supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

cf2191 scheme

Acta Cryst. (2008). E64, o793    [ doi:10.1107/S1600536808008489 ]

5-Bromo-2-methyl-3-phenylsulfonyl-1-benzofuran

H. D. Choi, P. J. Seo, B. W. Son and U. Lee

Abstract top

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 crystal structure is stabilized by C-H...[pi] 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 crystal structure exhibits intra- and intermolecular C-H...O interactions.

Comment top

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).

Related literature top

For the crystal structures of similar 5-bromo-2-methyl-1-benzofuran derivatives, see: Choi et al. (2007); Seo et al. (2007).

Experimental top

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 column chromatography (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) 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+].

Refinement top

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.

Computing details top

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: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoides drawn at the 50% probability level.
[Figure 2] Fig. 2. C—H···π and C—H···O interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry code: (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.]
5-Bromo-2-methyl-3-phenylsulfonyl-1-benzofuran top
Crystal data top
C15H11BrO3SF000 = 704
Mr = 351.21Dx = 1.693 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P_2ynCell parameters from 3065 reflections
a = 7.337 (1) Åθ = 2.5–27.7º
b = 11.345 (1) ŵ = 3.14 mm−1
c = 16.602 (2) ÅT = 173 (2) K
β = 94.582 (3)ºBlock, colorless
V = 1377.5 (3) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3009 independent reflections
Radiation source: fine-focus sealed tube2349 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
Detector resolution: 10.0 pixels mm-1θmax = 27.0º
T = 173(2) Kθmin = 2.5º
φ and ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)		k = −14→13
Tmin = 0.463, Tmax = 0.542l = −14→21
8005 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.0401P)2 + 0.6448P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3009 reflectionsΔρmax = 0.55 e Å−3
182 parametersΔρmin = −0.44 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C15H11BrO3SV = 1377.5 (3) Å3
Mr = 351.21Z = 4
Monoclinic, P21/nMo Kα
a = 7.337 (1) ŵ = 3.14 mm−1
b = 11.345 (1) ÅT = 173 (2) K
c = 16.602 (2) Å0.30 × 0.20 × 0.20 mm
β = 94.582 (3)º
Data collection top
Bruker SMART CCD
diffractometer		3009 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)		2349 reflections with I > 2σ(I)
Tmin = 0.463, Tmax = 0.542Rint = 0.033
8005 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033182 parameters
wR(F2) = 0.086H-atom parameters constrained
S = 1.03Δρmax = 0.55 e Å−3
