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The title compound, C12H14O2S, was prepared by the oxidation of 5-ethyl-2-methyl-3-methyl­sulfanyl-1-benzofuran using 3-chloro­perbenzoic acid. The O atom and the methyl group of the methyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran unit. The methyl group of the ethyl substituent is rotated out of the benzofuran plane by 113.5 (2)°. The crystal structure is stabilized by aromatic π–π stacking inter­actions, with centroid–centroid distances of 3.639 (3) and 3.604 (3) Å between benzene/furan and furan/furan rings, respectively, and (2-methyl group)CH2—H...π(benzene ring) inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702716X/gk2078sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680702716X/gk2078Isup2.hkl
Contains datablock I

CCDC reference: 654919

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.041
  • wR factor = 0.107
  • Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.17 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

As part of our continuing work related to the synthesis and structure of 2-methyl-3-methylsulfinyl-1-benzofuran derivatives, the crystal structures of 5-bromo-2-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007a) and 2,5-dimethyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b) have been reported. Here we present the molecular and crystal structure of the title compound (Fig. 1).

The benzofuran ring system is essentially planar, with a mean deviation of 0.003 Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by two different π···π interactions within each stack of molecules; one between the furan ring (Cg1) and an adjacent benzene ring(Cg2ii) {distance; 3.639 (3) Å} of benzofuran unit, and a second between the furan ring (Cg1) and an adjacent furan ring (Cg1i) of benzofuran unit {distance; 3.604 (3) Å}. The crystal packing (Fig. 2) is further stabilized by CH2—H···π interactions between the 2-methyl group and the benzene ring of benzofuran unit, with a C11—H11B···Cg2i separation of 2.75 Å (Fig. 2 and Table 1; Cg1 and Cg2 are the centroids of the C1/C2/C7/O1/C8 furan ring and the C2—C7 benzene ring, respectively; symmetry codes as in Fig. 2).

Related literature top

For crystal structures of isomeric compounds, see: Choi et al. (2007a,b).

Experimental top

3-Chloroperbenzoic acid (77%, 471 mg, 2.1 mmol) was added in small portions to a stirred solution of 5-ethyl-2-methyl-3-methylsulfanyl-1-benzofuran (412 mg, 2.0 mmol) in dichloromethane (30 ml) at 273 K. After being stirred at room temperature for 2hrs, 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 (ethyl acetate) to afford the title compound as a colorless solid [yield 92%, m.p. 361–362 K; Rf = 0.30 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of title compound (I) in acetone at room temperature.

Refinement top

All H atoms were geometrically located in ideal positions and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms and C—H = 0.96 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 work related to the synthesis and structure of 2-methyl-3-methylsulfinyl-1-benzofuran derivatives, the crystal structures of 5-bromo-2-methyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007a) and 2,5-dimethyl-3-methylsulfinyl-1-benzofuran (Choi et al., 2007b) have been reported. Here we present the molecular and crystal structure of the title compound (Fig. 1).

The benzofuran ring system is essentially planar, with a mean deviation of 0.003 Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by two different π···π interactions within each stack of molecules; one between the furan ring (Cg1) and an adjacent benzene ring(Cg2ii) {distance; 3.639 (3) Å} of benzofuran unit, and a second between the furan ring (Cg1) and an adjacent furan ring (Cg1i) of benzofuran unit {distance; 3.604 (3) Å}. The crystal packing (Fig. 2) is further stabilized by CH2—H···π interactions between the 2-methyl group and the benzene ring of benzofuran unit, with a C11—H11B···Cg2i separation of 2.75 Å (Fig. 2 and Table 1; Cg1 and Cg2 are the centroids of the C1/C2/C7/O1/C8 furan ring and the C2—C7 benzene ring, respectively; symmetry codes as in Fig. 2).

For crystal structures of isomeric compounds, see: Choi et al. (2007a,b).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

