Block, colorless |
| γ = 69.526 (1)° | 0.35 × 0.22 × 0.11 mm |
| V = 831.76 (2) Å3 |
| Bruker SMART CCD diffractometer | 3275 independent reflections |
| Radiation source: fine-focus sealed tube | 2716 reflections with I > 2σ(I) |
| graphite | Rint = 0.030 |
| Detector resolution: 10.0 pixels mm-1 | θmax = 26.0°, θmin = 1.8° |
| φ and ω scans | h = −10→10 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | k = −11→11 |
| Tmin = 0.462, Tmax = 0.763 | l = −14→14 |
| 13542 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)] = 0.035 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.095 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.3341P] where P = (Fo2 + 2Fc2)/3 |
| 3275 reflections | (Δ/σ)max = 0.001 |
| 217 parameters | Δρmax = 0.51 e Å−3 |
| 0 restraints | Δρmin = −0.59 e Å−3 |
| C20H13BrO2S | γ = 69.526 (1)° |
| Mr = 397.27 | V = 831.76 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.2670 (1) Å | Mo Kα radiation |
| b = 9.5233 (2) Å | µ = 2.61 mm−1 |
| c = 11.8663 (2) Å | T = 293 K |
| α = 72.187 (1)° | 0.35 × 0.22 × 0.11 mm |
| β = 80.772 (1)° |
| Bruker SMART CCD diffractometer | 3275 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2716 reflections with I > 2σ(I) |
| Tmin = 0.462, Tmax = 0.763 | Rint = 0.030 |
| 13542 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.095 | Δρmax = 0.51 e Å−3 |
| S = 1.05 | Δρmin = −0.59 e Å−3 |
| 3275 reflections | Absolute structure: ? |
| 217 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 | ||
| Br | 1.01046 (4) | 0.24078 (4) | 0.38069 (3) | 0.07875 (15) | |
| S | 0.60607 (8) | 0.10785 (7) | 0.86253 (6) | 0.05063 (17) | |
| O1 | 0.5011 (2) | 0.56165 (18) | 0.71087 (15) | 0.0552 (4) | |
| O2 | 0.7801 (2) | 0.0093 (2) | 0.8283 (2) | 0.0760 (6) | |
| C1 | 0.5823 (3) | 0.3012 (2) | 0.7751 (2) | 0.0453 (5) | |
| C2 | 0.6714 (3) | 0.3415 (3) | 0.6609 (2) | 0.0470 (5) | |
| C3 | 0.7888 (3) | 0.2607 (3) | 0.5871 (2) | 0.0516 (6) | |
| H3 | 0.8269 | 0.1525 | 0.6070 | 0.062* | |
| C4 | 0.8466 (3) | 0.3472 (3) | 0.4831 (2) | 0.0566 (6) | |
| C5 | 0.7910 (4) | 0.5094 (3) | 0.4506 (3) | 0.0655 (7) | |
| H5 | 0.8338 | 0.5632 | 0.3796 | 0.079* | |
| C6 | 0.6738 (4) | 0.5895 (3) | 0.5225 (3) | 0.0645 (7) | |
| H6 | 0.6343 | 0.6978 | 0.5017 | 0.077* | |
| C7 | 0.6166 (3) | 0.5035 (3) | 0.6272 (2) | 0.0518 (6) | |
| C8 | 0.4830 (3) | 0.4365 (3) | 0.8020 (2) | 0.0486 (5) | |
| C9 | 0.3645 (3) | 0.4760 (3) | 0.9012 (2) | 0.0505 (6) | |
| C10 | 0.3612 (4) | 0.3686 (3) | 1.0094 (3) | 0.0660 (7) | |
| H10 | 0.4365 | 0.2672 | 1.0207 | 0.079* | |
| C11 | 0.2474 (4) | 0.4101 (4) | 1.1009 (3) | 0.0750 (8) | |
| H11 | 0.2469 | 0.3363 | 1.1735 | 0.090* | |
