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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2551.
Published online 2010 September 11. doi:  10.1107/S1600536810035932
PMCID: PMC2983273

3-(4-Chloro­phenyl­sulfin­yl)-2,5-dimethyl-1-benzofuran

Abstract

In the crystal structure of the title compound, C16H13ClO2S, the 4-chloro­phenyl ring is oriented approximately perpendicular to the benzofuran ring plane [dihedral angle = 82.45 (5)°]. In the crystal, mol­ecules are linked by weak inter­molecular C—H(...)O and C—H(...)π inter­actions.

Related literature

For the structures of related 3-(4-fluoro­phenyl­sulfin­yl)-2,5-dimethyl-1-benzofuran derivatives, see: Choi et al. (2010a [triangle],b [triangle]).

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Object name is e-66-o2551-scheme1.jpg

Experimental

Crystal data

  • C16H13ClO2S
  • M r = 304.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2551-efi5.jpg
  • a = 12.7673 (19) Å
  • b = 11.0206 (18) Å
  • c = 11.1232 (17) Å
  • β = 113.674 (6)°
  • V = 1433.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.41 mm−1
  • T = 173 K
  • 0.50 × 0.30 × 0.20 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.654, T max = 0.746
  • 12779 measured reflections
  • 3542 independent reflections
  • 3118 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.124
  • S = 1.03
  • 3542 reflections
  • 184 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035932/nc2196sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035932/nc2196Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by Blue-Bio Industry RIC at Dongeui University as a RIC program under the Ministry of Knowledge Economy and Busan city.

supplementary crystallographic information

Comment

As a part of our study on the substituent effect on the solid state structures of 3-(4-fluorophenylsulfinyl)-2,5-dimethyl-1-benzofuran analogues (Choi et al., 2010a, b/), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.004 (2) Å from the least-squares plane defined by the nine constituent atoms. The 4-chlorophenyl ring is nearly perpendicular to the benzofuran plane with a dihedral angle of 82.45 (5)°. In the crystal structure weak intermolecular C—H···O hydrogen bonding and C—H···π interaction are found (Fig. 2 and Table 1).

Experimental

77% 3-chloroperoxybenzoic acid (269 mg, 1.2 mmol) was added in small portions to a stirred solution of 3-(4-chlorophenylsulfanyl)-2,5-dimethyl-1-benzofuran (317 mg, 1.1 mmol) in dichloromethane (40 mL) at 273 K. After being stirred at room temperature for 4h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by column chromatography (hexane–ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 77%, m.p. 440–441 K; R/f = 0.71 (hexane–ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of the solvent from a solution of the title compound in ethyl acetate at room temperature.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aryl, 0.97 Å for methyl H atoms. Uiso(H) = 1.2Ueq(C)for aryl and 1.5Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are presented as a small spheres of arbitrary radius.
Fig. 2.
C—H···O interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) - x + 2, y + 1/2, - z + 3/2; (ii) - x + 2, y -1/2, - z +3/2.]

Crystal data

C16H13ClO2SF(000) = 632
Mr = 304.77Dx = 1.412 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8210 reflections
a = 12.7673 (19) Åθ = 2.5–28.3°
b = 11.0206 (18) ŵ = 0.41 mm1
c = 11.1232 (17) ÅT = 173 K
β = 113.674 (6)°Block, colourless
V = 1433.4 (4) Å30.50 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer3542 independent reflections
Radiation source: rotating anode3118 reflections with I > 2σ(I)
graphite multilayerRint = 0.029
Detector resolution: 10.0 pixels mm-1θmax = 28.4°, θmin = 1.7°
[var phi] and ω scansh = −17→16
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −14→14
Tmin = 0.654, Tmax = 0.746l = −14→13
12779 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.124w = 1/[σ2(Fo2) + (0.0772P)2 + 0.5141P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3542 reflectionsΔρmax = 0.31 e Å3
184 parametersΔρmin = −0.31 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (2)

Special details

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)

