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Acta Cryst. (2010). E66, o104    [ doi:10.1107/S1600536809052519 ]

5-Bromo-2-(4-fluorophenyl)-3-methylsulfinyl-1-benzofuran

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

Abstract top

In the title compound, C15H10BrFO2S, the O atom and the methyl group of the methylsulfinyl substituent are located on opposite sides of the plane through the benzofuran fragment. The 4-fluorophenyl ring is rotated out of the benzofuran plane, as indicated by a dihedral angle of 26.23 (5)°. The crystal structure is stabilized by a non-classical intermolecular C-H...O hydrogen bond and a Br...O halogen bond [3.163 (2) Å].

Comment top

Molecules including benzofuran moiety are of considerable interest due to a variety of their pharmacological activities (Howlett et al., 1999; Twyman & Allsop, 1999) and these compounds are occurring in natural products (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our continuing studies of the effect of side chain substituents on the solid state structures of 2-(4-fluorophenyl)-3-methylsulfinyl-1-benzofuran analogues (Choi et al., 2009a, b), we report 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 and the 4-fluorophenyl ring is 26.23 (5)Å. The crystal packing (Fig. 2) is stabilized by a non-classical intermolecular C—H···O hydrogen bond between the 4-fluorophenyl H atom and the oxygen of the S═O unit, with a C14—H14···O2i (Table 1), and a Br···O halogen bond between the bromine and the oxygen of the S═O unit [Br···O2ii = 3.163 (2) Å; C—Br···O2ii = 173.37 (7)°] (Politzer et al., 2007).

Related literature top

For the crystal structures of similar 2-(4-fluorophenyl)-3-methylsulfinyl-1-benzofuran derivatives, see: Choi et al. (2009a,b). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999); Twyman & Allsop (1999). For natural products with benzofuran ring systems, see: Akgul & Anil (2003); Soekamto et al. (2003). For a review of halogen bonding, see: Politzer et al. (2007).

Experimental top

77% 3-Chloroperoxybenzoic acid (179 mg, 0.8 mmol) was added in small portions to a stirred solution of 5-bromo-2-(4-fluorophenyl)-3-methylsulfanyl-1-benzofuran (270 mg, 0.8 mmol) in dichloromethane (20 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 87%, m.p. 498–499 K; Rf = 0.6 (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 chloroforrm at room temperature.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and 0.96 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic H atoms and 1.5Ueq(C) for methyl H atoms.

Computing details top

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).