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. π···π and —CH2—H···π interactions (dasded lines). Cg denotes ring centroids. [Symmetry codes: (i) 1 - x, 1 - y, 2 - z; (ii) -x, 1 - y, 2 - z; (iii) x - 1, y., z.]
5-Ethyl-2-methyl-3-methylsulfinyl-1-benzofuran top
Crystal data top
C12H14O2SZ = 2
Mr = 222.29F(000) = 236
Triclinic, P1Dx = 1.347 Mg m3
Hall symbol: -P_1Mo Kα radiation, λ = 0.71073 Å
a = 8.0314 (6) ÅCell parameters from 2853 reflections
b = 8.7673 (7) Åθ = 2.5–28.2°
c = 8.9017 (7) ŵ = 0.27 mm1
α = 97.740 (1)°T = 173 K
β = 108.721 (1)°Block, colorless
γ = 107.289 (1)°0.52 × 0.43 × 0.25 mm
V = 548.17 (7) Å3
Data collection top
Bruker SMART CCD
diffractometer
2009 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Graphite monochromatorθmax = 26.0°, θmin = 2.5°
Detector resolution: 10.00 pixels mm-1h = 96
φ and ω scansk = 1010
3074 measured reflectionsl = 810
2107 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0502P)2 + 0.4774P]
where P = (Fo2 + 2Fc2)/3
2107 reflections(Δ/σ)max < 0.001
138 parametersΔρmax = 0.83 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C12H14O2Sγ = 107.289 (1)°
Mr = 222.29V = 548.17 (7) Å3
Triclinic, P1Z = 2
a = 8.0314 (6) ÅMo Kα radiation
b = 8.7673 (7) ŵ = 0.27 mm1
c = 8.9017 (7) ÅT = 173 K
α = 97.740 (1)°0.52 × 0.43 × 0.25 mm
β = 108.721 (1)°
Data collection top
Bruker SMART CCD
diffractometer
2009 reflections with I > 2σ(I)
3074 measured reflectionsRint = 0.034
2107 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.06Δρmax = 0.83 e Å3
2107 reflectionsΔρmin = 0.38 e Å3
138 parameters
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
S0.31899 (6)0.70982 (6)0.72234 (5)0.02583 (17)
O10.38885 (18)0.59991 (16)1.14540 (15)0.0242 (3)
O20.1366 (2)0.73454 (19)0.64848 (18)0.0352 (4)
C10.3101 (2)0.6141 (2)0.8823 (2)0.0205 (4)
C20.1751 (2)0.4623 (2)0.8850 (2)0.0207 (4)
C30.0173 (2)0.3325 (2)0.7693 (2)0.0239 (4)
H30.02370.33120.65630.029*
C40.0790 (3)0.2043 (2)0.8232 (2)0.0268 (4)
C50.0168 (3)0.2090 (2)0.9904 (3)0.0300 (4)
H50.08400.12111.02490.036*
C60.1394 (3)0.3372 (2)1.1079 (2)0.0290 (4)
H60.18040.33951.22120.035*
C70.2314 (3)0.4610 (2)1.0499 (2)0.0229 (4)
C80.4327 (2)0.6902 (2)1.0395 (2)0.0217 (4)
C90.2488 (3)0.0602 (3)0.7007 (3)0.0362 (5)
H9A0.31210.00720.76120.043*
H9B0.33920.10340.63290.043*
C100.1996 (3)0.0496 (3)0.5889 (3)0.0372 (5)
H10A0.11210.09490.65490.045*
H10B0.14010.01540.52610.045*
H10C0.31480.14030.51320.045*
C110.5995 (3)0.8462 (2)1.1159 (2)0.0280 (4)
H11A0.61440.90461.03190.042*
H11B0.71270.82081.16590.042*
H11C0.58160.91601.20050.042*
C120.3148 (3)0.5425 (3)0.5772 (2)0.0316 (4)
H12A0.19210.45230.53800.047*
H12B0.41480.50270.63060.047*
H12C0.33510.58180.48420.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0286 (3)0.0238 (3)0.0230 (3)0.00662 (19)0.00919 (19)0.00760 (18)
O10.0256 (7)0.0238 (7)0.0184 (6)0.0071 (5)0.0049 (5)0.0038 (5)
O20.0410 (8)0.0373 (8)0.0302 (7)0.0218 (7)0.0088 (6)0.0119 (6)
C10.0197 (8)0.0210 (8)0.0207 (8)0.0071 (7)0.0075 (7)0.0054 (7)
C20.0195 (8)0.0210 (8)0.0230 (9)0.0090 (7)0.0081 (7)0.0062 (7)
C30.0198 (8)0.0252 (9)0.0240 (9)0.0072 (7)0.0064 (7)0.0044 (7)
C40.0202 (9)0.0229 (9)0.0358 (10)0.0060 (7)0.0124 (8)0.0029 (8)
C50.0331 (10)0.0240 (9)0.0391 (11)0.0087 (8)0.0221 (9)0.0103 (8)
C60.0378 (11)0.0285 (10)0.0255 (9)0.0125 (8)0.0163 (8)0.0104 (8)
