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Acta Cryst. (2008). E64, o1016    [ doi:10.1107/S1600536808012877 ]

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

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

Abstract top

The title compound, C17H16O3S, was prepared by the oxidation of 5-ethyl-2-methyl-3-phenylsulfanyl-1-benzofuran with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 75.94 (8)° with the plane of the benzofuran fragment. The crystal structure is stabilized by [pi]-[pi] interactions between the furan rings of neighbouring molecules [centroid-centroid distance = 3.620 (4) Å]. In addition, the crystal structure exhibits C-H...[pi] interactions.

Comment top

As a part of our ongoing studies on the synthesis and structure of 3-phenyl-sulfonyl-1-benzofuran analogues, the crystal structure of 5-bromo-2-methyl-3-phenylsulfonyl-1-benzofuran (Choi et al., 2008a) and 2,5,7-trimethyl-3-phenylsulfonyl-1-benzofuran (Choi et al., 2008b) have been described in the literature. Here we report the crystal structure of the title compound, 5-ethyl-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 75.94 (8)° with the plane of the benzofuran fragment. The crystal packing (Fig. 2) is stabilized by aromatic π-π stacking interactions between the furan rings of neighbouring molecules. The Cg1···Cg1i distance is 3.620 (4) Å (Cg1 is the centroid of the O1/C8/C1/C2/C7 furan ring, symmetry code as in Fig. 2). The molecular packing is further stabilized by C—H···π interactions (Table 1 and Fig. 2); one between a methyl H atom and the benzene ring of the benzofuran unit, i.e. C15—H15C···Cg2i, a second between a methylene H atom of the ethyl group and the benzene ring of the benzofuran unit, i.e. C16—H16B···Cg2ii, respectively. In both cases the benzene ring (Cg2) is involved (Cg2 is the centroid of the C2–7 benzene ring, symmetry code as in Fig. 2).

Related literature top

For the crystal structures of similar 3-phenylsulfonyl-1-benzofuran compounds, see: Choi et al. (2008a,b).

Experimental top

3-Chloroperoxybenzoic acid (77%, 471 mg, 2.1 mmol) was added in small portions to a stirred solution of 5-ethyl-2-methyl-3-phenylsulfanyl-1-benzofuran (268 mg, 1.0 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 80%, m.p. 396- 397 K; Rf = 0.66 (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 benzene at room temperature. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 1.26 (t, J = 7.68 Hz, 3H), 2.74 (q, J = 7.72 Hz, 2H), 2.79 (s, 3H), 7.14 (d, J = 8.44 Hz and 1.48 Hz, 1H), 7.32 (d, J = 8.44 Hz, 1H), 7.48–7.61 (m, 3H), 7.69 (s, 1H), 8.01 (d, J = 6.96 Hz, 2H); EI—MS 300 [M+].

