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The title compound, C16H14O2S, was prepared by the oxidation of 2,5-dimethyl-3-phenyl­sulfanyl-1-benzofuran using 3-chloro­perbenzoic acid. The O atom and the phenyl group of the phenyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran system. The phenyl ring is almost perpendicular to the plane of the benzofuran unit [87.72 (6)°] and is tilted slightly towards it. The crystal structure is stabilized by inter­molecular C—H...π inter­actions between the 5-methyl group and the furan ring of the benzofuran system, and C—H...O=S hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043954/ci2457sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043954/ci2457Isup2.hkl
Contains datablock I

CCDC reference: 664199

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C)= 0.003 Å
  • R factor = 0.050
  • wR factor = 0.118
  • Data-to-parameter ratio = 16.5

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Comment top

As part of our continuing studies on the synthesis and structure of 2-methyl-3-phenysulfinyl-1-benzofuran analogues, we have recently described the crystal structures of 5-iodo-2-methyl-3-phenylsulfinyl-1-benzofuran (Choi et al., 2007) and 5-bromo-2-methyl-3-phenylsulfinyl-1-benzofuran (Seo et al., 2007). Here we report the molecular and crystal structure of the title compound, 2,5-dimethyl-3-phenylsulfinyl-1-benzofuran (Fig. 1).

The benzofuran ring system is essentially planar, with a mean deviation of 0.008 Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9—C14) is almost perpendicular to the plane of the benzofuran ring system [87.72 (6) °] and is tilted slightly towards it. The molecular packing (Fig. 2) is stabilized by intermolecular C—H···π interactions between a hydrogen of the 5-methyl group and the furan ring of the benzofuran system (Table 1, Cg is the centroid of the O1/C2/C1/C8/C3 furan ring), forming a chain along the b axis (Fig. 2). Further stability comes from weak C—H···O hydrogen bonds (Table 1).

Related literature top

For the crystal structures of isomers of the title compound, see: Choi et al. (2007); Seo et al. (2007).

Experimental top

3-Chloroperbenzoic acid (77%, 314 mg, 1.40 mmol) was added in small portions to a stirred solution of 2,5-dimethyl-3-phenylsulfanyl-1-benzofuran (330 mg, 1.30 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 2 h, 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 colourless solid [yield 83%, m.p. 406–407 K; Rf = 0.69 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a dilute solution of the title compound in chloroform at room temperature.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, and with Uiso(H) = 1.2Ueq(C) for aromatic H atoms and Uiso(H) = 1.5Ueq(C) for methyl H atoms.

Structure description top

As part of our continuing studies on the synthesis and structure of 2-methyl-3-phenysulfinyl-1-benzofuran analogues, we have recently described the crystal structures of 5-iodo-2-methyl-3-phenylsulfinyl-1-benzofuran (Choi et al., 2007) and 5-bromo-2-methyl-3-phenylsulfinyl-1-benzofuran (Seo et al., 2007). Here we report the molecular and crystal structure of the title compound, 2,5-dimethyl-3-phenylsulfinyl-1-benzofuran (Fig. 1).

The benzofuran ring system is essentially planar, with a mean deviation of 0.008 Å from the least-squares plane defined by the nine constituent atoms. The phenyl ring (C9—C14) is almost perpendicular to the plane of the benzofuran ring system [87.72 (6) °] and is tilted slightly towards it. The molecular packing (Fig. 2) is stabilized by intermolecular C—H···π interactions between a hydrogen of the 5-methyl group and the furan ring of the benzofuran system (Table 1, Cg is the centroid of the O1/C2/C1/C8/C3 furan ring), forming a chain along the b axis (Fig. 2). Further stability comes from weak C—H···O hydrogen bonds (Table 1).