| C12 | 0.1352 (4) | 0.5581 (4) | 1.0866 (3) | 0.0768 (9) | |
| H12 | 0.0581 | 0.5850 | 1.1487 | 0.092* | |
| C13 | 0.1375 (5) | 0.6667 (4) | 0.9799 (3) | 0.0868 (10) | |
| H13 | 0.0622 | 0.7680 | 0.9696 | 0.104* | |
| C14 | 0.2507 (4) | 0.6265 (3) | 0.8877 (3) | 0.0732 (8) | |
| H14 | 0.2511 | 0.7011 | 0.8156 | 0.088* | |
| C15 | 0.4515 (3) | 0.0742 (2) | 0.7931 (2) | 0.0455 (5) | |
| C16 | 0.5017 (4) | 0.0001 (3) | 0.7038 (3) | 0.0647 (7) | |
| H16 | 0.6170 | −0.0307 | 0.6762 | 0.078* | |
| C17 | 0.3767 (6) | −0.0275 (4) | 0.6558 (3) | 0.0833 (10) | |
| H17 | 0.4082 | −0.0778 | 0.5959 | 0.100* | |
| C18 | 0.2085 (5) | 0.0188 (4) | 0.6965 (4) | 0.0836 (10) | |
| H18 | 0.1254 | 0.0015 | 0.6629 | 0.100* | |
| C19 | 0.1600 (4) | 0.0901 (4) | 0.7856 (4) | 0.0791 (10) | |
| H19 | 0.0445 | 0.1200 | 0.8129 | 0.095* | |
| C20 | 0.2804 (3) | 0.1180 (3) | 0.8351 (3) | 0.0592 (6) | |
| H20 | 0.2474 | 0.1659 | 0.8964 | 0.071* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br | 0.0790 (2) | 0.0939 (3) | 0.0630 (2) | −0.03538 (18) | 0.01864 (16) | −0.02325 (17) |
| S | 0.0434 (3) | 0.0442 (3) | 0.0520 (4) | −0.0148 (2) | −0.0066 (3) | 0.0070 (2) |
| O1 | 0.0669 (11) | 0.0419 (8) | 0.0506 (10) | −0.0212 (8) | −0.0008 (8) | −0.0010 (7) |
| O2 | 0.0417 (10) | 0.0554 (10) | 0.1019 (16) | −0.0060 (8) | −0.0054 (10) | 0.0088 (10) |
| C1 | 0.0446 (12) | 0.0424 (11) | 0.0450 (13) | −0.0191 (9) | −0.0066 (10) | 0.0017 (9) |
| C2 | 0.0452 (12) | 0.0475 (12) | 0.0462 (13) | −0.0220 (10) | −0.0059 (10) | 0.0002 (10) |
| C3 | 0.0468 (13) | 0.0515 (13) | 0.0524 (14) | −0.0201 (10) | −0.0030 (11) | −0.0034 (11) |
| C4 | 0.0540 (14) | 0.0659 (15) | 0.0496 (15) | −0.0267 (12) | 0.0013 (11) | −0.0085 (12) |
| C5 | 0.0774 (19) | 0.0670 (17) | 0.0487 (15) | −0.0372 (15) | 0.0034 (13) | 0.0020 (13) |
| C6 | 0.0787 (19) | 0.0507 (14) | 0.0568 (16) | −0.0289 (13) | −0.0025 (14) | 0.0045 (12) |
| C7 | 0.0548 (14) | 0.0484 (12) | 0.0489 (14) | −0.0222 (11) | −0.0026 (11) | −0.0022 (10) |
| C8 | 0.0516 (13) | 0.0473 (12) | 0.0438 (13) | −0.0214 (10) | −0.0071 (10) | 0.0008 (10) |
| C9 | 0.0501 (13) | 0.0527 (13) | 0.0490 (14) | −0.0208 (11) | −0.0042 (11) | −0.0085 (11) |
| C10 | 0.0787 (19) | 0.0550 (15) | 0.0548 (16) | −0.0188 (13) | 0.0048 (14) | −0.0090 (12) |
| C11 | 0.088 (2) | 0.0731 (19) | 0.0537 (17) | −0.0271 (17) | 0.0110 (15) | −0.0100 (14) |
| C12 | 0.0691 (19) | 0.088 (2) | 0.070 (2) | −0.0255 (17) | 0.0152 (15) | −0.0269 (17) |
| C13 | 0.077 (2) | 0.0691 (19) | 0.089 (3) | −0.0030 (16) | 0.0095 (18) | −0.0164 (18) |
| C14 | 0.0709 (19) | 0.0611 (16) | 0.0660 (19) | −0.0098 (14) | 0.0026 (15) | −0.0036 (14) |