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms, 0.99 Å for methylene H atoms and 0.98 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene 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···π interactions (dotted lines) in the title compound. Cg denotes the ring centroids. [Symmetry code: (i) -x + 1, -y + 2, -z: (ii) -x + 3/2, y + 1/2, -z + 1/2; (iii) -x + 3/2, y - 1/2, -z + 1/2.]
5-Ethyl-2-methyl-3-phenylsulfonyl-1-benzofuran top
Crystal data top
C17H16O3SF000 = 632
Mr = 300.36Dx = 1.363 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P_2ynCell parameters from 2779 reflections
a = 8.7009 (4) Åθ = 2.4–27.9º
b = 8.2019 (4) ŵ = 0.23 mm−1
c = 20.682 (1) ÅT = 173 (2) K
β = 97.301 (1)ºBlock, colorless
V = 1463.98 (12) Å30.40 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3194 independent reflections
Radiation source: fine-focus sealed tube2264 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
Detector resolution: 10.0 pixels mm-1θmax = 27.0º
T = 173(2) Kθmin = 2.4º
φ and ω scansh = −8→11
Absorption correction: nonek = −8→10
8693 measured reflectionsl = −24→26
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)] = 0.056H-atom parameters constrained
wR(F2) = 0.148  w = 1/[σ2(Fo2) + (0.0725P)2 + 0.989P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3194 reflectionsΔρmax = 0.42 e Å−3
192 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C17H16O3SV = 1463.98 (12) Å3
Mr = 300.36Z = 4
Monoclinic, P21/nMo Kα
a = 8.7009 (4) ŵ = 0.23 mm−1
b = 8.2019 (4) ÅT = 173 (2) K
c = 20.682 (1) Å0.40 × 0.20 × 0.20 mm
β = 97.301 (1)º
Data collection top
Bruker SMART CCD
diffractometer		3194 independent reflections
Absorption correction: none2264 reflections with I > 2σ(I)
8693 measured reflectionsRint = 0.048
Refinement top
R[F2 > 2σ(F2)] = 0.056192 parameters
wR(F2) = 0.148H-atom parameters constrained
S = 1.03Δρmax = 0.42 e Å−3
3194 reflectionsΔρmin = −0.49 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
S0.22072 (7)0.75221 (8)0.07999 (3)0.01957 (19)
O10.6098 (2)0.7989 (3)0.00433 (10)0.0340 (5)
O20.1125 (2)0.7474 (2)0.02135 (9)0.0302 (5)
O30.1953 (2)0.8653 (2)0.13092 (9)0.0256 (4)
C10.4056 (3)0.7908 (3)0.06010 (12)0.0206 (6)
C20.5331 (3)0.8631 (3)0.10261 (13)0.0219 (6)
C30.5561 (3)0.9250 (3)0.16565 (13)0.0253 (6)
H30.47380.92640.19180.030*
C40.7023 (3)0.9852 (4)0.18992 (15)0.0318 (7)
C50.8208 (3)0.9848 (4)0.15001 (17)0.0362 (8)
H50.91951.02660.16710.043*
C60.8006 (3)0.9267 (4)0.08721 (16)0.0361 (8)
H60.88170.92860.06050.043*
C70.6548 (3)0.8648 (4)0.06503 (14)0.0286 (6)
C80.4583 (3)0.7531 (3)0.00219 (13)0.0283 (6)
C90.2322 (3)0.5547 (3)0.11444 (12)0.0184 (5)
C100.3091 (3)0.5341 (3)0.17728 (13)0.0246 (6)
H100.35520.62450.20100.030*
C110.3172 (3)0.3800 (4)0.20437 (13)0.0280 (6)
