organic compounds
5-Bromo-2-methyl-3-phenylsulfonyl-1-benzofuran
aDepartment of Chemistry, Dongeui University, San 24 Kaya-dong, Busanjin-gu, Busan 614-714, Republic of Korea, and bDepartment of Chemistry, Pukyong National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea
*Correspondence e-mail: uklee@pknu.ac.kr
The title compound, C15H11BrO3S, was prepared by the oxidation of 5-bromo-2-methyl-3-phenylsulfanyl-1-benzofuran with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 78.99 (8)° with the plane of the benzofuran fragment. The is stabilized by C—H⋯π interactions between a benzene H atom of the benzofuran unit and the phenyl ring of the phenylsulfonyl substituent from a neighbouring molecule. In addition, the exhibits intra- and intermolecular C—H⋯O interactions.
Related literature
For the crystal structures of similar 5-bromo-2-methyl-1-benzofuran derivatives, see: Choi et al. (2007); Seo et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536808008489/cf2191sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808008489/cf2191Isup2.hkl
3-Chloroperoxybenzoic acid (77%, 336 mg, 1.5 mmol) was added in small portions to a stirred solution of 5-bromo-2-methyl-3-phenylsulfonyl-1-benzofuran (223 mg, 0.7 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 4 h at room temperature, 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 δ 2.80 (s, 3H), 7.29 (d, J = 8.44 Hz, 1H), 7.41 (dd, J = 8.44 Hz and J = 1.84 Hz, 1H), 7.51–7.56 (m, 2H), 7.58–7.61 (m, 1H), 7.98–8.02 (m, 2H), 8.05 (d, J = 2.20 Hz, 1H); EI—MS 352 [M+2], 350 [M+].
(hexane-ethyl acetate, 2:1 v/v) to afford the title compound as a colorless solid [yield 78%, m.p. 464–465 K; Rf = 0.59 (hexane-ethyl acetate, 2:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in chloroform at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz)All H atoms were geometrically positioned and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 2001); cell
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: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C15H11BrO3S | F(000) = 704 |
Mr = 351.21 | Dx = 1.693 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P_2yn | Cell parameters from 3065 reflections |
a = 7.337 (1) Å | θ = 2.5–27.7° |
b = 11.345 (1) Å | µ = 3.14 mm−1 |
c = 16.602 (2) Å | T = 173 K |
β = 94.582 (3)° | Block, colorless |
V = 1377.5 (3) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 3009 independent reflections |
Radiation source: fine-focus sealed tube | 2349 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.0°, θmin = 2.5° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | k = −14→13 |
Tmin = 0.463, Tmax = 0.542 | l = −14→21 |
8005 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)] = 0.033 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0401P)2 + 0.6448P] where P = (Fo2 + 2Fc2)/3 |
3009 reflections | (Δ/σ)max < 0.001 |
182 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C15H11BrO3S | V = 1377.5 (3) Å3 |
Mr = 351.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.337 (1) Å | µ = 3.14 mm−1 |
b = 11.345 (1) Å | T = 173 K |
c = 16.602 (2) Å | 0.30 × 0.20 × 0.20 mm |
