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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3087.
Published online 2010 November 6. doi:  10.1107/S1600536810042339
PMCID: PMC3011414

3-[(4-Chloro­phen­yl)sulfin­yl]-2,4,6,7-tetra­methyl-1-benzofuran

Abstract

In the title compound, C18H17ClO2S, the 4-chloro­phenyl ring is oriented approximately perpendicular to the mean plane of the benzofuran ring [dihedral angle = 87.49 (5)°]. In the crystal, mol­ecules are linked through weak inter­molecular C—H(...)π inter­actions, forming left- and right-handed pseudo-helices along the a axis.

Related literature

For the biological activity of benzofuran compounds, see: Aslam et al. (2006 [triangle]); Galal et al. (2009 [triangle]); Khan et al. (2005 [triangle]). For natural products with benzofuran rings, see: Akgul & Anil (2003 [triangle]); Soekamto et al. (2003 [triangle]). For the structures of related 3-(4–chloro­phenyl­sulfin­yl)-2-methyl-1-benzofuran derivatives, see: Choi et al. (2010a [triangle],b [triangle],c [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3087-scheme1.jpg

Experimental

Crystal data

  • C18H17ClO2S
  • M r = 332.83
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3087-efi5.jpg
  • a = 12.2329 (4) Å
  • b = 20.1499 (7) Å
  • c = 6.4840 (2) Å
  • V = 1598.25 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.37 mm−1
  • T = 173 K
  • 0.33 × 0.16 × 0.10 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.651, T max = 0.746
  • 8651 measured reflections
  • 3392 independent reflections
  • 2809 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.090
  • S = 1.05
  • 3392 reflections
  • 203 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.25 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1382 Friedel pairs
  • Flack parameter: −0.03 (6)

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/S1600536810042339/bh2316sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042339/bh2316Isup2.hkl

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

supplementary crystallographic information

Comment

A series of benzofuran ring system have received much attention in view of their interesting pharmacological properties such as antifungal, antimicrobial, antitumor and antiviral activities (Aslam et al., 2006; Galal et al., 2009; Khan et al., 2005). These compounds widely occur in nature (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our study of the substituent effect on the solid state structures of 3-(4-chlorophenylsulfinyl)-2-methyl-1-benzofuran analogues (Choi et al., 2010a,b,c), we report herein on the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.011 (2) Å from the least-squares plane defined by the nine constituent atoms. The 4-chlorophenyl ring makes a dihedral angle of 87.49 (5)° with the mean plane of the benzofuran fragment. The crystal packing (Fig. 2) is stabilized by weak intermolecular C—H···π interactions; the first one between a methyl H atom and the 4-chlorophenyl ring (C11—H11A···Cg1i; Table 1, Cg1 is the centroid of the C13···C18 4–chlorophenyl ring), and the second one between a methyl H atom and the benzene ring (C12—H12B···Cg2ii; Table 1, Cg2 is the centroid of the C2···C7 benzene ring). The title compound crystallizes in the non-centrosymmetric space group Pna21 in spite of having no asymmetric C atoms. The space group is caused by a right-hand pseudo-helix along the a axis (Fig. 2).

Experimental

77% 3-chloroperoxybenzoic acid (269 mg, 1.2 mmol) was added in small portions to a stirred solution of 3-(4-chlorophenylsulfanyl)-2,4,6,7-tetramethyl-1-benzofuran (348 mg, 1.0 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, 2:1 v/v) to afford the title compound as a colorless solid [yield 76%, m.p. 442–443 K; Rf = 0.67 (hexane-ethyl acetate, 2:1 v/v)]. Single crystals suitable for X–ray diffraction were prepared by slow evaporation of 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 and 0.96 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. H atoms are presented as small spheres of arbitrary radius.
Fig. 2.
A view of the C—H···π interactions (dotted lines) in the crystal structure of the title compound. Cg1 and Cg2 denote the centroids of the C13···C18 4-chlorophenyl ring and the C2···C7 ...