| C15 | 0.0445 (12) | 0.0335 (10) | 0.0491 (13) | −0.0121 (9) | −0.0008 (10) | 0.0006 (9) |
| C16 | 0.0687 (17) | 0.0482 (13) | 0.0679 (18) | −0.0157 (12) | 0.0089 (14) | −0.0125 (12) |
| C17 | 0.127 (3) | 0.0537 (16) | 0.078 (2) | −0.0311 (19) | −0.018 (2) | −0.0209 (15) |
| C18 | 0.090 (3) | 0.0569 (17) | 0.112 (3) | −0.0276 (17) | −0.037 (2) | −0.0142 (18) |
| C19 | 0.0525 (17) | 0.0681 (18) | 0.116 (3) | −0.0219 (14) | −0.0125 (17) | −0.0174 (19) |
| C20 | 0.0474 (14) | 0.0579 (14) | 0.0708 (18) | −0.0168 (11) | 0.0004 (12) | −0.0174 (13) |
| Br—C4 | 1.899 (3) | C10—C11 | 1.377 (4) |
| S—O2 | 1.489 (2) | C10—H10 | 0.9300 |
| S—C1 | 1.775 (2) | C11—C12 | 1.366 (5) |
| S—C15 | 1.789 (2) | C11—H11 | 0.9300 |
| O1—C7 | 1.366 (3) | C12—C13 | 1.371 (5) |
| O1—C8 | 1.377 (3) | C12—H12 | 0.9300 |
| C1—C8 | 1.365 (4) | C13—C14 | 1.377 (5) |
| C1—C2 | 1.444 (3) | C13—H13 | 0.9300 |
| C2—C3 | 1.385 (4) | C14—H14 | 0.9300 |
| C2—C7 | 1.391 (3) | C15—C16 | 1.379 (4) |
| C3—C4 | 1.376 (3) | C15—C20 | 1.383 (3) |
| C3—H3 | 0.9300 | C16—C17 | 1.390 (5) |
| C4—C5 | 1.393 (4) | C16—H16 | 0.9300 |
| C5—C6 | 1.366 (4) | C17—C18 | 1.359 (5) |
| C5—H5 | 0.9300 | C17—H17 | 0.9300 |
| C6—C7 | 1.378 (4) | C18—C19 | 1.361 (5) |
| C6—H6 | 0.9300 | C18—H18 | 0.9300 |
| C8—C9 | 1.459 (4) | C19—C20 | 1.370 (4) |
| C9—C10 | 1.379 (4) | C19—H19 | 0.9300 |
| C9—C14 | 1.389 (4) | C20—H20 | 0.9300 |
| O2—S—C1 | 106.63 (11) | C11—C10—H10 | 119.7 |
| O2—S—C15 | 106.87 (13) | C9—C10—H10 | 119.7 |
| C1—S—C15 | 97.41 (10) | C12—C11—C10 | 120.9 (3) |
| C7—O1—C8 | 107.23 (18) | C12—C11—H11 | 119.6 |
| C8—C1—C2 | 107.74 (19) | C10—C11—H11 | 119.6 |
| C8—C1—S | 127.74 (19) | C11—C12—C13 | 119.3 (3) |
| C2—C1—S | 124.50 (18) | C11—C12—H12 | 120.3 |
| C3—C2—C7 | 119.5 (2) | C13—C12—H12 | 120.3 |
| C3—C2—C1 | 136.0 (2) | C12—C13—C14 | 120.3 (3) |
| C7—C2—C1 | 104.5 (2) | C12—C13—H13 | 119.9 |
| C4—C3—C2 | 117.2 (2) | C14—C13—H13 | 119.9 |
| C4—C3—H3 | 121.4 | C13—C14—C9 | 120.8 (3) |
| C2—C3—H3 | 121.4 | C13—C14—H14 | 119.6 |
| C3—C4—C5 | 122.7 (3) | C9—C14—H14 | 119.6 |
| C3—C4—Br | 118.6 (2) | C16—C15—C20 | 120.5 (3) |
| C5—C4—Br | 118.8 (2) | C16—C15—S | 121.3 (2) |
| C6—C5—C4 | 120.3 (2) | C20—C15—S | 118.1 (2) |
| C6—C5—H5 | 119.9 | C15—C16—C17 | 118.8 (3) |
| C4—C5—H5 | 119.9 | C15—C16—H16 | 120.6 |
| C5—C6—C7 | 117.3 (2) | C17—C16—H16 | 120.6 |
| C5—C6—H6 | 121.4 | C18—C17—C16 | 120.1 (3) |
| C7—C6—H6 | 121.4 | C18—C17—H17 | 120.0 |
| O1—C7—C6 | 126.1 (2) | C16—C17—H17 | 120.0 |
| O1—C7—C2 | 110.8 (2) | C17—C18—C19 | 120.9 (3) |
| C6—C7—C2 | 123.0 (3) | C17—C18—H18 | 119.5 |