xyzUiso*/Ueq
Cl0.76980 (4)0.23428 (4)0.27031 (4)0.04162 (15)
S0.92673 (3)0.68708 (4)0.64073 (4)0.02874 (14)
O10.66438 (10)0.90669 (11)0.50482 (12)0.0371 (3)
O20.95961 (10)0.64186 (13)0.77732 (11)0.0398 (3)
C10.79481 (13)0.76039 (14)0.59101 (14)0.0261 (3)
C20.69064 (12)0.71954 (15)0.60000 (14)0.0264 (3)
C30.65623 (13)0.61696 (16)0.64794 (15)0.0303 (3)
H30.70710.55360.68500.036*
C40.54444 (14)0.61099 (19)0.63938 (17)0.0386 (4)
C50.47007 (15)0.7081 (2)0.5827 (2)0.0485 (5)
H50.39560.70330.57720.058*
C60.50216 (16)0.8100 (2)0.5347 (2)0.0477 (5)
H60.45140.87340.49700.057*
C70.61371 (14)0.81344 (16)0.54552 (16)0.0333 (4)
C80.77512 (14)0.87155 (15)0.53477 (15)0.0315 (3)
C90.50414 (17)0.5015 (2)0.6895 (2)0.0520 (5)
H9A0.56320.44100.71700.078*
H9B0.43680.46920.62090.078*
H9C0.48670.52450.76270.078*
C100.84732 (19)0.95889 (18)0.50136 (19)0.0452 (4)
H10A0.87431.02050.56790.068*
H10B0.80310.99580.41810.068*
H10C0.91140.91700.49640.068*
C110.87780 (11)0.55732 (14)0.53501 (14)0.0253 (3)
C120.82630 (14)0.57394 (16)0.40013 (15)0.0319 (3)
H120.81420.65170.36460.038*
C130.79335 (14)0.47361 (16)0.31949 (15)0.0324 (3)
H130.75810.48310.22890.039*
C140.81304 (12)0.35892 (15)0.37406 (15)0.0272 (3)
C160.89862 (12)0.44303 (15)0.58916 (15)0.0293 (3)
H160.93470.43360.67970.035*
C150.86562 (14)0.34154 (16)0.50817 (16)0.0314 (3)
H150.87870.26370.54350.038*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0453 (3)0.0364 (3)0.0423 (3)−0.00681 (17)0.0167 (2)−0.01106 (18)
S0.0214 (2)0.0302 (2)0.0333 (2)−0.00229 (13)0.00965 (15)−0.00328 (15)
O10.0419 (6)0.0266 (6)0.0358 (6)0.0078 (5)0.0084 (5)−0.0007 (5)
O20.0369 (6)0.0435 (7)0.0287 (6)0.0039 (5)0.0025 (5)−0.0033 (5)
C10.0274 (7)0.0247 (7)0.0260 (7)0.0000 (5)0.0106 (5)−0.0024 (6)
C20.0236 (6)0.0305 (8)0.0239 (6)0.0025 (5)0.0084 (5)−0.0040 (6)
C30.0254 (7)0.0368 (9)0.0285 (7)−0.0012 (6)0.0106 (6)−0.0007 (6)
C40.0296 (8)0.0552 (12)0.0337 (8)−0.0072 (7)0.0155 (6)−0.0082 (8)
C50.0261 (8)0.0683 (14)0.0529 (11)0.0017 (8)0.0177 (8)−0.0129 (10)
C60.0315 (8)0.0547 (12)0.0513 (11)0.0167 (8)0.0106 (8)−0.0075 (9)
C70.0323 (8)0.0319 (9)0.0326 (8)0.0053 (6)0.0097 (6)−0.0066 (6)
C80.0389 (8)0.0262 (8)0.0264 (7)−0.0010 (6)0.0099 (6)−0.0048 (6)
C90.0408 (10)0.0737 (15)0.0464 (10)−0.0196 (10)0.0226 (8)−0.0039 (10)
C100.0619 (12)0.0323 (10)0.0402 (9)−0.0122 (8)0.0193 (8)0.0001 (8)
C110.0206 (6)0.0290 (7)0.0289 (7)0.0005 (5)0.0128 (5)−0.0009 (6)
C120.0385 (8)0.0286 (8)0.0291 (7)0.0031 (6)0.0141 (6)0.0056 (6)
C130.0361 (8)0.0362 (9)0.0252 (7)0.0021 (6)0.0125 (6)0.0028 (6)
C140.0238 (6)0.0300 (8)0.0300 (7)−0.0009 (5)0.0132 (6)−0.0027 (6)
C160.0285 (7)0.0326 (8)0.0257 (7)0.0035 (6)0.0097 (6)0.0048 (6)
C150.0325 (7)0.0276 (8)0.0331 (8)0.0020 (6)0.0122 (6)0.0035 (6)

Geometric parameters (Å, °)