Crystal data

C18H17ClO2SDx = 1.383 Mg m3
Mr = 332.83Melting point: 442 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 2945 reflections
a = 12.2329 (4) Åθ = 2.6–26.8°
b = 20.1499 (7) ŵ = 0.37 mm1
c = 6.4840 (2) ÅT = 173 K
V = 1598.25 (9) Å3Block, colourless
Z = 40.33 × 0.16 × 0.10 mm
F(000) = 696

Data collection

Bruker SMART APEXII CCD diffractometer3392 independent reflections
Radiation source: rotating anode2809 reflections with I > 2σ(I)
graphite multilayerRint = 0.034
Detector resolution: 10.0 pixels mm-1θmax = 27.6°, θmin = 2.0°
[var phi] and ω scansh = −15→11
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −26→20
Tmin = 0.651, Tmax = 0.746l = −8→8
8651 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)] = 0.038H-atom parameters constrained
wR(F2) = 0.090w = 1/[σ2(Fo2) + (0.0426P)2 + 0.1096P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3392 reflectionsΔρmax = 0.20 e Å3
203 parametersΔρmin = −0.25 e Å3
1 restraintAbsolute structure: Flack (1983), 1382 Friedel pairs
0 constraintsFlack parameter: −0.03 (6)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl0.48480 (5)0.93993 (4)1.24227 (15)0.0644 (2)
S0.37852 (4)0.74513 (3)0.51507 (13)0.03587 (15)
O10.64405 (11)0.64000 (7)0.4393 (2)0.0317 (4)
O20.27233 (11)0.71240 (9)0.5638 (3)0.0462 (5)
C10.48689 (15)0.68792 (10)0.5388 (4)0.0304 (5)
C20.51433 (16)0.63782 (11)0.6943 (4)0.0308 (5)
C30.47011 (16)0.61312 (12)0.8785 (4)0.0350 (5)
C40.52973 (19)0.56352 (12)0.9760 (4)0.0394 (6)
H40.50300.54691.10000.047*
C50.62780 (17)0.53683 (12)0.8996 (4)0.0368 (6)
C60.67069 (16)0.55999 (10)0.7143 (4)0.0331 (5)
C70.61165 (16)0.61008 (11)0.6216 (4)0.0301 (5)
C80.56685 (15)0.68753 (11)0.3949 (4)0.0312 (5)
C90.36522 (17)0.63876 (14)0.9713 (4)0.0443 (7)
H9A0.37720.68231.02720.066*
H9B0.34180.60941.07910.066*
H9C0.30990.64090.86650.066*
C100.6861 (2)0.48422 (12)1.0225 (5)0.0506 (7)
H10A0.76220.49531.03290.076*
H10B0.67830.44210.95480.076*
H10C0.65490.48171.15810.076*
C110.77427 (18)0.53408 (12)0.6181 (4)0.0423 (6)
H11A0.83620.55150.69120.063*
H11B0.77770.54770.47640.063*
H11C0.77500.48650.62550.063*
C120.58942 (18)0.72823 (11)0.2117 (4)0.0370 (5)
H12A0.65210.75570.23700.055*
H12B0.52730.75570.18240.055*
H12C0.60360.69980.09590.055*
C130.41185 (16)0.79762 (10)0.7289 (4)0.0322 (5)
C140.33260 (16)0.81193 (11)0.8759 (4)0.0353 (5)
H140.26420.79200.86720.042*
C150.35484 (16)0.85543 (11)1.0343 (5)0.0361 (5)
H150.30250.86441.13460.043*
C160.45579 (17)0.88545 (11)1.0414 (4)0.0381 (6)
C170.53552 (17)0.87296 (12)0.8939 (4)0.0405 (6)
H170.60290.89420.90080.049*
C180.51360 (16)0.82887 (11)0.7378 (4)0.0367 (6)
H180.56630.81990.63840.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0533 (4)0.0701 (5)0.0699 (5)−0.0190 (3)0.0152 (4)−0.0291 (4)
S0.0257 (2)0.0485 (3)0.0334 (3)0.0036 (2)−0.0013 (3)0.0026 (3)
O10.0293 (6)0.0334 (8)0.0324 (9)0.0032 (6)0.0014 (7)0.0023 (7)
O20.0239 (7)0.0632 (11)0.0516 (12)−0.0027 (7)−0.0036 (8)−0.0053 (9)
C10.0256 (9)0.0357 (12)0.0299 (12)−0.0028 (8)−0.0019 (11)−0.0005 (11)
C20.0251 (9)0.0363 (13)0.0310 (13)−0.0064 (8)−0.0011 (10)0.0004 (10)
C30.0307 (10)0.0434 (14)0.0310 (13)−0.0115 (10)0.0007 (11)0.0016 (11)
C40.0425 (12)0.0428 (14)0.0330 (15)−0.0160 (10)−0.0024 (11)0.0065 (11)
C50.0388 (11)0.0315 (13)0.0401 (14)−0.0094 (9)−0.0084 (12)0.0049 (12)
C60.0318 (10)0.0291 (12)0.0384 (14)−0.0052 (9)−0.0054 (11)0.0002 (11)
C70.0288 (10)0.0324 (12)0.0292 (13)−0.0075 (9)−0.0007 (10)0.0017 (10)
C80.0268 (10)0.0343 (12)0.0324 (12)−0.0009 (9)−0.0042 (11)−0.0024 (10)
C90.0385 (11)0.0578 (16)0.0366 (17)−0.0109 (11)0.0089 (12)0.0031 (12)
C100.0594 (14)0.0451 (15)0.0472 (15)−0.0088 (12)−0.0102 (16)0.0129 (14)
C110.0396 (12)0.0361 (13)0.0513 (17)0.0052 (10)−0.0004 (13)0.0006 (12)
C120.0341 (11)0.0457 (14)0.0312 (13)−0.0004 (10)0.0025 (12)0.0069 (12)
C130.0268 (9)0.0334 (12)0.0363 (13)0.0047 (9)0.0039 (11)0.0074 (12)
C140.0238 (9)0.0403 (13)0.0419 (14)0.0029 (9)0.0036 (12)0.0044 (12)
C150.0297 (10)0.0376 (12)0.0410 (15)0.0037 (9)0.0109 (13)0.0020 (13)
C160.0355 (10)0.0360 (13)0.0426 (15)−0.0007 (9)0.0038 (12)−0.0022 (12)
C170.0282 (10)0.0423 (14)0.0510 (16)−0.0048 (10)0.0047 (12)0.0017 (13)
C180.0275 (10)0.0405 (13)0.0421 (14)0.0035 (9)0.0086 (12)0.0070 (13)