β = 94.582 (3)° |
Bruker SMART CCD diffractometer | 3009 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | 2349 reflections with I > 2σ(I) |
Tmin = 0.463, Tmax = 0.542 | Rint = 0.033 |
8005 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.55 e Å−3 |
3009 reflections | Δρmin = −0.44 e Å−3 |
182 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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 | 0.79772 (5) | 0.88457 (2) | 0.038216 (19) | 0.03963 (12) | |
S | 0.65781 (9) | 0.40138 (5) | 0.19581 (4) | 0.02489 (16) | |
O1 | 0.7486 (3) | 0.36914 (16) | −0.03375 (11) | 0.0296 (4) | |
O2 | 0.5677 (3) | 0.50746 (16) | 0.21839 (12) | 0.0327 (5) | |
O3 | 0.5740 (3) | 0.28903 (15) | 0.20838 (12) | 0.0344 (5) | |
C1 | 0.6960 (4) | 0.4145 (2) | 0.09406 (16) | 0.0242 (5) | |
C2 | 0.7309 (3) | 0.5236 (2) | 0.05267 (15) | 0.0227 (5) | |
C3 | 0.7410 (4) | 0.6429 (2) | 0.07353 (16) | 0.0255 (5) | |
H3 | 0.7209 | 0.6693 | 0.1264 | 0.031* | |
C4 | 0.7819 (4) | 0.7208 (2) | 0.01307 (17) | 0.0287 (6) | |
C5 | 0.8107 (4) | 0.6854 (2) | −0.06521 (16) | 0.0305 (6) | |
H5 | 0.8372 | 0.7425 | −0.1045 | 0.037* | |
C6 | 0.8010 (4) | 0.5675 (3) | −0.08587 (16) | 0.0308 (6) | |
H6 | 0.8198 | 0.5412 | −0.1389 | 0.037* | |
C7 | 0.7626 (3) | 0.4899 (2) | −0.02563 (16) | 0.0245 (5) | |
C8 | 0.7097 (4) | 0.3254 (2) | 0.03977 (16) | 0.0271 (6) | |
C9 | 0.8786 (4) | 0.3998 (2) | 0.24546 (16) | 0.0259 (6) | |
C10 | 0.9716 (4) | 0.2932 (2) | 0.25599 (16) | 0.0321 (6) | |
H10 | 0.9160 | 0.2218 | 0.2368 | 0.039* | |
C11 | 1.1457 (5) | 0.2921 (3) | 0.29469 (19) | 0.0446 (8) | |
H11 | 1.2105 | 0.2200 | 0.3024 | 0.054* | |
C12 | 1.2249 (5) | 0.3974 (3) | 0.32221 (19) | 0.0506 (9) | |
H12 | 1.3445 | 0.3969 | 0.3488 | 0.061* | |
C13 | 1.1314 (5) | 0.5031 (3) | 0.31132 (19) | 0.0467 (8) | |
H13 | 1.1870 | 0.5745 | 0.3304 | 0.056* | |
C14 | 0.9580 (4) | 0.5048 (2) | 0.27289 (17) | 0.0333 (6) | |
H14 | 0.8935 | 0.5771 | 0.2652 | 0.040* | |
C15 | 0.6972 (4) | 0.1947 (2) | 0.04402 (19) | 0.0374 (7) | |
H15A | 0.8193 | 0.1605 | 0.0419 | 0.056* | |
H15B | 0.6169 | 0.1657 | −0.0017 | 0.056* | |
H15C | 0.6471 | 0.1719 | 0.0947 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0526 (2) | 0.02501 (16) | 0.0412 (2) | −0.00489 (13) | 0.00320 (14) | 0.00437 (12) |
S | 0.0301 (4) | 0.0189 (3) | 0.0269 (3) | −0.0004 (2) | 0.0096 (3) | 0.0010 (2) |
O1 | 0.0328 (11) | 0.0301 (10) | 0.0263 (10) | 0.0005 (8) | 0.0042 (8) | −0.0057 (8) |
O2 | 0.0393 (12) | 0.0266 (9) | 0.0341 (11) | 0.0064 (8) | 0.0149 (9) | −0.0020 (8) |
O3 | 0.0392 (12) | 0.0259 (10) | 0.0398 (12) | −0.0066 (8) | 0.0140 (9) | 0.0038 (8) |
C1 | 0.0256 (14) | 0.0230 (12) | 0.0246 (13) | 0.0000 (10) | 0.0059 (11) | −0.0002 (10) |
C2 | 0.0191 (13) | 0.0259 (12) | 0.0235 (13) | 0.0019 (10) | 0.0038 (10) | 0.0020 (10) |
C3 | 0.0302 (14) | 0.0242 (12) | 0.0224 (13) | 0.0021 (10) | 0.0046 (11) | −0.0006 (10) |
C4 | 0.0273 (15) | 0.0262 (13) | 0.0325 (15) | −0.0024 (11) | 0.0019 (12) | 0.0024 (11) |
C5 | 0.0288 (15) | 0.0371 (15) | 0.0258 (14) | 0.0000 (12) | 0.0039 (11) | 0.0081 (12) |
C6 | 0.0296 (15) | 0.0427 (15) | 0.0202 (14) | 0.0016 (12) | 0.0033 (11) | −0.0001 (12) |