Cl—C141.7355 (16)C8—C101.480 (2)
S—O21.4902 (13)C9—H9A0.9600
S—C11.7457 (15)C9—H9B0.9600
S—C111.7966 (16)C9—H9C0.9600
O1—C81.372 (2)C10—H10A0.9600
O1—C71.384 (2)C10—H10B0.9600
C1—C81.352 (2)C10—H10C0.9600
C1—C21.445 (2)C11—C161.375 (2)
C2—C71.387 (2)C11—C121.387 (2)
C2—C31.394 (2)C12—C131.379 (2)
C3—C41.393 (2)C12—H120.9300
C3—H30.9300C13—C141.381 (2)
C4—C51.401 (3)C13—H130.9300
C4—C91.504 (3)C14—C151.381 (2)
C5—C61.375 (3)C16—C151.391 (2)
C5—H50.9300C16—H160.9300
C6—C71.381 (3)C15—H150.9300
C6—H60.9300
O2—S—C1108.59 (7)C4—C9—H9B109.5
O2—S—C11106.42 (8)H9A—C9—H9B109.5
C1—S—C1197.08 (7)C4—C9—H9C109.5
C8—O1—C7106.41 (13)H9A—C9—H9C109.5
C8—C1—C2107.99 (14)H9B—C9—H9C109.5
C8—C1—S122.84 (12)C8—C10—H10A109.5
C2—C1—S129.17 (12)C8—C10—H10B109.5
C7—C2—C3119.70 (14)H10A—C10—H10B109.5
C7—C2—C1104.31 (14)C8—C10—H10C109.5
C3—C2—C1135.99 (14)H10A—C10—H10C109.5
C4—C3—C2118.93 (16)H10B—C10—H10C109.5
C4—C3—H3120.5C16—C11—C12121.26 (15)
C2—C3—H3120.5C16—C11—S119.15 (11)
C3—C4—C5119.02 (18)C12—C11—S119.47 (12)
C3—C4—C9120.41 (18)C13—C12—C11119.08 (15)
C5—C4—C9120.57 (17)C13—C12—H12120.5
C6—C5—C4123.03 (17)C11—C12—H12120.5
C6—C5—H5118.5C12—C13—C14119.60 (14)
C4—C5—H5118.5C12—C13—H13120.2
C5—C6—C7116.50 (17)C14—C13—H13120.2
C5—C6—H6121.8C13—C14—C15121.69 (15)
C7—C6—H6121.8C13—C14—Cl118.62 (12)
C6—C7—O1126.38 (17)C15—C14—Cl119.68 (13)
C6—C7—C2122.83 (18)C11—C16—C15119.85 (14)
O1—C7—C2110.79 (14)C11—C16—H16120.1
C1—C8—O1110.50 (14)C15—C16—H16120.1
C1—C8—C10133.36 (16)C14—C15—C16118.51 (15)
O1—C8—C10116.14 (16)C14—C15—H15120.7
C4—C9—H9A109.5C16—C15—H15120.7
O2—S—C1—C8131.30 (14)C1—C2—C7—O10.08 (17)
C11—S—C1—C8−118.68 (14)C2—C1—C8—O1−0.52 (17)
O2—S—C1—C2−48.63 (16)S—C1—C8—O1179.54 (10)
C11—S—C1—C261.39 (15)C2—C1—C8—C10179.19 (17)
C8—C1—C2—C70.26 (17)S—C1—C8—C10−0.7 (3)
S—C1—C2—C7−179.80 (12)C7—O1—C8—C10.56 (17)
C8—C1—C2—C3−179.12 (17)C7—O1—C8—C10−179.21 (14)
S—C1—C2—C30.8 (3)O2—S—C11—C16−13.00 (13)
C7—C2—C3—C40.3 (2)C1—S—C11—C16−124.81 (12)
C1—C2—C3—C4179.60 (16)O2—S—C11—C12171.00 (12)
C2—C3—C4—C50.1 (2)C1—S—C11—C1259.20 (13)
C2—C3—C4—C9179.73 (16)C16—C11—C12—C131.4 (2)
C3—C4—C5—C6−0.1 (3)S—C11—C12—C13177.30 (12)
C9—C4—C5—C6−179.70 (19)C11—C12—C13—C14−0.6 (2)
C4—C5—C6—C7−0.3 (3)C12—C13—C14—C15−0.3 (2)
C5—C6—C7—O1−179.62 (17)C12—C13—C14—Cl179.56 (12)
C5—C6—C7—C20.8 (3)C12—C11—C16—C15−1.3 (2)
C8—O1—C7—C6179.97 (17)S—C11—C16—C15−177.26 (12)
C8—O1—C7—C2−0.38 (17)C13—C14—C15—C160.3 (2)
C3—C2—C7—C6−0.7 (2)Cl—C14—C15—C16−179.50 (11)
C1—C2—C7—C6179.74 (16)C11—C16—C15—C140.5 (2)
C3—C2—C7—O1179.58 (13)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1, C2, C7, O1, C8 furan ring.
D—H···AD—HH···AD···AD—H···A
C10—H10A···O2i0.962.513.366 (2)148
C15—H15···O2ii0.932.603.353 (2)139
C13—H13···Cg1iii0.932.853.566 (2)135

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, y−1/2, −z+3/2; (iii) x, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2196).

References

  • Brandenburg, K. (1998). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2009). APEX2 SADABS and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010a). Acta Cryst. E66, o472. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst E66, o543. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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