For the crystal structures of isomers of the title compound, see: Choi et al. (2007); Seo et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

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. The C—H···π interaction (blue dotted lines) and C—H···O hydrogen bonds (red dotted lines) in the title compound. [Symmetry code: (i) x, 1 + y, z; (ii) x, y - 1, z; (iii) 1 - x, y + 1/2, 1/2 - z; (iv) 1 - x, 2 - y, 1/2 - z.]
2,5-Dimethyl-3-phenylsulfinyl-1-benzofuran top
Crystal data top
C16H14O2SF(000) = 568
Mr = 270.33Dx = 1.355 Mg m3
Monoclinic, P21/cMelting point = 406–407 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 11.4663 (6) ÅCell parameters from 3453 reflections
b = 6.2309 (3) Åθ = 2.6–28.0°
c = 18.847 (1) ŵ = 0.24 mm1
β = 100.343 (1)°T = 173 K
V = 1324.65 (12) Å3Plate, colourless
Z = 40.40 × 0.30 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2365 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
Graphite monochromatorθmax = 27.0°, θmin = 1.8°
Detector resolution: 10.0 pixels mm-1h = 1414
φ and ω scansk = 77
7756 measured reflectionsl = 2315
2877 independent 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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0467P)2 + 0.8059P]
where P = (Fo2 + 2Fc2)/3
2877 reflections(Δ/σ)max = 0.001
174 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C16H14O2SV = 1324.65 (12) Å3
Mr = 270.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.4663 (6) ŵ = 0.24 mm1
b = 6.2309 (3) ÅT = 173 K
c = 18.847 (1) Å0.40 × 0.30 × 0.10 mm
β = 100.343 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2365 reflections with I > 2σ(I)
7756 measured reflectionsRint = 0.040
2877 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.13Δρmax = 0.43 e Å3
2877 reflectionsΔρmin = 0.32 e Å3
174 parameters
Special details top

Experimental. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 2.22 (s, 3H), 2.71 (s, 3H), 6.97–7.01 (m, 2H), 7.23 (d, J = 2.92 Hz, 1H), 7.39–7.49 (m, 3H), 7.62–7.66 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ 13.11, 21.23, 110.66, 118.29, 119.87, 123.78, 124.55, 126.04, 129.09, 130.35, 133.35, 142.97, 152.55, 159.76; EI—MS 270 [M+].