Figures top
[Figure 1] 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] Fig. 2. C—H···O and C—Br···O interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) - x + 1, - y + 1, - z; (ii) - x + 1, - y + 1, - z + 1.]
5-Bromo-2-(4-fluorophenyl)-3-methylsulfinyl-1-benzofuran top
Crystal data top
C15H10BrFO2SZ = 2
Mr = 353.20F(000) = 352
Triclinic, P1Dx = 1.782 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8908 (3) ÅCell parameters from 8308 reflections
b = 8.3434 (3) Åθ = 2.6–27.6°
c = 10.8349 (5) ŵ = 3.29 mm−1
α = 94.886 (2)°T = 173 K
β = 91.995 (2)°Block, colourless
γ = 111.760 (2)°0.27 × 0.25 × 0.24 mm
V = 658.39 (5) Å3
Data collection top
Bruker SMART APEXII CCD
diffractometer		3049 independent reflections
Radiation source: Rotating Anode2844 reflections with I > 2σ(I)
HELIOSRint = 0.023
Detector resolution: 10.0 pixels mm-1θmax = 27.6°, θmin = 1.9°
φ and ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		k = −10→10
Tmin = 0.470, Tmax = 0.506l = −14→13
11517 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0401P)2 + 0.3987P]
where P = (Fo2 + 2Fc2)/3
3049 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 1.46 e Å−3
0 restraintsΔρmin = −0.41 e Å−3
Crystal data top
C15H10BrFO2Sγ = 111.760 (2)°
Mr = 353.20V = 658.39 (5) Å3
Triclinic, P1Z = 2
a = 7.8908 (3) ÅMo Kα radiation
b = 8.3434 (3) ŵ = 3.29 mm−1
c = 10.8349 (5) ÅT = 173 K
α = 94.886 (2)°0.27 × 0.25 × 0.24 mm
β = 91.995 (2)°
Data collection top
Bruker SMART APEXII CCD
diffractometer		3049 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		2844 reflections with I > 2σ(I)
Tmin = 0.470, Tmax = 0.506Rint = 0.023
11517 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.068Δρmax = 1.46 e Å−3
S = 1.06Δρmin = −0.41 e Å−3
3049 reflectionsAbsolute structure: ?
182 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
Br0.59276 (3)0.78959 (2)0.522986 (16)0.02546 (8)
S0.18837 (6)0.20974 (6)0.09974 (4)0.02096 (11)
F−0.07131 (19)0.23126 (17)−0.50519 (11)0.0366 (3)
O10.33521 (19)0.67998 (17)−0.01307 (12)0.0208 (3)
O20.3267 (2)0.18958 (19)0.18682 (15)0.0317 (3)
C10.2611 (3)0.4325 (2)0.07889 (17)0.0188 (3)
C20.3627 (2)0.5753 (2)0.17069 (17)0.0187 (3)
C30.4185 (3)0.5927 (2)0.29638 (17)0.0203 (4)
H30.39110.49690.34100.024*
C40.5166 (3)0.7593 (2)0.35152 (17)0.0206 (4)
C50.5612 (3)0.9066 (2)0.28757 (18)0.0224 (4)
H50.62871.01570.32870.027*
C60.5049 (3)0.8900 (2)0.16288 (18)0.0222 (4)
H60.53200.98580.11830.027*
C70.4070 (3)0.7241 (2)0.10865 (16)0.0193 (3)
C80.2486 (2)0.5018 (2)−0.02943 (17)0.0194 (3)
C90.1628 (3)0.4294 (2)−0.15344 (16)0.0191 (3)
C100.0112 (3)0.2737 (3)−0.17292 (18)0.0232 (4)
H10−0.03750.2150−0.10530.028*
C11−0.0679 (3)0.2050 (3)−0.29139 (19)0.0251 (4)
H11−0.16760.1002−0.30450.030*
C120.0057 (3)0.2968 (3)−0.38902 (17)0.0250 (4)
C130.1530 (3)0.4522 (3)−0.37401 (18)0.0246 (4)
H130.19810.5111−0.44220.029*
C140.2329 (3)0.5193 (2)−0.25552 (17)0.0213 (4)
H140.33290.6240−0.24360.026*
C15−0.0043 (3)0.1923 (3)0.1874 (2)0.0305 (4)
H15A−0.06110.07550.20820.046*
H15B−0.09080.22140.13890.046*
H15C0.03550.27050.26220.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.03353 (13)0.02421 (11)0.01639 (11)0.00930 (8)−0.00282 (7)−0.00101 (7)
S0.0236 (2)0.0167 (2)0.0229 (2)0.00744 (17)0.00343 (17)0.00380 (17)
F0.0438 (8)0.0409 (7)0.0172 (6)0.0084 (6)−0.0084 (5)0.0006 (5)
O10.0264 (7)0.0196 (6)0.0153 (6)0.0072 (5)−0.0008 (5)0.0030 (5)
O20.0285 (8)0.0287 (7)0.0405 (9)0.0118 (6)−0.0019 (6)0.0135 (6)
C10.0219 (9)0.0174 (8)0.0172 (8)0.0073 (7)0.0020 (7)0.0022 (6)
C20.0209 (9)0.0181 (8)0.0184 (8)0.0085 (7)0.0022 (7)0.0029 (7)