H110.36970.36370.24700.034*
C120.2487 (3)0.2487 (3)0.16934 (14)0.0294 (6)
H120.25420.14290.18820.035*
C130.1722 (3)0.2713 (3)0.10688 (14)0.0280 (6)
H130.12550.18090.08330.034*
C140.1637 (3)0.4242 (3)0.07899 (13)0.0236 (6)
H140.11190.44000.03620.028*
C150.3901 (4)0.6744 (4)−0.05890 (14)0.0389 (8)
H15A0.28230.6446−0.05560.058*
H15B0.44940.5762−0.06640.058*
H15C0.39330.7503−0.09530.058*
C160.7384 (4)1.0484 (5)0.25879 (18)0.0546 (10)
H16A0.83320.99240.27910.066*
H16B0.76391.16570.25610.066*
C170.6211 (5)1.0323 (6)0.30328 (18)0.0597 (11)
H17A0.52721.09120.28550.090*
H17B0.66121.07820.34590.090*
H17C0.59650.91680.30830.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0181 (3)0.0187 (3)0.0212 (3)0.0015 (2)−0.0004 (2)0.0000 (3)
O10.0302 (11)0.0407 (13)0.0338 (12)0.0061 (9)0.0137 (9)0.0073 (10)
O20.0274 (10)0.0313 (11)0.0295 (10)0.0013 (8)−0.0058 (8)0.0035 (9)
O30.0231 (10)0.0222 (10)0.0323 (11)0.0004 (8)0.0063 (8)−0.0056 (8)
C10.0222 (13)0.0177 (13)0.0225 (13)0.0017 (10)0.0049 (10)0.0029 (11)
C20.0177 (13)0.0195 (13)0.0289 (14)0.0024 (10)0.0045 (11)0.0070 (11)
C30.0202 (14)0.0259 (15)0.0299 (15)−0.0016 (11)0.0037 (11)0.0014 (12)
C40.0241 (15)0.0291 (16)0.0404 (17)−0.0061 (12)−0.0025 (12)0.0039 (13)
C50.0175 (14)0.0372 (18)0.052 (2)−0.0044 (12)−0.0009 (13)0.0117 (16)
C60.0208 (15)0.0384 (18)0.051 (2)0.0047 (12)0.0116 (14)0.0179 (16)
C70.0264 (15)0.0277 (15)0.0329 (15)0.0067 (12)0.0082 (12)0.0084 (13)
C80.0306 (15)0.0293 (15)0.0256 (14)0.0069 (12)0.0058 (12)0.0089 (13)
C90.0171 (12)0.0192 (13)0.0191 (13)−0.0002 (10)0.0037 (10)−0.0006 (10)
C100.0263 (14)0.0255 (15)0.0212 (13)−0.0015 (11)−0.0001 (11)−0.0037 (11)
C110.0324 (16)0.0306 (16)0.0198 (13)0.0005 (12)−0.0008 (11)0.0012 (12)
C120.0373 (16)0.0208 (14)0.0317 (15)0.0006 (12)0.0104 (13)0.0044 (13)
C130.0333 (15)0.0224 (15)0.0289 (15)−0.0044 (11)0.0062 (12)−0.0055 (12)
C140.0258 (14)0.0239 (14)0.0209 (13)−0.0016 (11)0.0023 (11)−0.0019 (11)
C150.052 (2)0.0423 (19)0.0232 (15)0.0102 (16)0.0090 (14)−0.0009 (14)
C160.0393 (19)0.066 (3)0.058 (2)−0.0246 (18)0.0013 (17)−0.017 (2)
C170.059 (2)0.077 (3)0.042 (2)−0.018 (2)−0.0003 (18)−0.019 (2)
Geometric parameters (Å, °) top
S—O21.4386 (19)C9—C101.395 (3)
S—O31.4417 (19)C10—C111.381 (4)
S—C11.740 (3)C10—H100.950
S—C91.767 (3)C11—C121.389 (4)
O1—C81.367 (3)C11—H110.950
O1—C71.377 (4)C12—C131.388 (4)
C1—C81.371 (4)C12—H120.950
C1—C21.451 (4)C13—C141.379 (4)
C2—C31.390 (4)C13—H130.950
C2—C71.391 (4)C14—H140.950
C3—C41.397 (4)C15—H15A0.980
C3—H30.950C15—H15B0.980
C4—C51.400 (4)C15—H15C0.980
C4—C161.511 (5)C16—C171.464 (5)
C5—C61.374 (5)C16—H16A0.990
C5—H50.950C16—H16B0.990
C6—C71.389 (4)C17—H17A0.980
C6—H60.950C17—H17B0.980
C8—C151.474 (4)C17—H17C0.980
C9—C141.388 (4)
O2—S—O3119.24 (12)C11—C10—C9118.9 (2)