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
S0.43404 (5)0.66525 (9)0.09835 (3)0.02556 (16)
O10.19127 (14)0.5264 (3)0.21547 (8)0.0288 (4)
O20.47042 (14)0.8958 (3)0.10329 (9)0.0357 (4)
C10.30788 (18)0.6429 (3)0.13955 (11)0.0231 (4)
C20.29523 (19)0.4935 (4)0.18964 (11)0.0261 (5)
C30.13892 (19)0.7081 (3)0.18066 (11)0.0251 (5)
C40.0339 (2)0.8019 (4)0.19060 (13)0.0326 (5)
H40.01210.74440.22330.039*
C50.0008 (2)0.9845 (4)0.15038 (13)0.0316 (5)
H50.07221.05400.15620.038*
C60.0654 (2)1.0711 (4)0.10119 (12)0.0282 (5)
C70.17043 (19)0.9709 (4)0.09248 (12)0.0262 (5)
H70.21641.02720.05960.031*
C80.20766 (18)0.7869 (3)0.13254 (11)0.0222 (4)
C90.36209 (17)0.6185 (3)0.00667 (11)0.0220 (4)
C100.3169 (2)0.4165 (4)0.01264 (13)0.0299 (5)
H100.32190.30540.02230.036*
C110.2644 (2)0.3788 (4)0.08342 (14)0.0370 (6)
H110.23130.24190.09710.044*
C120.2599 (2)0.5390 (4)0.13439 (13)0.0370 (6)
H120.22280.51280.18290.044*
C130.3091 (2)0.7374 (4)0.11498 (13)0.0347 (6)
H130.30780.84610.15050.042*
C140.36065 (19)0.7789 (4)0.04388 (13)0.0279 (5)
H140.39430.91540.03030.033*
C150.3687 (2)0.3092 (4)0.22060 (13)0.0363 (6)
H15A0.43900.29900.19790.054*
H15B0.32240.17670.21170.054*
H15C0.39330.33010.27270.054*
C160.0237 (2)1.2711 (4)0.05914 (14)0.0373 (6)
H16A0.05051.39790.08830.056*
H16B0.06311.27090.04710.056*
H16C0.05661.27450.01460.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0192 (3)0.0303 (3)0.0272 (3)0.0016 (2)0.0041 (2)0.0018 (2)
O10.0338 (9)0.0320 (9)0.0221 (8)0.0026 (7)0.0087 (7)0.0035 (6)
O20.0326 (9)0.0370 (10)0.0379 (9)0.0148 (7)0.0075 (7)0.0042 (8)
C10.0230 (10)0.0236 (11)0.0227 (10)0.0023 (8)0.0038 (8)0.0004 (9)
C20.0289 (11)0.0289 (12)0.0198 (10)0.0031 (9)0.0022 (8)0.0015 (9)
C30.0276 (11)0.0267 (11)0.0210 (10)0.0038 (9)0.0044 (8)0.0036 (9)
C40.0296 (12)0.0416 (14)0.0285 (12)0.0051 (11)0.0101 (9)0.0023 (10)
C50.0255 (11)0.0362 (13)0.0332 (13)0.0005 (10)0.0056 (9)0.0106 (10)
C60.0289 (11)0.0251 (11)0.0293 (12)0.0013 (9)0.0014 (9)0.0082 (9)
C70.0253 (11)0.0248 (11)0.0287 (11)0.0045 (9)0.0053 (9)0.0009 (9)
C80.0217 (10)0.0227 (11)0.0224 (10)0.0046 (8)0.0046 (8)0.0045 (8)
C90.0182 (9)0.0237 (11)0.0249 (10)0.0004 (8)0.0057 (8)0.0009 (8)
C100.0308 (12)0.0251 (12)0.0353 (13)0.0031 (9)0.0102 (10)0.0022 (10)
C110.0313 (12)0.0332 (13)0.0463 (15)0.0040 (10)0.0062 (11)0.0117 (11)
C120.0282 (12)0.0526 (16)0.0288 (12)0.0083 (11)0.0012 (10)0.0077 (11)
C130.0330 (12)0.0411 (14)0.0307 (12)0.0091 (11)0.0070 (10)0.0086 (11)
C140.0250 (11)0.0246 (11)0.0348 (12)0.0007 (9)0.0074 (9)0.0043 (9)
C150.0444 (14)0.0353 (14)0.0277 (12)0.0036 (11)0.0022 (10)0.0078 (10)
C160.0354 (13)0.0289 (13)0.0456 (15)0.0040 (10)0.0017 (11)0.0005 (11)
Geometric parameters (Å, º) top
S—O21.494 (2)C9—C141.379 (3)
S—C11.766 (2)C9—C101.385 (3)
S—C91.800 (2)C10—C111.381 (3)
O1—C21.381 (3)C10—H100.95
O1—C31.390 (3)C11—C121.380 (4)
C1—C21.352 (3)C11—H110.95
C1—C81.445 (3)C12—C131.381 (4)
C2—C151.481 (3)C12—H120.95
C3—C41.381 (3)C13—C141.388 (3)
C3—C81.393 (3)C13—H130.95
