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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o770.
Published online 2010 March 6. doi:  10.1107/S1600536810008172
PMCID: PMC2984045

2-(4-Chloro­phen­yl)-3-ethyl­sulfinyl-5-fluoro-1-benzofuran

Abstract

In the title compound, C16H12ClFO2S, the 4-chloro­phenyl ring is rotated out of the benzofuran plane, as indicated by the dihedral angle of 19.79 (8)°. The crystal structure exhibits weak inter­molecular C—H(...)O hydrogen bonds and C—H(...)π inter­actions.

Related literature

For the crystal structures of similar 3-ethyl­sulfinyl-2-(4-fluoro­phen­yl)-5-halo-1-benzofuran derivatives, see: Choi et al. (2010a [triangle],b [triangle],c [triangle]). For the pharmacological 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]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o770-scheme1.jpg

Experimental

Crystal data

  • C16H12ClFO2S
  • M r = 322.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o770-efi9.jpg
  • a = 11.5257 (9) Å
  • b = 7.9655 (6) Å
  • c = 16.395 (1) Å
  • β = 106.518 (1)°
  • V = 1443.07 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.42 mm−1
  • T = 173 K
  • 0.40 × 0.35 × 0.35 mm

Data collection

  • Bruker SMART APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.850, T max = 0.867
  • 12345 measured reflections
  • 3290 independent reflections
  • 2713 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.085
  • S = 1.05
  • 3290 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.27 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/S1600536810008172/bh2275sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008172/bh2275Isup2.hkl

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

supplementary crystallographic information

Comment

Compounds containing benzofuran moiety show diverse pharmacological activities such as antifungal (Aslam et al., 2006), antitumor and antiviral (Galal et al., 2009), antimicrobial (Khan et al., 2005) properties. These compounds are widely occurring in nature (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our ongoing studies of the effect of side chain substituents on the solid state structures of 3-ethylsulfinyl-2-(4-fluorophenyl)-5-halo-1-benzofuran analogues (Choi et al., 2010a,b,c), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.012 (1) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle formed by the benzofuran plane and the 4-fluorophenyl ring is 19.79 (8)°. The crystal packing (Fig. 2) is stabilized by two different C—H···O hydrogen bonds; the first between the benzene H atom and the oxygen of the S═O unit, with a C6—H6···O2i, and the second between the 4-chlorophenyl H atom and the oxygen of the S═O unit, with a C11—H11···O2ii, respectively (Table 1). The crystal packing (Fig. 2) is further stabilized by a C—H···π interaction between the methylene H atom and the 4-chlorophenyl ring, with a C15—H15A···Cgii (Table 1; Cg is the centroid of the C9–C14 4-chlorophenyl ring).

Experimental

77% 3-Chloroperoxybenzoic acid (291 mg, 1.3 mmol) was added in small portions to a stirred solution of 2-(4-chlorophenyl)-3-ethylsulfanyl-5-fluoro-1-benzofuran (368 mg, 1.2 mmol) in dichloromethane (30 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 79%, m.p. 405–406 K; Rf = 0.64 (hexane–ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in acetone 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 methylene, and 0.96 Å for methyl H atoms. Uiso(H) = 1.2Ueq(C) for aryl and methylene H atoms, 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.
C—H···O and C—H···π interactions (dotted lines) in the crystal structure of the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) x, - y + 3/2, z - 1/2; (ii) - x ...

Crystal data

C16H12ClFO2SF(000) = 664
Mr = 322.77Dx = 1.486 Mg m3
Monoclinic, P21/cMelting point = 405–406 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 11.5257 (9) ÅCell parameters from 5508 reflections
b = 7.9655 (6) Åθ = 2.6–27.4°
c = 16.395 (1) ŵ = 0.42 mm1
β = 106.518 (1)°T = 173 K
V = 1443.07 (18) Å3Block, colourless
Z = 40.40 × 0.35 × 0.35 mm

Data collection

Bruker SMART APEXII CCD diffractometer3290 independent reflections
Radiation source: Rotating Anode2713 reflections with I > 2σ(I)
Bruker HELIOS graded multilayer opticsRint = 0.028
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 1.8°
[var phi] and ω scansh = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2009)k = −10→10
Tmin = 0.850, Tmax = 0.867l = −21→20
12345 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: difference Fourier map
wR(F2) = 0.085H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0338P)2 + 0.7418P] where P = (Fo2 + 2Fc2)/3
3290 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = −0.27 e Å3
0 constraints

