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Acta Cryst. (2008). E64, o1687    [ doi:10.1107/S1600536808024276 ]

3-Methylsulfinyl-2-phenyl-1-benzofuran

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

Abstract top

The title compound, C15H12O2S, was prepared by the oxidation of 3-methylsulfanyl-2-phenyl-1-benzofuran with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 37.65 (8)° with the plane of the benzofuran fragment. The O atom and the methyl group of the methylsulfinyl substituent lie on opposite sides of the plane of the benzofuran ring system. The crystal structure is stabilized by aromatic [pi]-[pi] interactions between the benzene rings of neighbouring molecules [centroid-centroid distance = 3.549 (2) Å] and by intermolecular C-H...O interactions.

Comment top

This work is related to our previous communications on the synthesis and structure of 3-methylsulfinyl-2-phenyl-1-benzofuran analogues, viz. 5-chloro-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 5-methyl-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007b). Here we report the crystal structure of 3-methylsulfinyl-2-phenyl-1-benzofuran (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.009 (2) Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9—C14) makes a dihedral angle of 37.65 (8)° with the plane of the benzofuran fragment. The molecular packing (Fig. 2) is stabilized by aromatic π—π stacking interactions between the benzene rings from the adjacent molecules. The Cg···Cgii distance is 3.549 (2) Å (Cg is the centroid of C2—C7 benzene ring, symmetry code as in Fig. 2). The crystal structure is further stabilized by C—H···O (Fig. 2) interactions between a methyl H atom and the oxygen of the S=O unit, with a C15—H15C···O2i separation of 2.36 Å (Fig. 2 and Table 1; symmetry code as in Fig. 2).

Related literature top

For the crystal structures of similar 3-methylsulfinyl-2-phenyl-1-benzofuran compounds, see: Choi et al. (2007a,b).

