supplementary materials


gg2118 scheme

Acta Cryst. (2013). E69, o1187    [ doi:10.1107/S1600536813017583 ]

5-Fluoro-2-(4-fluorophenyl)-7-methyl-3-phenylsulfinyl-1-benzofuran

P. J. Seo, H. D. Choi and U. Lee

Abstract top

In the title compound, C21H14F2O2S, the dihedral angles between the mean plane [r.m.s. deviation = 0.007 (2) Å] of the benzofuran ring system and the pendant 4-fluorophenyl and phenyl rings are 5.93 (9) and 80.23 (5)°, respectively. In the crystal, molecules are linked by weak C-H...O and C-H...[pi] interactions, forming a three-dimensional network.

Comment top

As a part of our continuing study of 2-(4-fluorophenyl)-3-phenylsulfinyl-1-benzofuran derivatives containing chloro (Choi et al., 2011), bromo (Seo et al., 2011) and iodo (Choi et al., 2012) substituents in 5-position, we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.007 (2) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angles between the mean plane of the benzofuran ring system and the pendant 4-fluorophenyl and phenyl rings are 5.93 (9) and 80.23 (5)°, respectively. In the crystal structure (Fig. 2), molecules are connected by weak C–H···O and C–H···π interactions (Table 1, Cg1 is the centroid of the C16-C21 phenyl ring), forming a three-dimensional network.

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2011, 2012); Seo et al. (2011).