C70.0227 (9)0.0212 (9)0.0238 (9)0.0081 (7)0.0084 (7)0.0036 (7)
C80.0203 (8)0.0215 (9)0.0236 (9)0.0085 (7)0.0083 (7)0.0045 (7)
C90.0252 (10)0.0297 (10)0.0444 (12)0.0011 (8)0.0127 (9)0.0018 (9)
C100.0373 (12)0.0297 (10)0.0337 (11)0.0051 (9)0.0091 (9)0.0011 (9)
C110.0232 (9)0.0232 (9)0.0287 (10)0.0048 (8)0.0045 (8)0.0007 (7)
C120.0353 (11)0.0366 (11)0.0245 (10)0.0148 (9)0.0126 (8)0.0062 (8)
Geometric parameters (Å, º) top
S—O21.495 (2)C6—C71.383 (3)
S—C11.758 (2)C6—H60.9500
S—C121.804 (2)C8—C111.484 (3)
O1—C81.374 (2)C9—C101.514 (3)
O1—C71.385 (2)C9—H9A0.9900
C1—C81.359 (3)C9—H9B0.9900
C1—C21.454 (2)C10—H10A0.9800
C2—C71.393 (3)C10—H10B0.9800
C2—C31.397 (3)C10—H10C0.9800
C3—C41.400 (3)C11—H11A0.9800
C3—H30.9500C11—H11B0.9800
C4—C51.400 (3)C11—H11C0.9800
C4—C91.515 (3)C12—H12A0.9800
C5—C61.391 (3)C12—H12B0.9800
C5—H50.9500C12—H12C0.9800
O2—S—C1108.54 (9)C1—C8—C11133.31 (17)
O2—S—C12106.41 (9)O1—C8—C11115.67 (15)
C1—S—C1299.54 (9)C10—C9—C4113.45 (17)
C8—O1—C7106.28 (13)C10—C9—H9A108.9
C8—C1—C2107.40 (16)C4—C9—H9A108.9
C8—C1—S121.09 (14)C10—C9—H9B108.9
C2—C1—S131.20 (14)C4—C9—H9B108.9
C7—C2—C3119.36 (17)H9A—C9—H9B107.7
C7—C2—C1104.43 (16)C9—C10—H10A109.5
C3—C2—C1136.21 (17)C9—C10—H10B109.5
C2—C3—C4118.64 (17)H10A—C10—H10B109.5
C2—C3—H3120.7C9—C10—H10C109.5
C4—C3—H3120.7H10A—C10—H10C109.5
C3—C4—C5119.79 (17)H10B—C10—H10C109.5
C3—C4—C9120.04 (18)C8—C11—H11A109.5
C5—C4—C9120.17 (18)C8—C11—H11B109.5
C6—C5—C4122.62 (17)H11A—C11—H11B109.5
C6—C5—H5118.7C8—C11—H11C109.5
C4—C5—H5118.7H11A—C11—H11C109.5
C7—C6—C5115.92 (18)H11B—C11—H11C109.5
C7—C6—H6122.0S—C12—H12A109.5
C5—C6—H6122.0S—C12—H12B109.5
C6—C7—O1125.44 (17)H12A—C12—H12B109.5
C6—C7—C2123.67 (18)S—C12—H12C109.5
O1—C7—C2110.88 (15)H12A—C12—H12C109.5
C1—C8—O1111.02 (16)H12B—C12—H12C109.5
O2—S—C1—C8117.99 (16)C5—C6—C7—C20.3 (3)
C12—S—C1—C8130.99 (16)C8—O1—C7—C6179.47 (18)
O2—S—C1—C254.83 (19)C8—O1—C7—C20.01 (19)
C12—S—C1—C256.18 (19)C3—C2—C7—C60.0 (3)
C8—C1—C2—C70.05 (19)C1—C2—C7—C6179.51 (17)
S—C1—C2—C7173.62 (14)C3—C2—C7—O1179.53 (15)
C8—C1—C2—C3179.4 (2)C1—C2—C7—O10.03 (19)
S—C1—C2—C35.8 (3)C2—C1—C8—O10.1 (2)
C7—C2—C3—C40.3 (3)S—C1—C8—O1174.41 (12)
C1—C2—C3—C4179.69 (19)C2—C1—C8—C11179.73 (19)
C2—C3—C4—C50.4 (3)S—C1—C8—C115.9 (3)
C2—C3—C4—C9179.01 (17)C7—O1—C8—C10.04 (19)
C3—C4—C5—C60.2 (3)C7—O1—C8—C11179.78 (15)
C9—C4—C5—C6179.24 (18)C3—C4—C9—C1068.7 (3)
C4—C5—C6—C70.2 (3)C5—C4—C9—C10110.7 (2)
C5—C6—C7—O1179.69 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11B···Cgi0.982.753.532 (3)137
Symmetry code: (i) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC12H14O2S
Mr222.29
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)8.0314 (6), 8.7673 (7), 8.9017 (7)
α, β, γ (°)97.740 (1), 108.721 (1), 107.289 (1)
V3)548.17 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.52 × 0.43 × 0.25
Data collection
DiffractometerBruker SMART CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3074, 2107, 2009
Rint0.034
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.107, 1.06
No. of reflections2107
No. of parameters138
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.83, 0.38

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11B···Cgi0.982.753.532 (3)137
Symmetry code: (i) x+1, y+1, z+2.
 

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