C30.0251 (9)0.0194 (8)0.0178 (8)0.0095 (7)0.0016 (7)0.0033 (7)
C40.0226 (9)0.0238 (9)0.0154 (8)0.0095 (7)0.0000 (7)0.0000 (7)
C50.0244 (9)0.0186 (8)0.0221 (9)0.0063 (7)0.0013 (7)−0.0008 (7)
C60.0258 (9)0.0188 (8)0.0220 (9)0.0073 (7)0.0036 (7)0.0054 (7)
C70.0220 (9)0.0211 (8)0.0152 (8)0.0085 (7)0.0011 (7)0.0025 (7)
C80.0198 (9)0.0186 (8)0.0194 (8)0.0067 (7)0.0020 (7)0.0021 (7)
C90.0222 (9)0.0216 (9)0.0158 (8)0.0109 (7)0.0014 (7)0.0025 (7)
C100.0233 (9)0.0272 (9)0.0186 (9)0.0081 (8)0.0009 (7)0.0056 (7)
C110.0235 (9)0.0250 (9)0.0233 (9)0.0055 (8)−0.0019 (7)0.0024 (7)
C120.0289 (10)0.0313 (10)0.0158 (9)0.0137 (8)−0.0046 (7)−0.0011 (7)
C130.0298 (10)0.0294 (10)0.0168 (9)0.0126 (8)0.0034 (7)0.0066 (7)
C140.0230 (9)0.0227 (9)0.0185 (9)0.0084 (7)0.0024 (7)0.0033 (7)
C150.0285 (10)0.0310 (10)0.0355 (11)0.0124 (9)0.0119 (9)0.0124 (9)
Geometric parameters (Å, °) top
Br—C41.899 (2)C6—C71.376 (3)
Br—O2i3.163 (2)C6—H60.9300
S—O21.484 (2)C8—C91.457 (3)
S—C11.767 (2)C9—C101.395 (3)
S—C151.788 (2)C9—C141.403 (3)
F—C121.355 (2)C10—C111.385 (3)
O1—C81.379 (2)C10—H100.9300
O1—C71.381 (2)C11—C121.376 (3)
C1—C81.368 (2)C11—H110.9300
C1—C21.445 (2)C12—C131.375 (3)
C2—C31.395 (2)C13—C141.385 (3)
C2—C71.397 (2)C13—H130.9300
C3—C41.385 (3)C14—H140.9300
C3—H30.9300C15—H15A0.9600
C4—C51.399 (3)C15—H15B0.9600
C5—C61.386 (3)C15—H15C0.9600
C5—H50.9300
C4—Br—O2i173.37 (7)C1—C8—C9134.25 (17)
O2—S—C1107.27 (9)O1—C8—C9115.24 (15)
O2—S—C15106.10 (10)C10—C9—C14119.18 (17)
C1—S—C1598.44 (9)C10—C9—C8121.53 (17)
C8—O1—C7106.96 (14)C14—C9—C8119.28 (17)
C8—C1—C2107.05 (16)C11—C10—C9121.04 (18)
C8—C1—S126.79 (14)C11—C10—H10119.5
C2—C1—S125.87 (14)C9—C10—H10119.5
C3—C2—C7118.99 (17)C12—C11—C10117.90 (19)
C3—C2—C1135.57 (17)C12—C11—H11121.0
C7—C2—C1105.44 (15)C10—C11—H11121.0
C4—C3—C2116.87 (16)F—C12—C13118.59 (18)
C4—C3—H3121.6F—C12—C11118.35 (18)
C2—C3—H3121.6C13—C12—C11123.06 (18)
C3—C4—C5123.33 (17)C12—C13—C14118.82 (18)
C3—C4—Br118.36 (14)C12—C13—H13120.6
C5—C4—Br118.31 (14)C14—C13—H13120.6
C6—C5—C4119.97 (17)C13—C14—C9119.98 (18)
C6—C5—H5120.0C13—C14—H14120.0
C4—C5—H5120.0C9—C14—H14120.0
C7—C6—C5116.46 (17)S—C15—H15A109.5
C7—C6—H6121.8S—C15—H15B109.5
C5—C6—H6121.8H15A—C15—H15B109.5
C6—C7—O1125.57 (16)S—C15—H15C109.5
C6—C7—C2124.38 (17)H15A—C15—H15C109.5
O1—C7—C2110.04 (15)H15B—C15—H15C109.5
C1—C8—O1110.50 (16)
O2—S—C1—C8141.05 (17)C1—C2—C7—O11.3 (2)
C15—S—C1—C8−109.09 (18)C2—C1—C8—O1−0.1 (2)
O2—S—C1—C2−31.88 (19)S—C1—C8—O1−174.17 (13)
C15—S—C1—C277.98 (18)C2—C1—C8—C9−178.79 (19)
C8—C1—C2—C3178.7 (2)S—C1—C8—C97.2 (3)
S—C1—C2—C3−7.2 (3)C7—O1—C8—C10.9 (2)
C8—C1—C2—C7−0.7 (2)C7—O1—C8—C9179.87 (15)
S—C1—C2—C7173.40 (14)C1—C8—C9—C1026.6 (3)
C7—C2—C3—C4−0.4 (3)O1—C8—C9—C10−152.03 (17)
C1—C2—C3—C4−179.7 (2)C1—C8—C9—C14−154.2 (2)
C2—C3—C4—C5−0.3 (3)O1—C8—C9—C1427.2 (2)
C2—C3—C4—Br179.24 (13)C14—C9—C10—C111.5 (3)
C3—C4—C5—C60.8 (3)C8—C9—C10—C11−179.23 (18)
Br—C4—C5—C6−178.77 (14)C9—C10—C11—C12−1.1 (3)
C4—C5—C6—C7−0.5 (3)C10—C11—C12—F−179.63 (17)
C5—C6—C7—O1178.50 (17)C10—C11—C12—C130.0 (3)
C5—C6—C7—C2−0.2 (3)F—C12—C13—C14−179.66 (17)
C8—O1—C7—C6179.73 (18)C11—C12—C13—C140.7 (3)
C8—O1—C7—C2−1.4 (2)C12—C13—C14—C9−0.3 (3)
C3—C2—C7—C60.7 (3)C10—C9—C14—C13−0.8 (3)
C1—C2—C7—C6−179.82 (18)C8—C9—C14—C13179.95 (16)
C3—C2—C7—O1−178.21 (16)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O2ii0.932.583.433 (3)153
Symmetry codes: (ii) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O2i0.932.583.433 (3)153
Symmetry codes: (i) −x+1, −y+1, −z.
Acknowledgements top

No Acknowledgement.

references
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