C7 | 0.0224 (13) | 0.0252 (12) | 0.0258 (14) | 0.0019 (10) | 0.0007 (11) | −0.0038 (10) |
C8 | 0.0243 (14) | 0.0275 (13) | 0.0298 (15) | −0.0014 (11) | 0.0032 (11) | −0.0022 (11) |
C9 | 0.0337 (15) | 0.0256 (13) | 0.0196 (13) | −0.0007 (10) | 0.0096 (11) | 0.0012 (10) |
C10 | 0.0420 (18) | 0.0317 (14) | 0.0239 (14) | 0.0033 (12) | 0.0101 (12) | 0.0077 (11) |
C11 | 0.043 (2) | 0.059 (2) | 0.0330 (17) | 0.0144 (16) | 0.0095 (14) | 0.0149 (15) |
C12 | 0.0376 (19) | 0.087 (3) | 0.0264 (17) | −0.0062 (18) | 0.0010 (14) | 0.0063 (17) |
C13 | 0.053 (2) | 0.059 (2) | 0.0276 (16) | −0.0175 (17) | 0.0033 (14) | −0.0068 (15) |
C14 | 0.0444 (18) | 0.0305 (14) | 0.0258 (14) | −0.0048 (12) | 0.0087 (13) | −0.0023 (11) |
C15 | 0.0437 (19) | 0.0249 (14) | 0.0443 (18) | −0.0021 (12) | 0.0074 (14) | −0.0072 (12) |
Br—C4 | 1.906 (3) | C6—H6 | 0.950 |
S—O2 | 1.4372 (18) | C8—C15 | 1.487 (4) |
S—O3 | 1.4377 (18) | C9—C14 | 1.387 (4) |
S—C1 | 1.740 (3) | C9—C10 | 1.393 (4) |
S—C9 | 1.758 (3) | C10—C11 | 1.383 (4) |
O1—C8 | 1.369 (3) | C10—H10 | 0.950 |
O1—C7 | 1.380 (3) | C11—C12 | 1.389 (5) |
C1—C8 | 1.363 (4) | C11—H11 | 0.950 |
C1—C2 | 1.448 (3) | C12—C13 | 1.387 (5) |
C2—C7 | 1.392 (3) | C12—H12 | 0.950 |
C2—C3 | 1.398 (3) | C13—C14 | 1.377 (4) |
C3—C4 | 1.388 (4) | C13—H13 | 0.950 |
C3—H3 | 0.950 | C14—H14 | 0.950 |
C4—C5 | 1.392 (4) | C15—H15A | 0.980 |
C5—C6 | 1.381 (4) | C15—H15B | 0.980 |
C5—H5 | 0.950 | C15—H15C | 0.980 |
C6—C7 | 1.378 (4) | ||
O2—S—O3 | 119.57 (12) | C1—C8—O1 | 110.7 (2) |
O2—S—C1 | 107.14 (12) | C1—C8—C15 | 134.4 (3) |
O3—S—C1 | 108.70 (12) | O1—C8—C15 | 114.9 (2) |
O2—S—C9 | 108.19 (12) | C14—C9—C10 | 121.1 (3) |
O3—S—C9 | 108.15 (12) | C14—C9—S | 119.5 (2) |
C1—S—C9 | 104.02 (12) | C10—C9—S | 119.5 (2) |
C8—O1—C7 | 106.97 (19) | C11—C10—C9 | 119.4 (3) |
C8—C1—C2 | 107.1 (2) | C11—C10—H10 | 120.3 |
C8—C1—S | 127.2 (2) | C9—C10—H10 | 120.3 |
C2—C1—S | 125.57 (19) | C10—C11—C12 | 119.5 (3) |
C7—C2—C3 | 119.2 (2) | C10—C11—H11 | 120.3 |
C7—C2—C1 | 104.9 (2) | C12—C11—H11 | 120.3 |
C3—C2—C1 | 135.9 (2) | C13—C12—C11 | 120.7 (3) |
C4—C3—C2 | 116.6 (2) | C13—C12—H12 | 119.6 |
C4—C3—H3 | 121.7 | C11—C12—H12 | 119.6 |
C2—C3—H3 | 121.7 | C14—C13—C12 | 120.1 (3) |
C3—C4—C5 | 123.3 (2) | C14—C13—H13 | 119.9 |
C3—C4—Br | 118.4 (2) | C12—C13—H13 | 119.9 |
C5—C4—Br | 118.32 (19) | C13—C14—C9 | 119.2 (3) |
C6—C5—C4 | 120.1 (2) | C13—C14—H14 | 120.4 |
C6—C5—H5 | 119.9 | C9—C14—H14 | 120.4 |
C4—C5—H5 | 119.9 | C8—C15—H15A | 109.5 |
C7—C6—C5 | 116.6 (2) | C8—C15—H15B | 109.5 |
C7—C6—H6 | 121.7 | H15A—C15—H15B | 109.5 |
C5—C6—H6 | 121.7 | C8—C15—H15C | 109.5 |
C6—C7—O1 | 125.5 (2) | H15A—C15—H15C | 109.5 |
C6—C7—C2 | 124.2 (2) | H15B—C15—H15C | 109.5 |
O1—C7—C2 | 110.3 (2) | ||
O2—S—C1—C8 | −152.5 (2) | C3—C2—C7—O1 | 179.2 (2) |
O3—S—C1—C8 | −22.0 (3) | C1—C2—C7—O1 | 0.1 (3) |
C9—S—C1—C8 | 93.1 (3) | C2—C1—C8—O1 | −0.8 (3) |
O2—S—C1—C2 | 31.8 (3) | S—C1—C8—O1 | −177.14 (19) |
O3—S—C1—C2 | 162.3 (2) | C2—C1—C8—C15 | 177.1 (3) |
C9—S—C1—C2 | −82.7 (2) | S—C1—C8—C15 | 0.8 (5) |
C8—C1—C2—C7 | 0.4 (3) | C7—O1—C8—C1 | 0.8 (3) |
S—C1—C2—C7 | 176.8 (2) | C7—O1—C8—C15 | −177.5 (2) |