Experimental top

77% 3-Chloroperoxybenzoic acid (359 mg, 1.6 mmol) was added in small portions to a stirred solution of 3-methylsulfanyl-2-phenyl-1-benzofuran (360 mg, 1.5 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 2 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 under vacuum. The residue was purified by column chromatography (hexane-ethyl acetate, 1: 2 v/v) to afford the title compound as a colorless solid [yield 76%, m.p. 408–409 K; Rf = 0.79 (hexane-ethyl acetate, 1:2 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in benzene at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 3.13 (s, 3H), 7.33–7.44 (m, 3H), 7.48–7.54 (m, 2H), 7.59 (d, J = 8.03 Hz, 1H), 7.84 (dd, J = 8.08 Hz and J = 1.48 Hz, 2H), 8.22 (d, J = 7.32 Hz, 1H); EI—MS 256 [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, 0.98 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic H atoms and 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 ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. π—π and C—H···O interactions (dotted lines) in the title compound. Cg denotes ring centroid. [Symmetry code: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y, -z + 1.]
3-Methylsulfinyl-2-phenyl-1-benzofuran top
Crystal data top
C15H12O2SZ = 2
Mr = 256.32F000 = 268
Triclinic, P1Dx = 1.397 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.0185 (8) ÅCell parameters from 2383 reflections
b = 9.4381 (9) Åθ = 2.5–28.2º
c = 9.7749 (9) ŵ = 0.26 mm−1
α = 115.574 (2)ºT = 173 (2) K
β = 109.179 (2)ºBlock, colorless
γ = 94.296 (2)º0.30 × 0.10 × 0.10 mm
V = 609.51 (10) Å3
Data collection top
Bruker SMART CCD
diffractometer		2120 independent reflections
Radiation source: fine-focus sealed tube1878 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
Detector resolution: 10.0 pixels mm-1θmax = 25.0º
T = 173(2) Kθmin = 2.5º
φ and ω scansh = −8→9
Absorption correction: nonek = −11→11
3185 measured reflectionsl = −11→5
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.0341P)2 + 0.3746P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2120 reflectionsΔρmax = 0.32 e Å−3
164 parametersΔρmin = −0.24 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C15H12O2Sγ = 94.296 (2)º
Mr = 256.32V = 609.51 (10) Å3
Triclinic, P1Z = 2
a = 8.0185 (8) ÅMo Kα
b = 9.4381 (9) ŵ = 0.26 mm−1
c = 9.7749 (9) ÅT = 173 (2) K
α = 115.574 (2)º0.30 × 0.10 × 0.10 mm
β = 109.179 (2)º
Data collection top
Bruker SMART CCD
diffractometer		2120 independent reflections
Absorption correction: none1878 reflections with I > 2σ(I)
3185 measured reflectionsRint = 0.030
Refinement top
R[F2 > 2σ(F2)] = 0.037164 parameters
wR(F2) = 0.090H-atom parameters constrained
S = 1.10Δρmax = 0.32 e Å−3
2120 reflectionsΔρmin = −0.24 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
S0.33893 (6)0.23694 (6)0.35764 (6)0.02368 (16)
O1−0.05250 (18)−0.15771 (15)0.17293 (16)0.0238 (3)
O20.4116 (2)0.33041 (18)0.54205 (18)0.0356 (4)
C10.1412 (3)0.0880 (2)0.2927 (2)0.0210 (4)
C20.0021 (3)0.1096 (2)0.3590 (2)0.0219 (4)
C3−0.0353 (3)0.2390 (3)0.4755 (3)0.0280 (5)
H30.04200.34570.53360.034*
C4−0.1883 (3)0.2063 (3)0.5031 (3)0.0321 (5)
H4−0.21700.29280.58070.039*
C5−0.3018 (3)0.0500 (3)0.4202 (3)0.0326 (5)
H5−0.40600.03290.44250.039*
C6−0.2666 (3)−0.0807 (3)0.3064 (3)0.0291 (5)
H6−0.3429−0.18770.25000.035*
C7−0.1131 (3)−0.0453 (2)0.2802 (2)0.0226 (4)
C80.1044 (2)−0.0725 (2)0.1847 (2)0.0212 (4)
C90.1918 (3)−0.1716 (2)0.0813 (2)0.0221 (4)
C100.1916 (3)−0.3292 (2)0.0565 (3)0.0299 (5)
H100.1393−0.36950.11100.036*
C110.2669 (3)−0.4265 (3)−0.0468 (3)0.0370 (5)
H110.2666−0.5331−0.06240.044*
C120.3428 (3)−0.3693 (3)−0.1276 (3)0.0364 (5)
H120.3931−0.4370−0.19950.044*
C130.3451 (3)−0.2136 (3)−0.1033 (3)0.0315 (5)
H130.3986−0.1738−0.15750.038*
C140.2695 (3)−0.1150 (2)0.0000 (2)0.0255 (4)
H140.2707−0.00830.01540.031*
C150.2300 (3)0.3619 (3)0.2805 (3)0.0352 (5)
H15A0.13340.38960.32030.053*
H15B0.17680.30270.15920.053*