C4—C51.385 (3)C14—H140.95
C4—H40.95C15—H15A0.98
C5—C61.407 (3)C15—H15B0.98
C5—H50.95C15—H15C0.98
C6—C71.392 (3)C16—H16A0.98
C6—C161.508 (3)C16—H16B0.98
C7—C81.397 (3)C16—H16C0.98
C7—H70.95
O2—S—C1106.86 (9)C14—C9—S119.5 (2)
O2—S—C9106.9 (1)C10—C9—S119.0 (2)
C1—S—C997.98 (9)C11—C10—C9119.1 (2)
C2—O1—C3106.3 (2)C11—C10—H10120.5
C2—C1—C8107.9 (2)C9—C10—H10120.5
C2—C1—S124.1 (2)C12—C11—C10120.3 (2)
C8—C1—S127.7 (2)C12—C11—H11119.8
C1—C2—O1110.6 (2)C10—C11—H11119.8
C1—C2—C15133.2 (2)C11—C12—C13120.0 (2)
O1—C2—C15116.2 (2)C11—C12—H12120.0
C4—C3—O1126.4 (2)C13—C12—H12120.0
C4—C3—C8123.2 (2)C12—C13—C14120.4 (2)
O1—C3—C8110.3 (2)C12—C13—H13119.8
C3—C4—C5116.4 (2)C14—C13—H13119.8
C3—C4—H4121.8C9—C14—C13118.8 (2)
C5—C4—H4121.8C9—C14—H14120.6
C4—C5—C6122.7 (2)C13—C14—H14120.6
C4—C5—H5118.7C2—C15—H15A109.5
C6—C5—H5118.7C2—C15—H15B109.5
C7—C6—C5119.1 (2)H15A—C15—H15B109.5
C7—C6—C16120.5 (2)C2—C15—H15C109.5
C5—C6—C16120.4 (2)H15A—C15—H15C109.5
C6—C7—C8119.4 (2)H15B—C15—H15C109.5
C6—C7—H7120.3C6—C16—H16A109.5
C8—C7—H7120.3C6—C16—H16B109.5
C3—C8—C7119.2 (2)H16A—C16—H16B109.5
C3—C8—C1104.8 (2)C6—C16—H16C109.5
C7—C8—C1136.0 (2)H16A—C16—H16C109.5
C14—C9—C10121.3 (2)H16B—C16—H16C109.5
O2—S—C1—C2131.0 (2)C4—C3—C8—C1179.8 (2)
C9—S—C1—C2118.6 (2)O1—C3—C8—C10.3 (2)
O2—S—C1—C842.3 (2)C6—C7—C8—C30.3 (3)
C9—S—C1—C868.1 (2)C6—C7—C8—C1179.1 (2)
C8—C1—C2—O11.2 (2)C2—C1—C8—C30.6 (2)
S—C1—C2—O1175.6 (1)S—C1—C8—C3174.7 (2)
C8—C1—C2—C15178.8 (2)C2—C1—C8—C7178.4 (2)
S—C1—C2—C154.4 (4)S—C1—C8—C74.3 (4)
C3—O1—C2—C11.4 (2)O2—S—C9—C146.0 (2)
C3—O1—C2—C15178.6 (2)C1—S—C9—C14116.4 (2)
C2—O1—C3—C4179.1 (2)O2—S—C9—C10178.7 (2)
C2—O1—C3—C81.1 (2)C1—S—C9—C1068.3 (2)
O1—C3—C4—C5179.4 (2)C14—C9—C10—C113.1 (3)
C8—C3—C4—C50.8 (3)S—C9—C10—C11178.3 (2)
C3—C4—C5—C60.6 (3)C9—C10—C11—C121.6 (4)
C4—C5—C6—C70.3 (3)C10—C11—C12—C130.8 (4)
C4—C5—C6—C16179.6 (2)C11—C12—C13—C141.7 (4)
C5—C6—C7—C80.1 (3)C10—C9—C14—C132.2 (3)
C16—C6—C7—C8179.4 (2)S—C9—C14—C13177.4 (2)
C4—C3—C8—C70.7 (3)C12—C13—C14—C90.3 (3)
O1—C3—C8—C7179.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···Cgi0.982.753.640 (3)151
C14—H14···O2ii0.952.543.145 (3)122
C15—H15C···O2iii0.982.603.537 (3)160
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+2, z; (iii) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H14O2S
Mr270.33
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)11.4663 (6), 6.2309 (3), 18.847 (1)
β (°) 100.343 (1)
V3)1324.65 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.40 × 0.30 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7756, 2877, 2365
Rint0.040
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.118, 1.13
No. of reflections2877
No. of parameters174
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16A···Cgi0.982.753.640 (3)151
C14—H14···O2ii0.952.543.145 (3)122
C15—H15C···O2iii0.982.603.537 (3)160
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+2, z; (iii) x+1, y1/2, z+1/2.
 

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