3009 reflectionsΔρmin = −0.44 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br0.79772 (5)0.88457 (2)0.038216 (19)0.03963 (12)
S0.65781 (9)0.40138 (5)0.19581 (4)0.02489 (16)
O10.7486 (3)0.36914 (16)−0.03375 (11)0.0296 (4)
O20.5677 (3)0.50746 (16)0.21839 (12)0.0327 (5)
O30.5740 (3)0.28903 (15)0.20838 (12)0.0344 (5)
C10.6960 (4)0.4145 (2)0.09406 (16)0.0242 (5)
C20.7309 (3)0.5236 (2)0.05267 (15)0.0227 (5)
C30.7410 (4)0.6429 (2)0.07353 (16)0.0255 (5)
H30.72090.66930.12640.031*
C40.7819 (4)0.7208 (2)0.01307 (17)0.0287 (6)
C50.8107 (4)0.6854 (2)−0.06521 (16)0.0305 (6)
H50.83720.7425−0.10450.037*
C60.8010 (4)0.5675 (3)−0.08587 (16)0.0308 (6)
H60.81980.5412−0.13890.037*
C70.7626 (3)0.4899 (2)−0.02563 (16)0.0245 (5)
C80.7097 (4)0.3254 (2)0.03977 (16)0.0271 (6)
C90.8786 (4)0.3998 (2)0.24546 (16)0.0259 (6)
C100.9716 (4)0.2932 (2)0.25599 (16)0.0321 (6)
H100.91600.22180.23680.039*
C111.1457 (5)0.2921 (3)0.29469 (19)0.0446 (8)
H111.21050.22000.30240.054*
C121.2249 (5)0.3974 (3)0.32221 (19)0.0506 (9)
H121.34450.39690.34880.061*
C131.1314 (5)0.5031 (3)0.31132 (19)0.0467 (8)
H131.18700.57450.33040.056*
C140.9580 (4)0.5048 (2)0.27289 (17)0.0333 (6)
H140.89350.57710.26520.040*
C150.6972 (4)0.1947 (2)0.04402 (19)0.0374 (7)
H15A0.81930.16050.04190.056*
H15B0.61690.1657−0.00170.056*
H15C0.64710.17190.09470.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.0526 (2)0.02501 (16)0.0412 (2)−0.00489 (13)0.00320 (14)0.00437 (12)
S0.0301 (4)0.0189 (3)0.0269 (3)−0.0004 (2)0.0096 (3)0.0010 (2)
O10.0328 (11)0.0301 (10)0.0263 (10)0.0005 (8)0.0042 (8)−0.0057 (8)
O20.0393 (12)0.0266 (9)0.0341 (11)0.0064 (8)0.0149 (9)−0.0020 (8)
O30.0392 (12)0.0259 (10)0.0398 (12)−0.0066 (8)0.0140 (9)0.0038 (8)
C10.0256 (14)0.0230 (12)0.0246 (13)0.0000 (10)0.0059 (11)−0.0002 (10)
C20.0191 (13)0.0259 (12)0.0235 (13)0.0019 (10)0.0038 (10)0.0020 (10)
C30.0302 (14)0.0242 (12)0.0224 (13)0.0021 (10)0.0046 (11)−0.0006 (10)
C40.0273 (15)0.0262 (13)0.0325 (15)−0.0024 (11)0.0019 (12)0.0024 (11)
C50.0288 (15)0.0371 (15)0.0258 (14)0.0000 (12)0.0039 (11)0.0081 (12)
C60.0296 (15)0.0427 (15)0.0202 (14)0.0016 (12)0.0033 (11)−0.0001 (12)
C70.0224 (13)0.0252 (12)0.0258 (14)0.0019 (10)0.0007 (11)−0.0038 (10)
C80.0243 (14)0.0275 (13)0.0298 (15)−0.0014 (11)0.0032 (11)−0.0022 (11)
C90.0337 (15)0.0256 (13)0.0196 (13)−0.0007 (10)0.0096 (11)0.0012 (10)
C100.0420 (18)0.0317 (14)0.0239 (14)0.0033 (12)0.0101 (12)0.0077 (11)
C110.043 (2)0.059 (2)0.0330 (17)0.0144 (16)0.0095 (14)0.0149 (15)
C120.0376 (19)0.087 (3)0.0264 (17)−0.0062 (18)0.0010 (14)0.0063 (17)
C130.053 (2)0.059 (2)0.0276 (16)−0.0175 (17)0.0033 (14)−0.0068 (15)
C140.0444 (18)0.0305 (14)0.0258 (14)−0.0048 (12)0.0087 (13)−0.0023 (11)
C150.0437 (19)0.0249 (14)0.0443 (18)−0.0021 (12)0.0074 (14)−0.0072 (12)
Geometric parameters (Å, °) top
Br—C41.906 (3)C6—H60.950
S—O21.4372 (18)C8—C151.487 (4)