Geometric parameters (Å, °)

Cl—C161.740 (3)C9—H9C0.9600
S—O21.4907 (15)C10—H10A0.9600
S—C11.763 (2)C10—H10B0.9600
S—C131.791 (3)C10—H10C0.9600
O1—C81.375 (2)C11—H11A0.9600
O1—C71.385 (3)C11—H11B0.9600
C1—C81.352 (3)C11—H11C0.9600
C1—C21.466 (3)C12—H12A0.9600
C2—C71.397 (3)C12—H12B0.9600
C2—C31.402 (3)C12—H12C0.9600
C3—C41.389 (3)C13—C141.390 (3)
C3—C91.508 (3)C13—C181.396 (3)
C4—C51.405 (3)C14—C151.377 (4)
C4—H40.9300C14—H140.9300
C5—C61.391 (4)C15—C161.376 (3)
C5—C101.506 (3)C15—H150.9300
C6—C71.379 (3)C16—C171.389 (3)
C6—C111.506 (3)C17—C181.373 (4)
C8—C121.470 (3)C17—H170.9300
C9—H9A0.9600C18—H180.9300
C9—H9B0.9600
O2—S—C1110.33 (10)C5—C10—H10B109.5
O2—S—C13107.20 (11)H10A—C10—H10B109.5
C1—S—C1398.48 (10)C5—C10—H10C109.5
C8—O1—C7106.57 (16)H10A—C10—H10C109.5
C8—C1—C2107.76 (18)H10B—C10—H10C109.5
C8—C1—S119.19 (18)C6—C11—H11A109.5
C2—C1—S133.01 (17)C6—C11—H11B109.5
C7—C2—C3118.3 (2)H11A—C11—H11B109.5
C7—C2—C1103.78 (19)C6—C11—H11C109.5
C3—C2—C1137.9 (2)H11A—C11—H11C109.5
C4—C3—C2116.1 (2)H11B—C11—H11C109.5
C4—C3—C9120.8 (2)C8—C12—H12A109.5
C2—C3—C9123.1 (2)C8—C12—H12B109.5
C3—C4—C5124.3 (2)H12A—C12—H12B109.5
C3—C4—H4117.9C8—C12—H12C109.5
C5—C4—H4117.9H12A—C12—H12C109.5
C6—C5—C4119.9 (2)H12B—C12—H12C109.5
C6—C5—C10121.0 (2)C14—C13—C18120.0 (2)
C4—C5—C10119.1 (2)C14—C13—S119.65 (17)
C7—C6—C5115.1 (2)C18—C13—S120.10 (19)
C7—C6—C11120.9 (2)C15—C14—C13120.4 (2)
C5—C6—C11124.0 (2)C15—C14—H14119.8
C6—C7—O1122.7 (2)C13—C14—H14119.8
C6—C7—C2126.3 (2)C16—C15—C14118.8 (2)
O1—C7—C2110.98 (19)C16—C15—H15120.6
C1—C8—O1110.9 (2)C14—C15—H15120.6
C1—C8—C12133.7 (2)C15—C16—C17121.8 (2)
O1—C8—C12115.38 (18)C15—C16—Cl119.1 (2)
C3—C9—H9A109.5C17—C16—Cl119.11 (17)
C3—C9—H9B109.5C18—C17—C16119.2 (2)
H9A—C9—H9B109.5C18—C17—H17120.4
C3—C9—H9C109.5C16—C17—H17120.4
H9A—C9—H9C109.5C17—C18—C13119.8 (2)
H9B—C9—H9C109.5C17—C18—H18120.1
C5—C10—H10A109.5C13—C18—H18120.1
O2—S—C1—C8137.63 (18)C8—O1—C7—C20.1 (2)
C13—S—C1—C8−110.40 (19)C3—C2—C7—C6−0.4 (3)
O2—S—C1—C2−44.6 (3)C1—C2—C7—C6−179.7 (2)