O2—S—C1109.38 (12)C11—C10—H10120.6
O3—S—C1106.76 (12)C9—C10—H10120.6
O2—S—C9108.19 (12)C10—C11—C12120.1 (3)
O3—S—C9107.54 (11)C10—C11—H11119.9
C1—S—C9104.81 (12)C12—C11—H11119.9
C8—O1—C7107.4 (2)C11—C12—C13120.3 (3)
C8—C1—C2107.9 (2)C11—C12—H12119.8
C8—C1—S126.0 (2)C13—C12—H12119.8
C2—C1—S126.13 (19)C14—C13—C12120.3 (3)
C3—C2—C7119.4 (2)C14—C13—H13119.9
C3—C2—C1136.5 (2)C12—C13—H13119.9
C7—C2—C1104.1 (2)C13—C14—C9118.9 (2)
C2—C3—C4118.8 (3)C13—C14—H14120.5
C2—C3—H3120.6C9—C14—H14120.5
C4—C3—H3120.6C8—C15—H15A109.5
C3—C4—C5119.5 (3)C8—C15—H15B109.5
C3—C4—C16122.0 (3)H15A—C15—H15B109.5
C5—C4—C16118.4 (3)C8—C15—H15C109.5
C6—C5—C4122.9 (3)H15A—C15—H15C109.5
C6—C5—H5118.6H15B—C15—H15C109.5
C4—C5—H5118.6C17—C16—C4118.9 (3)
C5—C6—C7116.2 (3)C17—C16—H16A107.6
C5—C6—H6121.9C4—C16—H16A107.6
C7—C6—H6121.9C17—C16—H16B107.6
O1—C7—C6125.9 (3)C4—C16—H16B107.6
O1—C7—C2110.9 (2)H16A—C16—H16B107.0
C6—C7—C2123.2 (3)C16—C17—H17A109.5
O1—C8—C1109.7 (2)C16—C17—H17B109.5
O1—C8—C15115.4 (2)H17A—C17—H17B109.5
C1—C8—C15134.8 (3)C16—C17—H17C109.5
C14—C9—C10121.5 (2)H17A—C17—H17C109.5
C14—C9—S119.7 (2)H17B—C17—H17C109.5
C10—C9—S118.85 (19)
O2—S—C1—C8−26.7 (3)C1—C2—C7—C6179.3 (3)
O3—S—C1—C8−157.0 (2)C7—O1—C8—C10.8 (3)
C9—S—C1—C889.1 (3)C7—O1—C8—C15−178.2 (2)
O2—S—C1—C2155.7 (2)C2—C1—C8—O1−1.1 (3)
O3—S—C1—C225.4 (3)S—C1—C8—O1−179.00 (19)
C9—S—C1—C2−88.5 (2)C2—C1—C8—C15177.7 (3)
C8—C1—C2—C3−179.7 (3)S—C1—C8—C15−0.2 (5)
S—C1—C2—C3−1.8 (5)O2—S—C9—C1410.3 (2)
C8—C1—C2—C70.9 (3)O3—S—C9—C14140.3 (2)
S—C1—C2—C7178.8 (2)C1—S—C9—C14−106.4 (2)
C7—C2—C3—C4−1.0 (4)O2—S—C9—C10−169.12 (19)
C1—C2—C3—C4179.6 (3)O3—S—C9—C10−39.1 (2)
C2—C3—C4—C51.3 (4)C1—S—C9—C1074.3 (2)
C2—C3—C4—C16−177.6 (3)C14—C9—C10—C110.2 (4)
C3—C4—C5—C6−0.3 (5)S—C9—C10—C11179.6 (2)
C16—C4—C5—C6178.6 (3)C9—C10—C11—C12−0.4 (4)
C4—C5—C6—C7−0.9 (5)C10—C11—C12—C130.2 (4)
C8—O1—C7—C6−179.9 (3)C11—C12—C13—C140.1 (4)
C8—O1—C7—C2−0.2 (3)C12—C13—C14—C9−0.3 (4)
C5—C6—C7—O1−179.2 (3)C10—C9—C14—C130.1 (4)
C5—C6—C7—C21.2 (4)S—C9—C14—C13−179.2 (2)
C3—C2—C7—O1−179.9 (2)C3—C4—C16—C175.8 (6)
C1—C2—C7—O1−0.4 (3)C5—C4—C16—C17−173.1 (3)
C3—C2—C7—C6−0.3 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15C···Cg2i0.982.803.592 (4)139
C16—H16B···Cg2ii0.983.213.903 (4)128
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+3/2, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15C···Cg2i0.982.803.592 (4)139
C16—H16B···Cg2ii0.983.213.903 (4)128
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −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. (2008a). Acta Cryst. E64, o793.

Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008b). Acta Cryst. E64, o794.

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

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