H15C0.32030.46160.32000.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0189 (3)0.0221 (3)0.0235 (3)0.00303 (19)0.0068 (2)0.0072 (2)
O10.0233 (7)0.0214 (7)0.0253 (7)0.0042 (5)0.0117 (6)0.0089 (6)
O20.0311 (8)0.0359 (9)0.0232 (8)−0.0025 (7)0.0057 (7)0.0058 (7)
C10.0201 (10)0.0212 (10)0.0202 (10)0.0065 (8)0.0080 (8)0.0088 (8)
C20.0204 (10)0.0264 (10)0.0206 (10)0.0093 (8)0.0080 (8)0.0122 (9)
C30.0305 (11)0.0281 (11)0.0246 (11)0.0125 (9)0.0107 (9)0.0116 (9)
C40.0357 (12)0.0421 (13)0.0277 (11)0.0238 (10)0.0181 (10)0.0185 (10)
C50.0303 (12)0.0506 (14)0.0401 (13)0.0229 (10)0.0236 (10)0.0324 (12)
C60.0256 (11)0.0365 (12)0.0348 (12)0.0106 (9)0.0138 (9)0.0235 (10)
C70.0234 (10)0.0275 (10)0.0213 (10)0.0105 (8)0.0112 (8)0.0132 (9)
C80.0187 (9)0.0235 (10)0.0208 (10)0.0035 (8)0.0067 (8)0.0113 (8)
C90.0198 (9)0.0214 (10)0.0181 (10)0.0034 (8)0.0056 (8)0.0055 (8)
C100.0334 (12)0.0255 (11)0.0309 (12)0.0068 (9)0.0163 (10)0.0113 (9)
C110.0423 (13)0.0239 (11)0.0400 (14)0.0113 (10)0.0199 (11)0.0085 (10)
C120.0317 (12)0.0366 (13)0.0305 (12)0.0101 (10)0.0167 (10)0.0041 (10)
C130.0254 (11)0.0409 (12)0.0227 (11)0.0036 (9)0.0114 (9)0.0104 (9)
C140.0235 (10)0.0277 (11)0.0213 (10)0.0048 (8)0.0070 (8)0.0103 (9)
C150.0292 (11)0.0263 (11)0.0451 (14)0.0039 (9)0.0081 (10)0.0186 (11)
Geometric parameters (Å, °) top
S—O21.492 (2)C6—H60.9500
S—C11.769 (2)C8—C91.461 (3)
S—C151.792 (2)C9—C141.396 (3)
O1—C71.384 (2)C9—C101.400 (3)
O1—C81.384 (2)C10—C111.382 (3)
C1—C81.358 (3)C10—H100.9500
C1—C21.449 (3)C11—C121.386 (3)
C2—C71.394 (3)C11—H110.9500
C2—C31.398 (3)C12—C131.382 (3)
C3—C41.381 (3)C12—H120.9500
C3—H30.9500C13—C141.389 (3)
C4—C51.394 (3)C13—H130.9500
C4—H40.9500C14—H140.9500
C5—C61.383 (3)C15—H15A0.9800
C5—H50.9500C15—H15B0.9800
C6—C71.383 (3)C15—H15C0.9800
O2—S—C1106.42 (9)C1—C8—C9134.62 (17)
O2—S—C15107.19 (10)O1—C8—C9114.80 (16)
C1—S—C1598.28 (10)C14—C9—C10118.74 (18)
C7—O1—C8106.40 (14)C14—C9—C8121.25 (17)
C8—C1—C2107.57 (17)C10—C9—C8119.95 (18)
C8—C1—S125.35 (15)C11—C10—C9120.4 (2)
C2—C1—S126.67 (14)C11—C10—H10119.8
C7—C2—C3118.79 (18)C9—C10—H10119.8
C7—C2—C1104.81 (16)C10—C11—C12120.3 (2)
C3—C2—C1136.38 (19)C10—C11—H11119.8
C4—C3—C2117.8 (2)C12—C11—H11119.8
C4—C3—H3121.1C13—C12—C11119.9 (2)
C2—C3—H3121.1C13—C12—H12120.1
C3—C4—C5121.8 (2)C11—C12—H12120.1
C3—C4—H4119.1C12—C13—C14120.2 (2)
C5—C4—H4119.1C12—C13—H13119.9
C6—C5—C4121.76 (19)C14—C13—H13119.9
C6—C5—H5119.1C13—C14—C9120.40 (19)
C4—C5—H5119.1C13—C14—H14119.8
C7—C6—C5115.5 (2)C9—C14—H14119.8
C7—C6—H6122.3S—C15—H15A109.5
C5—C6—H6122.3S—C15—H15B109.5
C6—C7—O1125.00 (18)H15A—C15—H15B109.5
C6—C7—C2124.38 (18)S—C15—H15C109.5
O1—C7—C2110.62 (16)H15A—C15—H15C109.5
C1—C8—O1110.58 (16)H15B—C15—H15C109.5
O2—S—C1—C8−130.84 (18)C1—C2—C7—O10.4 (2)
C15—S—C1—C8118.42 (19)C2—C1—C8—O11.2 (2)
O2—S—C1—C240.85 (19)S—C1—C8—O1174.25 (13)
C15—S—C1—C2−69.89 (19)C2—C1—C8—C9−178.8 (2)
C8—C1—C2—C7−1.0 (2)S—C1—C8—C9−5.8 (3)
S—C1—C2—C7−173.87 (15)C7—O1—C8—C1−1.0 (2)
C8—C1—C2—C3177.6 (2)C7—O1—C8—C9179.06 (16)
S—C1—C2—C34.7 (3)C1—C8—C9—C14−38.8 (3)
C7—C2—C3—C4−1.6 (3)O1—C8—C9—C14141.18 (18)
C1—C2—C3—C4179.9 (2)C1—C8—C9—C10144.1 (2)
C2—C3—C4—C50.8 (3)O1—C8—C9—C10−36.0 (3)
C3—C4—C5—C60.3 (3)C14—C9—C10—C110.0 (3)
C4—C5—C6—C7−0.4 (3)C8—C9—C10—C11177.18 (19)
C5—C6—C7—O1179.56 (18)C9—C10—C11—C12−0.3 (3)
C5—C6—C7—C2−0.5 (3)C10—C11—C12—C130.7 (4)
C8—O1—C7—C6−179.69 (19)C11—C12—C13—C14−0.9 (3)
C8—O1—C7—C20.3 (2)C12—C13—C14—C90.5 (3)
C3—C2—C7—C61.5 (3)C10—C9—C14—C13−0.1 (3)
C1—C2—C7—C6−179.59 (19)C8—C9—C14—C13−177.25 (18)
C3—C2—C7—O1−178.49 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15C···O2i0.982.343.290 (3)164
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15C···O2i0.982.343.290 (3)164
Symmetry codes: (i) −x+1, −y+1, −z+1.
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. (2007a). Acta Cryst. E63, o1291–o1292.

Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o2922.

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

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