| C1—C8—O1 | 109.7 (2) | C19—C18—H18 | 119.5 |
| C1—C8—C9 | 135.1 (2) | C18—C19—C20 | 120.3 (3) |
| O1—C8—C9 | 115.3 (2) | C18—C19—H19 | 119.8 |
| C10—C9—C14 | 118.1 (3) | C20—C19—H19 | 119.8 |
| C10—C9—C8 | 122.2 (2) | C19—C20—C15 | 119.3 (3) |
| C14—C9—C8 | 119.6 (2) | C19—C20—H20 | 120.3 |
| C11—C10—C9 | 120.6 (3) | C15—C20—H20 | 120.3 |
| O2—S—C1—C8 | −152.9 (2) | C7—O1—C8—C1 | −1.4 (3) |
| C15—S—C1—C8 | 96.9 (2) | C7—O1—C8—C9 | 179.5 (2) |
| O2—S—C1—C2 | 25.7 (2) | C1—C8—C9—C10 | 16.4 (5) |
| C15—S—C1—C2 | −84.4 (2) | O1—C8—C9—C10 | −164.9 (2) |
| C8—C1—C2—C3 | 179.1 (3) | C1—C8—C9—C14 | −163.9 (3) |
| S—C1—C2—C3 | 0.2 (4) | O1—C8—C9—C14 | 14.8 (4) |
| C8—C1—C2—C7 | 0.1 (3) | C14—C9—C10—C11 | 0.3 (5) |
| S—C1—C2—C7 | −178.80 (18) | C8—C9—C10—C11 | −180.0 (3) |
| C7—C2—C3—C4 | 0.5 (4) | C9—C10—C11—C12 | 0.1 (5) |
| C1—C2—C3—C4 | −178.4 (3) | C10—C11—C12—C13 | −0.6 (6) |
| C2—C3—C4—C5 | −0.4 (4) | C11—C12—C13—C14 | 0.6 (6) |
| C2—C3—C4—Br | 179.02 (18) | C12—C13—C14—C9 | −0.1 (6) |
| C3—C4—C5—C6 | −0.3 (4) | C10—C9—C14—C13 | −0.3 (5) |
| Br—C4—C5—C6 | −179.7 (2) | C8—C9—C14—C13 | 179.9 (3) |
| C4—C5—C6—C7 | 0.8 (4) | O2—S—C15—C16 | −14.1 (2) |
| C8—O1—C7—C6 | −178.7 (3) | C1—S—C15—C16 | 95.8 (2) |
| C8—O1—C7—C2 | 1.5 (3) | O2—S—C15—C20 | 162.89 (18) |
| C5—C6—C7—O1 | 179.6 (3) | C1—S—C15—C20 | −87.2 (2) |
| C5—C6—C7—C2 | −0.7 (4) | C20—C15—C16—C17 | 0.9 (4) |
| C3—C2—C7—O1 | 179.8 (2) | S—C15—C16—C17 | 177.9 (2) |
| C1—C2—C7—O1 | −1.0 (3) | C15—C16—C17—C18 | 0.3 (4) |
| C3—C2—C7—C6 | 0.0 (4) | C16—C17—C18—C19 | −1.2 (5) |
| C1—C2—C7—C6 | 179.2 (3) | C17—C18—C19—C20 | 0.7 (5) |
| C2—C1—C8—O1 | 0.9 (3) | C18—C19—C20—C15 | 0.5 (5) |
| S—C1—C8—O1 | 179.67 (17) | C16—C15—C20—C19 | −1.3 (4) |
| C2—C1—C8—C9 | 179.6 (3) | S—C15—C20—C19 | −178.4 (2) |
| S—C1—C8—C9 | −1.6 (4) |
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Molecules containing benzofuran moiety have received much attenttion in the field of their pharmacological properties (Howlett et al., 1999; Twyman & Allsop, 1999), and these compounds are ubiquitous in nature (Akgul & Anil, 2003; Reuss & König, 2004). As a part of our ongoing studies of the effect of side chain substituents on the solid state structures of 5-halo-2-phenyl-3-phenylsulfinyl-1-benzofuran analogues (Choi et al., 2009a,b), we present the crystal structure of the title compound (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.010 (2) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle formed by the plane of the benzofuran unit and the plane of 2-phenyl ring is 16.0 (1)°. The phenyl ring (C15-C20) is almost perpendicular to the plane of the benzofuran unit [80.35 (8)°].