Experimental top

3-Chloroperoxybenzoic acid (77%, 202 mg, 0.9 mmol) was added in small portions to a stirred solution of 5-fluoro-2-(4-fluorophenyl)-7-methyl-3-phenylsulfanyl-1-benzofuran (282 mg, 0.8 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 5h, 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 (benzene) to afford the title compound as a colorless solid [yield 54%, m.p. 466-467 K; Rf = 0.42 (benzene)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in benzene at room temperature.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C–H = 0.95 Å for aryl and 0.98Å for methyl H atoms. Uiso(H) = 1.2Ueq(C) for aryl and 1.5Ueq(C) for methyl H atoms. The positions of methyl hydrogens were optimized rotationally.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. A view of the C–H..O and C–H···π interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) x, y - 1, z; (ii) x - 1/2, - y + 3/2, z - 1/2; (iii) x, y + 1, z; (iv) x + 1/2, - y + 3/2, z + 1/2.]
5-Fluoro-2-(4-fluorophenyl)-7-methyl-3-phenylsulfinyl-1-benzofuran top
Crystal data top
C21H14F2O2SF(000) = 760
Mr = 368.38Dx = 1.443 Mg m3
Monoclinic, P21/nMelting point = 466–467 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 12.3698 (8) ÅCell parameters from 6581 reflections
b = 7.9967 (5) Åθ = 2.2–27.5°
c = 17.4195 (10) ŵ = 0.22 mm1
β = 100.323 (4)°T = 173 K
V = 1695.20 (18) Å3Block, colourless
Z = 40.30 × 0.26 × 0.10 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
4267 independent reflections
Radiation source: rotating anode3147 reflections with I > 2σ(I)
Graphite multilayer monochromatorRint = 0.065
Detector resolution: 10.0 pixels mm-1θmax = 28.5°, θmin = 1.9°
φ and ω scansh = 1616
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
k = 1010
Tmin = 0.655, Tmax = 0.746l = 2323
30145 measured 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)] = 0.044Hydrogen site location: difference Fourier map
wR(F2) = 0.123H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0545P)2 + 0.6509P]
where P = (Fo2 + 2Fc2)/3
4267 reflections(Δ/σ)max = 0.001
236 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C21H14F2O2SV = 1695.20 (18) Å3
Mr = 368.38Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.3698 (8) ŵ = 0.22 mm1
b = 7.9967 (5) ÅT = 173 K
c = 17.4195 (10) Å0.30 × 0.26 × 0.10 mm
β = 100.323 (4)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
4267 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
3147 reflections with I > 2σ(I)
Tmin = 0.655, Tmax = 0.746Rint = 0.065
30145 measured reflectionsθmax = 28.5°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.123Δρmax = 0.34 e Å3
S = 1.04Δρmin = 0.29 e Å3
4267 reflectionsAbsolute structure: ?
236 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
S10.75286 (4)0.76155 (6)0.66805 (2)0.02982 (13)
F10.88756 (12)1.08879 (19)0.40581 (8)0.0604 (4)
F20.24627 (11)0.3963 (2)0.67822 (8)0.0594 (4)
O10.52531 (10)0.79604 (17)0.47682 (6)0.0331 (3)
O20.82873 (12)0.90671 (18)0.68234 (8)0.0421 (4)
C10.66892 (15)0.7947 (2)0.57601 (9)0.0293 (4)
C20.70298 (15)0.8786 (2)0.51067 (9)0.0308 (4)
C30.79965 (17)0.9521 (3)0.49652 (11)0.0368 (4)
H30.86430.95750.53520.044*
C40.79512 (19)1.0161 (3)0.42283 (12)0.0420 (5)
C50.70310 (19)1.0131 (3)0.36455 (11)0.0426 (5)
H50.70611.06120.31510.051*
C60.60661 (18)0.9404 (3)0.37787 (10)0.0372 (5)
C70.61135 (16)0.8754 (2)0.45189 (10)0.0317 (4)
C80.56166 (15)0.7471 (2)0.55269 (9)0.0295 (4)
C90.50397 (19)0.9291 (3)0.31700 (11)0.0468 (6)
H9A0.49790.81650.29440.070*
H9B0.50741.01140.27590.070*
H9C0.43970.95190.34110.070*
C100.48089 (15)0.6561 (2)0.58759 (10)0.0310 (4)
C110.49926 (16)0.6069 (3)0.66553 (11)0.0388 (5)