C13—S—C1—C267.3 (2)C3—C2—C7—O1−179.92 (18)
C8—C1—C2—C7−1.4 (2)C1—C2—C7—O10.7 (2)
S—C1—C2—C7−179.29 (18)C2—C1—C8—O11.5 (2)
C8—C1—C2—C3179.5 (3)S—C1—C8—O1179.78 (14)
S—C1—C2—C31.6 (4)C2—C1—C8—C12−175.5 (2)
C7—C2—C3—C41.6 (3)S—C1—C8—C122.8 (4)
C1—C2—C3—C4−179.4 (2)C7—O1—C8—C1−1.1 (2)
C7—C2—C3—C9−179.6 (2)C7—O1—C8—C12176.55 (19)
C1—C2—C3—C9−0.5 (4)O2—S—C13—C14−13.4 (2)
C2—C3—C4—C5−1.3 (4)C1—S—C13—C14−127.83 (19)
C9—C3—C4—C5179.8 (2)O2—S—C13—C18172.49 (18)
C3—C4—C5—C6−0.2 (4)C1—S—C13—C1858.0 (2)
C3—C4—C5—C10178.6 (2)C18—C13—C14—C15−1.9 (3)
C4—C5—C6—C71.4 (3)S—C13—C14—C15−176.00 (19)
C10—C5—C6—C7−177.4 (2)C13—C14—C15—C161.4 (4)
C4—C5—C6—C11−179.2 (2)C14—C15—C16—C17−0.1 (4)
C10—C5—C6—C112.0 (3)C14—C15—C16—Cl−179.48 (19)
C5—C6—C7—O1178.34 (19)C15—C16—C17—C18−0.8 (4)
C11—C6—C7—O1−1.1 (3)Cl—C16—C17—C18178.60 (19)
C5—C6—C7—C2−1.1 (3)C16—C17—C18—C130.3 (4)
C11—C6—C7—C2179.4 (2)C14—C13—C18—C171.0 (3)
C8—O1—C7—C6−179.4 (2)S—C13—C18—C17175.08 (18)

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C13–C18 4-chlorophenyl ring and the C2–C7 benzene ring, respectively.
D—H···AD—HH···AD···AD—H···A
C11—H11A···Cg1i0.962.763.613 (3)148
C12—H12B···Cg2ii0.962.833.653 (3)144

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2316).

References

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  • 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, o2325. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst. E66, o2551. [PMC free article] [PubMed]
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  • Galal, S. A., Abd El-All, A. S., Abdallah, M. M. & El-Diwani, H. I. (2009). Bioorg. Med. Chem. Lett 19, 2420–2428. [PubMed]
  • Khan, M. W., Alam, M. J., Rashid, M. A. & Chowdhury, R. (2005). Bioorg. Med. Chem 13, 4796–4805. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Soekamto, N. H., Achmad, S. A., Ghisalberti, E. L., Hakim, E. H. & Syah, Y. M. (2003). Phytochemistry, 64, 831–834. [PubMed]

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