C8—C1—C2—C3 | −178.5 (3) | O2—S—C9—C14 | −21.6 (2) |
S—C1—C2—C3 | −2.0 (5) | O3—S—C9—C14 | −152.5 (2) |
C7—C2—C3—C4 | 0.3 (4) | C1—S—C9—C14 | 92.0 (2) |
C1—C2—C3—C4 | 179.1 (3) | O2—S—C9—C10 | 158.9 (2) |
C2—C3—C4—C5 | 0.5 (4) | O3—S—C9—C10 | 28.0 (2) |
C2—C3—C4—Br | −179.92 (19) | C1—S—C9—C10 | −87.4 (2) |
C3—C4—C5—C6 | −0.6 (4) | C14—C9—C10—C11 | 0.2 (4) |
Br—C4—C5—C6 | 179.8 (2) | S—C9—C10—C11 | 179.7 (2) |
C4—C5—C6—C7 | −0.2 (4) | C9—C10—C11—C12 | −0.2 (4) |
C5—C6—C7—O1 | −179.4 (2) | C10—C11—C12—C13 | 0.1 (5) |
C5—C6—C7—C2 | 1.1 (4) | C11—C12—C13—C14 | 0.0 (5) |
C8—O1—C7—C6 | 179.8 (3) | C12—C13—C14—C9 | 0.1 (4) |
C8—O1—C7—C2 | −0.6 (3) | C10—C9—C14—C13 | −0.2 (4) |
C3—C2—C7—C6 | −1.2 (4) | S—C9—C14—C13 | −179.6 (2) |
C1—C2—C7—C6 | 179.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Cgi | 0.95 | 2.74 | 3.561 (3) | 145 |
C10—H10···O2ii | 0.95 | 2.54 | 3.285 (3) | 135 |
C14—H14···O3iii | 0.95 | 2.45 | 3.249 (3) | 141 |
C15—H15C···O3 | 0.98 | 2.40 | 3.131 (4) | 131 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H11BrO3S |
Mr | 351.21 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 7.337 (1), 11.345 (1), 16.602 (2) |
β (°) | 94.582 (3) |
V (Å3) | 1377.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.14 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1999) |
Tmin, Tmax | 0.463, 0.542 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8005, 3009, 2349 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.086, 1.03 |
No. of reflections | 3009 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.44 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Cgi | 0.95 | 2.74 | 3.561 (3) | 145.2 |
C10—H10···O2ii | 0.95 | 2.54 | 3.285 (3) | 135.0 |
C14—H14···O3iii | 0.95 | 2.45 | 3.249 (3) | 141.4 |
C15—H15C···O3 | 0.98 | 2.40 | 3.131 (4) | 130.6 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2. |
References
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o521–o522. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o3204. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1999). SADABS. University of Göttingen, Germany. Google Scholar
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This work is related to earlier communications on the synthesis and structure of 5-bromo-2-methyl-1-benzofuran analogues, viz. 5-bromo-2-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007) and 5-bromo-2-methyl-3-phenylsulfinyl-1-benzofuran (Seo et al., 2007). Here we report the crystal structure of the title compound, 5-bromo-2-methyl-3-phenylsulfonyl-1-benzofuran (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.007 Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9–C14) makes a dihedral angle of 78.99 (8)° with the plane of the benzofuran fragment. The crystal packing (Fig. 2) is stabilized by intermolecular C—H···π interactions between a benzene H atom of the benzofuran unit and the phenyl ring of the phenylsulfonyl substituent from an adjacent molecule, with a C6—H6···Cgi separation of 2.74 Å (Fig. 2; Cg is the centroid of the C9–C14 phenyl ring, symmetry code as in Fig. 2). Additionally, intra- and intermolecular C—H···O interactions in the structure are observed (Fig. 2).