S—O31.4377 (18)C9—C141.387 (4)
S—C11.740 (3)C9—C101.393 (4)
S—C91.758 (3)C10—C111.383 (4)
O1—C81.369 (3)C10—H100.950
O1—C71.380 (3)C11—C121.389 (5)
C1—C81.363 (4)C11—H110.950
C1—C21.448 (3)C12—C131.387 (5)
C2—C71.392 (3)C12—H120.950
C2—C31.398 (3)C13—C141.377 (4)
C3—C41.388 (4)C13—H130.950
C3—H30.950C14—H140.950
C4—C51.392 (4)C15—H15A0.980
C5—C61.381 (4)C15—H15B0.980
C5—H50.950C15—H15C0.980
C6—C71.378 (4)
O2—S—O3119.57 (12)C1—C8—O1110.7 (2)
O2—S—C1107.14 (12)C1—C8—C15134.4 (3)
O3—S—C1108.70 (12)O1—C8—C15114.9 (2)
O2—S—C9108.19 (12)C14—C9—C10121.1 (3)
O3—S—C9108.15 (12)C14—C9—S119.5 (2)
C1—S—C9104.02 (12)C10—C9—S119.5 (2)
C8—O1—C7106.97 (19)C11—C10—C9119.4 (3)
C8—C1—C2107.1 (2)C11—C10—H10120.3
C8—C1—S127.2 (2)C9—C10—H10120.3
C2—C1—S125.57 (19)C10—C11—C12119.5 (3)
C7—C2—C3119.2 (2)C10—C11—H11120.3
C7—C2—C1104.9 (2)C12—C11—H11120.3
C3—C2—C1135.9 (2)C13—C12—C11120.7 (3)
C4—C3—C2116.6 (2)C13—C12—H12119.6
C4—C3—H3121.7C11—C12—H12119.6
C2—C3—H3121.7C14—C13—C12120.1 (3)
C3—C4—C5123.3 (2)C14—C13—H13119.9
C3—C4—Br118.4 (2)C12—C13—H13119.9
C5—C4—Br118.32 (19)C13—C14—C9119.2 (3)
C6—C5—C4120.1 (2)C13—C14—H14120.4
C6—C5—H5119.9C9—C14—H14120.4
C4—C5—H5119.9C8—C15—H15A109.5
C7—C6—C5116.6 (2)C8—C15—H15B109.5
C7—C6—H6121.7H15A—C15—H15B109.5
C5—C6—H6121.7C8—C15—H15C109.5
C6—C7—O1125.5 (2)H15A—C15—H15C109.5
C6—C7—C2124.2 (2)H15B—C15—H15C109.5
O1—C7—C2110.3 (2)
O2—S—C1—C8−152.5 (2)C3—C2—C7—O1179.2 (2)
O3—S—C1—C8−22.0 (3)C1—C2—C7—O10.1 (3)
C9—S—C1—C893.1 (3)C2—C1—C8—O1−0.8 (3)
O2—S—C1—C231.8 (3)S—C1—C8—O1−177.14 (19)
O3—S—C1—C2162.3 (2)C2—C1—C8—C15177.1 (3)
C9—S—C1—C2−82.7 (2)S—C1—C8—C150.8 (5)
C8—C1—C2—C70.4 (3)C7—O1—C8—C10.8 (3)
S—C1—C2—C7176.8 (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—C40.3 (4)C1—S—C9—C1492.0 (2)
C1—C2—C3—C4179.1 (3)O2—S—C9—C10158.9 (2)
C2—C3—C4—C50.5 (4)O3—S—C9—C1028.0 (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—C110.2 (4)
Br—C4—C5—C6179.8 (2)S—C9—C10—C11179.7 (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—C130.1 (5)
C5—C6—C7—C21.1 (4)C11—C12—C13—C140.0 (5)
C8—O1—C7—C6179.8 (3)C12—C13—C14—C90.1 (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—C6179.7 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···Cgi0.952.743.561 (3)145
C10—H10···O2ii0.952.543.285 (3)135
C14—H14···O3iii0.952.453.249 (3)141
C15—H15C···O30.982.403.131 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···Cgi0.952.743.561 (3)145
C10—H10···O2ii0.952.543.285 (3)135
C14—H14···O3iii0.952.453.249 (3)141
C15—H15C···O30.982.403.131 (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.
references
References top

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o521–o522.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o3204.

Sheldrick, G. M. (1999). SADABS. University of Gottingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.