H110.56740.63300.69800.047*
C120.42033 (17)0.5211 (3)0.69639 (12)0.0433 (5)
H120.43320.48850.74970.052*
C130.32297 (17)0.4839 (3)0.64853 (12)0.0412 (5)
C140.30143 (17)0.5288 (3)0.57126 (12)0.0448 (5)
H140.23350.50010.53920.054*
C150.37990 (16)0.6160 (3)0.54113 (11)0.0374 (5)
H150.36540.64960.48800.045*
C160.83023 (15)0.5900 (2)0.64087 (9)0.0285 (4)
C170.92867 (16)0.6178 (3)0.61585 (11)0.0404 (5)
H170.95490.72810.61050.049*
C180.9876 (2)0.4805 (4)0.59885 (13)0.0560 (7)
H181.05500.49670.58090.067*
C190.9509 (2)0.3218 (4)0.60738 (13)0.0593 (7)
H190.99310.22910.59570.071*
C200.8531 (2)0.2952 (3)0.63286 (12)0.0502 (6)
H200.82740.18460.63820.060*
C210.79281 (17)0.4303 (2)0.65049 (10)0.0346 (4)
H210.72600.41360.66910.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0319 (2)0.0365 (3)0.01842 (18)0.0017 (2)0.00255 (15)0.00149 (16)
F10.0605 (9)0.0742 (10)0.0490 (7)0.0177 (8)0.0169 (7)0.0140 (7)
F20.0472 (8)0.0810 (11)0.0534 (8)0.0180 (7)0.0181 (6)0.0046 (7)
O10.0336 (7)0.0419 (8)0.0206 (5)0.0028 (6)0.0039 (5)0.0011 (5)
O20.0475 (9)0.0385 (8)0.0342 (7)0.0110 (7)0.0085 (6)0.0043 (6)
C10.0323 (9)0.0332 (10)0.0203 (7)0.0009 (8)0.0009 (7)0.0005 (6)
C20.0355 (10)0.0335 (10)0.0220 (7)0.0032 (8)0.0010 (7)0.0006 (7)
C30.0402 (11)0.0401 (11)0.0291 (8)0.0035 (9)0.0038 (8)0.0001 (8)
C40.0492 (13)0.0424 (12)0.0364 (10)0.0045 (10)0.0131 (9)0.0019 (9)
C50.0597 (14)0.0422 (12)0.0262 (8)0.0027 (11)0.0089 (9)0.0048 (8)
C60.0512 (12)0.0358 (11)0.0226 (8)0.0083 (9)0.0009 (8)0.0005 (7)
C70.0365 (10)0.0335 (10)0.0237 (8)0.0025 (8)0.0017 (7)0.0010 (7)
C80.0319 (9)0.0346 (10)0.0195 (7)0.0048 (8)0.0020 (6)0.0018 (7)
C90.0606 (15)0.0510 (13)0.0233 (8)0.0095 (11)0.0073 (9)0.0016 (8)
C100.0282 (9)0.0351 (10)0.0282 (8)0.0040 (8)0.0010 (7)0.0048 (7)
C110.0316 (10)0.0525 (13)0.0297 (9)0.0033 (9)0.0020 (7)0.0011 (8)
C120.0386 (12)0.0578 (14)0.0330 (9)0.0011 (10)0.0050 (8)0.0044 (9)
C130.0334 (11)0.0481 (13)0.0445 (11)0.0044 (9)0.0135 (9)0.0064 (9)
C140.0311 (11)0.0622 (15)0.0398 (10)0.0052 (10)0.0031 (8)0.0127 (10)
C150.0307 (10)0.0519 (13)0.0276 (8)0.0014 (9)0.0003 (7)0.0071 (8)
C160.0269 (9)0.0384 (10)0.0177 (7)0.0006 (8)0.0030 (6)0.0017 (7)
C170.0341 (11)0.0562 (13)0.0297 (9)0.0007 (10)0.0021 (8)0.0097 (9)
C180.0421 (13)0.091 (2)0.0365 (11)0.0184 (13)0.0116 (9)0.0080 (12)
C190.0697 (17)0.0669 (18)0.0392 (11)0.0320 (15)0.0044 (11)0.0020 (11)
C200.0690 (16)0.0418 (13)0.0359 (10)0.0090 (12)0.0012 (10)0.0012 (9)
C210.0385 (11)0.0374 (11)0.0253 (8)0.0025 (9)0.0010 (7)0.0021 (7)
Geometric parameters (Å, º) top
S1—O21.4855 (14)C10—C111.392 (2)
S1—C11.7671 (17)C10—C151.399 (3)
S1—C161.7846 (19)C11—C121.379 (3)
F1—C41.362 (2)C11—H110.9500
F2—C131.354 (2)C12—C131.369 (3)
O1—C81.3745 (19)C12—H120.9500
O1—C71.375 (2)C13—C141.372 (3)
C1—C81.370 (3)C14—C151.374 (3)
C1—C21.447 (2)C14—H140.9500
C2—C71.385 (2)C15—H150.9500
C2—C31.393 (3)C16—C211.378 (3)
C3—C41.374 (3)C16—C171.383 (3)
C3—H30.9500C17—C181.379 (3)
C4—C51.383 (3)C17—H170.9500
C5—C61.384 (3)C18—C191.365 (4)
C5—H50.9500C18—H180.9500
C6—C71.382 (2)C19—C201.378 (4)
C6—C91.504 (3)C19—H190.9500
C8—C101.454 (3)C20—C211.379 (3)
C9—H9A0.9800C20—H200.9500
C9—H9B0.9800C21—H210.9500
C9—H9C0.9800
O2—S1—C1106.59 (8)C11—C10—C8122.99 (16)
O2—S1—C16107.00 (9)C15—C10—C8118.84 (16)
C1—S1—C1697.50 (8)C12—C11—C10121.16 (18)
C8—O1—C7107.27 (14)C12—C11—H11119.4
C8—C1—C2107.38 (15)C10—C11—H11119.4
C8—C1—S1127.41 (14)C13—C12—C11118.55 (19)
C2—C1—S1125.21 (14)C13—C12—H12120.7
C7—C2—C3119.46 (16)C11—C12—H12120.7
C7—C2—C1104.94 (16)F2—C13—C12118.68 (19)
C3—C2—C1135.60 (17)F2—C13—C14118.93 (19)
C4—C3—C2115.45 (18)C12—C13—C14122.4 (2)