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

xyzUiso*/Ueq
Cl1.01429 (4)0.47181 (6)0.72194 (3)0.03651 (13)
S0.37916 (4)0.44605 (5)0.71678 (2)0.02292 (11)
F−0.02836 (9)0.79231 (16)0.49298 (7)0.0447 (3)
O10.45081 (10)0.71492 (14)0.53223 (7)0.0262 (3)
O20.30653 (12)0.54333 (16)0.76279 (8)0.0335 (3)
C10.38345 (15)0.56819 (19)0.62737 (10)0.0228 (3)
C20.28142 (15)0.6562 (2)0.57188 (10)0.0242 (3)
C30.15813 (15)0.6723 (2)0.56551 (11)0.0282 (4)
H30.12310.61780.60280.034*
C40.09200 (16)0.7732 (2)0.50110 (12)0.0321 (4)
C50.13881 (17)0.8572 (2)0.44327 (11)0.0328 (4)
H50.08860.92300.40080.039*
C60.26012 (17)0.8427 (2)0.44906 (11)0.0292 (4)
H60.29420.89690.41120.035*
C70.32842 (15)0.7429 (2)0.51444 (10)0.0249 (3)
C80.48285 (15)0.6093 (2)0.60191 (10)0.0233 (3)
C90.61217 (15)0.5719 (2)0.63190 (10)0.0236 (3)
C100.65770 (15)0.4350 (2)0.68435 (11)0.0262 (4)
H100.60450.36280.70020.031*
C110.78105 (15)0.4052 (2)0.71314 (11)0.0274 (4)
H110.81080.31490.74890.033*
C120.85925 (15)0.5115 (2)0.68801 (11)0.0270 (4)
C130.81697 (16)0.6470 (2)0.63528 (11)0.0308 (4)
H130.87060.71660.61830.037*
C140.69410 (16)0.6776 (2)0.60811 (11)0.0288 (4)
H140.66530.76980.57350.035*
C150.28229 (16)0.2801 (2)0.66061 (11)0.0285 (4)
H15A0.25020.21790.70020.034*
H15B0.21460.32870.61770.034*
C160.3499 (2)0.1613 (2)0.61849 (13)0.0414 (5)
H16A0.38080.22230.57860.062*
H16B0.29590.07500.58910.062*
H16C0.41590.11130.66100.062*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0231 (2)0.0483 (3)0.0378 (3)0.00038 (19)0.00815 (18)−0.0005 (2)
S0.0255 (2)0.0234 (2)0.0200 (2)0.00029 (16)0.00665 (15)0.00033 (15)
F0.0275 (6)0.0575 (8)0.0458 (7)0.0124 (5)0.0052 (5)0.0073 (6)
O10.0286 (6)0.0259 (6)0.0249 (6)0.0006 (5)0.0091 (5)0.0030 (5)
O20.0433 (8)0.0313 (7)0.0311 (7)0.0041 (6)0.0192 (6)−0.0023 (5)
C10.0251 (8)0.0207 (8)0.0223 (8)0.0015 (6)0.0065 (6)0.0010 (6)
C20.0293 (9)0.0213 (8)0.0218 (8)0.0021 (7)0.0072 (7)−0.0013 (6)
C30.0279 (9)0.0302 (9)0.0269 (9)0.0025 (7)0.0085 (7)0.0007 (7)
C40.0275 (9)0.0348 (10)0.0315 (9)0.0059 (8)0.0043 (7)−0.0031 (8)
C50.0400 (11)0.0291 (9)0.0246 (9)0.0081 (8)0.0017 (8)0.0012 (7)
C60.0407 (10)0.0249 (9)0.0218 (8)0.0019 (7)0.0086 (7)0.0001 (7)
C70.0284 (9)0.0226 (8)0.0240 (8)0.0017 (7)0.0077 (7)−0.0024 (6)
C80.0292 (9)0.0191 (8)0.0218 (8)−0.0012 (7)0.0077 (7)−0.0008 (6)
C90.0254 (8)0.0234 (8)0.0227 (8)−0.0014 (6)0.0080 (7)−0.0040 (6)
C100.0264 (9)0.0224 (8)0.0322 (9)−0.0027 (7)0.0123 (7)−0.0007 (7)
C110.0290 (9)0.0233 (8)0.0300 (9)0.0030 (7)0.0086 (7)0.0006 (7)
C120.0221 (8)0.0329 (9)0.0260 (8)−0.0008 (7)0.0070 (7)−0.0068 (7)
C130.0303 (9)0.0343 (10)0.0298 (9)−0.0074 (8)0.0115 (8)0.0017 (8)
C140.0313 (9)0.0293 (9)0.0258 (9)−0.0029 (7)0.0082 (7)0.0037 (7)
C150.0308 (9)0.0234 (8)0.0286 (9)−0.0050 (7)0.0038 (7)0.0005 (7)
C160.0585 (13)0.0296 (10)0.0344 (11)0.0016 (9)0.0105 (9)−0.0066 (8)

Geometric parameters (Å, °)

Cl—C121.7427 (17)C8—C91.461 (2)
S—O21.4930 (12)C9—C101.395 (2)
S—C11.7717 (16)C9—C141.401 (2)
S—C151.8047 (17)C10—C111.385 (2)
F—C41.364 (2)C10—H100.9300
O1—C71.375 (2)C11—C121.382 (2)
O1—C81.3820 (19)C11—H110.9300
C1—C81.366 (2)C12—C131.382 (2)
C1—C21.447 (2)C13—C141.380 (2)
C2—C71.395 (2)C13—H130.9300
C2—C31.401 (2)C14—H140.9300
C3—C41.373 (2)C15—C161.512 (3)
C3—H30.9300C15—H15A0.9700
C4—C51.389 (3)C15—H15B0.9700
C5—C61.379 (3)C16—H16A0.9600
C5—H50.9300C16—H16B0.9600
C6—C71.386 (2)C16—H16C0.9600
C6—H60.9300
O2—S—C1106.53 (7)C10—C9—C8122.36 (15)
O2—S—C15106.47 (8)C14—C9—C8119.21 (15)
C1—S—C1597.97 (8)C11—C10—C9120.90 (16)
C7—O1—C8106.91 (12)C11—C10—H10119.5
C8—C1—C2107.11 (14)C9—C10—H10119.5
C8—C1—S127.41 (13)C12—C11—C10119.14 (16)
C2—C1—S125.26 (12)C12—C11—H11120.4
C7—C2—C3118.97 (15)C10—C11—H11120.4
C7—C2—C1105.19 (14)C11—C12—C13121.38 (16)
C3—C2—C1135.83 (16)C11—C12—Cl119.38 (14)
C4—C3—C2116.15 (16)C13—C12—Cl119.23 (14)
C4—C3—H3121.9C14—C13—C12119.14 (16)
C2—C3—H3121.9C14—C13—H13120.4
F—C4—C3117.85 (16)C12—C13—H13120.4
F—C4—C5117.48 (16)C13—C14—C9121.00 (16)
C3—C4—C5124.67 (17)C13—C14—H14119.5
C6—C5—C4119.71 (16)C9—C14—H14119.5
C6—C5—H5120.1C16—C15—S111.53 (13)
C4—C5—H5120.1C16—C15—H15A109.3
C5—C6—C7116.30 (16)S—C15—H15A109.3
C5—C6—H6121.8C16—C15—H15B109.3
C7—C6—H6121.8S—C15—H15B109.3
O1—C7—C6125.43 (15)H15A—C15—H15B108.0
O1—C7—C2110.38 (14)C15—C16—H16A109.5
C6—C7—C2124.18 (16)C15—C16—H16B109.5
C1—C8—O1110.38 (14)H16A—C16—H16B109.5
C1—C8—C9135.43 (15)C15—C16—H16C109.5
O1—C8—C9114.16 (14)H16A—C16—H16C109.5
C10—C9—C14118.43 (16)H16B—C16—H16C109.5
O2—S—C1—C8130.71 (15)C2—C1—C8—O1−1.44 (18)
C15—S—C1—C8−119.40 (16)S—C1—C8—O1−176.28 (11)
O2—S—C1—C2−43.25 (16)C2—C1—C8—C9176.59 (17)
C15—S—C1—C266.64 (15)S—C1—C8—C91.8 (3)
C8—C1—C2—C71.33 (18)C7—O1—C8—C10.97 (17)
S—C1—C2—C7176.32 (12)C7—O1—C8—C9−177.52 (13)
C8—C1—C2—C3−177.60 (19)C1—C8—C9—C1020.4 (3)
S—C1—C2—C3−2.6 (3)O1—C8—C9—C10−161.65 (14)
C7—C2—C3—C40.7 (2)C1—C8—C9—C14−158.99 (19)
C1—C2—C3—C4179.52 (18)O1—C8—C9—C1419.0 (2)
C2—C3—C4—F−179.86 (15)C14—C9—C10—C110.8 (2)
C2—C3—C4—C50.3 (3)C8—C9—C10—C11−178.60 (15)
F—C4—C5—C6179.66 (16)C9—C10—C11—C12−1.2 (3)
C3—C4—C5—C6−0.5 (3)C10—C11—C12—C130.4 (3)
C4—C5—C6—C7−0.3 (3)C10—C11—C12—Cl−178.48 (13)
C8—O1—C7—C6179.89 (16)C11—C12—C13—C140.8 (3)
C8—O1—C7—C2−0.08 (17)Cl—C12—C13—C14179.64 (14)
C5—C6—C7—O1−178.60 (15)C12—C13—C14—C9−1.2 (3)
C5—C6—C7—C21.4 (3)C10—C9—C14—C130.4 (3)
C3—C2—C7—O1178.38 (14)C8—C9—C14—C13179.81 (16)
C1—C2—C7—O1−0.77 (18)O2—S—C15—C16−174.17 (12)
C3—C2—C7—C6−1.6 (3)C1—S—C15—C1675.90 (14)
C1—C2—C7—C6179.26 (15)

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C9–C14 4-chlorophenyl ring.
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.523.371 (2)152
C11—H11···O2ii0.932.533.116 (2)121
C15—H15A···Cgii0.972.663.560 (2)155

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2275).

References

  • Akgul, Y. Y. & Anil, H. (2003). Phytochemistry, 63, 939–943. [PubMed]
  • Aslam, S. N., Stevenson, P. C., Phythian, S. J., Veitch, N. C. & Hall, D. R. (2006). Tetrahedron, 62, 4214–4226.
  • 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, o323. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010b). Acta Cryst. E66, o402. [PMC free article] [PubMed]
  • Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2010c). Acta Cryst. E66, o629. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • 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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