C4—C3—H3122.3C13—C14—C15118.77 (19)
C2—C3—H3122.3C13—C14—H14120.6
F1—C4—C3117.86 (19)C15—C14—H14120.6
F1—C4—C5117.40 (18)C14—C15—C10120.96 (18)
C3—C4—C5124.7 (2)C14—C15—H15119.5
C4—C5—C6120.34 (18)C10—C15—H15119.5
C4—C5—H5119.8C21—C16—C17121.41 (19)
C6—C5—H5119.8C21—C16—S1118.17 (14)
C7—C6—C5114.88 (18)C17—C16—S1120.28 (16)
C7—C6—C9121.7 (2)C18—C17—C16118.0 (2)
C5—C6—C9123.46 (17)C18—C17—H17121.0
O1—C7—C6124.24 (17)C16—C17—H17121.0
O1—C7—C2110.63 (15)C19—C18—C17121.2 (2)
C6—C7—C2125.12 (19)C19—C18—H18119.4
C1—C8—O1109.77 (15)C17—C18—H18119.4
C1—C8—C10135.78 (15)C18—C19—C20120.5 (2)
O1—C8—C10114.43 (15)C18—C19—H19119.8
C6—C9—H9A109.5C20—C19—H19119.8
C6—C9—H9B109.5C19—C20—C21119.5 (2)
H9A—C9—H9B109.5C19—C20—H20120.3
C6—C9—H9C109.5C21—C20—H20120.3
H9A—C9—H9C109.5C16—C21—C20119.5 (2)
H9B—C9—H9C109.5C16—C21—H21120.3
C11—C10—C15118.17 (18)C20—C21—H21120.3
O2—S1—C1—C8147.60 (17)S1—C1—C8—C101.9 (3)
C16—S1—C1—C8102.09 (18)C7—O1—C8—C10.2 (2)
O2—S1—C1—C232.64 (19)C7—O1—C8—C10178.35 (15)
C16—S1—C1—C277.66 (17)C1—C8—C10—C116.8 (4)
C8—C1—C2—C70.2 (2)O1—C8—C10—C11175.11 (18)
S1—C1—C2—C7179.97 (14)C1—C8—C10—C15173.3 (2)
C8—C1—C2—C3178.9 (2)O1—C8—C10—C154.8 (3)
S1—C1—C2—C30.9 (3)C15—C10—C11—C120.0 (3)
C7—C2—C3—C40.3 (3)C8—C10—C11—C12179.87 (19)
C1—C2—C3—C4178.7 (2)C10—C11—C12—C130.4 (3)
C2—C3—C4—F1179.76 (18)C11—C12—C13—F2178.5 (2)
C2—C3—C4—C50.6 (3)C11—C12—C13—C140.1 (4)
F1—C4—C5—C6179.68 (19)F2—C13—C14—C15179.3 (2)
C3—C4—C5—C60.7 (4)C12—C13—C14—C150.8 (4)
C4—C5—C6—C70.4 (3)C13—C14—C15—C101.2 (3)
C4—C5—C6—C9178.7 (2)C11—C10—C15—C140.7 (3)
C8—O1—C7—C6179.07 (18)C8—C10—C15—C14179.34 (19)
C8—O1—C7—C20.1 (2)O2—S1—C16—C21157.93 (13)
C5—C6—C7—O1179.11 (18)C1—S1—C16—C2192.11 (14)
C9—C6—C7—O10.0 (3)O2—S1—C16—C1717.86 (15)
C5—C6—C7—C20.1 (3)C1—S1—C16—C1792.11 (15)
C9—C6—C7—C2179.01 (19)C21—C16—C17—C181.5 (3)
C3—C2—C7—O1179.17 (17)S1—C16—C17—C18177.18 (15)
C1—C2—C7—O10.1 (2)C16—C17—C18—C190.9 (3)
C3—C2—C7—C60.0 (3)C17—C18—C19—C200.4 (3)
C1—C2—C7—C6179.23 (18)C18—C19—C20—C210.6 (3)
C2—C1—C8—O10.3 (2)C17—C16—C21—C201.8 (3)
S1—C1—C8—O1179.93 (13)S1—C16—C21—C20177.49 (14)
C2—C1—C8—C10177.8 (2)C19—C20—C21—C161.3 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C16-C21 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C20—H20···O2i0.952.353.252 (3)158
C9—H9B···Cg1ii0.982.793.519 (2)132
Symmetry codes: (i) x, y1, z; (ii) x1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC21H14F2O2S
Mr368.38
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)12.3698 (8), 7.9967 (5), 17.4195 (10)
β (°) 100.323 (4)
V3)1695.20 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.30 × 0.26 × 0.10
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.655, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
30145, 4267, 3147
Rint0.065
(sin θ/λ)max1)0.670
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.123, 1.04
No. of reflections4267
No. of parameters236
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.29

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C16-C21 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C20—H20···O2i0.952.353.252 (3)158.4
C9—H9B···Cg1ii0.982.793.519 (2)132.3
Symmetry codes: (i) x, y1, z; (ii) x1/2, y+3/2, z1/2.
Acknowledgements top

This work was supported by a Dong-eui University grant (No. 2013AA076).

references
References top

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. & Lee, U. (2012). Acta Cryst. E68, o1237.

Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2011). Acta Cryst. E67, o498.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2011). Acta Cryst. E67, o2346.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.