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

Choi, H.D.; Seo, P.J.; Son, B.W.; Lee, U.

doi:10.1107/S1600536810003740

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

H. D. Choi, P. J. Seo, B. W. Son and U. Lee

In the title compound, C₁₆H₁₃FO₂S, the O atom and the 4-fluorophenyl group of the 4-fluorophenylsulfinyl substituent are located on opposite sides of the plane through the benzofuran fragment; the 4-fluorophenyl ring is nearly perpendicular to this plane, making a dihedral angle of 87.41 (3). The crystal structure exhibits a weak intermolecular C—H

O hydrogen bond.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810003740/fk2012sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810003740/fk2012Isup2.hkl Contains datablock I

CCDC reference: 769951

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.035
wR factor = 0.099
Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10B   ..  O2      ..       2.62 Ang.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Molecules containing benzofuran skeleton show various pharmacological activities such as antifungal (Aslam et al., 2006), antitumor and antiviral (Galal et al., 2009), antimicrobial (Khan et al., 2005) properties, and 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 2-methyl-3-phenylsulfinyl-1-benzofuran analogues (Choi et al., 2007, 2008a,b), we report the crystal structure of the title compound (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.009 (1) ° from the least-squares plane defined by the nine constituent atoms. The 4-fluorophenyl ring is almost perpendicular to the plane of the benzofuran fragment [87.41 (3)°] and is tilted slightly towards it. The crystal packing (Fig. 2) is stabilized by a weak intermolecular C—H···O hydrogen bond between the methyl H atom and the oxygen of the S═O unit, with a C10—H10B···O2ⁱ (Table 1).

Related literature top

For the crystal structures of similar 2-methyl-3-phenylsulfinyl-1-benzofuran derivatives, see: Choi et al. (2007, 2008a,b). For the pharmacological activity of benzofuran compounds, see: Aslam et al. (2006); Galal et al. (2009); Khan et al. (2005). For natural products with benzofuran rings, see: Akgul & Anil (2003); Soekamto et al. (2003).

Experimental top

77% 3-Chloroperoxybenzoic acid (291 mg, 1.3 mmol) was added in small portions to a stirred solution of 3-(4-fluorophenylsulfanyl)-2,5-dimethyl-1-benzofuran (326 mg, 1.2 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 3h, 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 (hexane-ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 80%, m.p. 420-421 K; R_f = 0.69 (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 ethyl acetate at room temperature.

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, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	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 a small spheres of arbitrary radius.
	Fig. 2. C–H···O interaction (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.]

3-(4-Fluorophenylsulfinyl)-2,5-dimethyl-1-benzofuran top

Crystal data top

C₁₆H₁₃FO₂S	F(000) = 600
M_r = 288.32	D_x = 1.416 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9959 reflections
a = 11.3951 (5) Å	θ = 2.5–27.6°
b = 6.1223 (3) Å	µ = 0.25 mm⁻¹
c = 19.6899 (9) Å	T = 173 K
β = 100.155 (2)°	Block, colourless
V = 1352.13 (11) Å³	0.30 × 0.30 × 0.21 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	3115 independent reflections
Radiation source: Rotating Anode	2830 reflections with I > 2σ(I)
Bruker HELIOS graded multilayer optics monochromator	R_int = 0.032
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.6°, θ_min = 1.8°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −7→7
T_min = 0.645, T_max = 0.746	l = −25→25
22996 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: difference Fourier map
wR(F²) = 0.099	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0508P)² + 0.5136P] where P = (F_o² + 2F_c²)/3
3115 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₆H₁₃FO₂S	V = 1352.13 (11) Å³
M_r = 288.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.3951 (5) Å	µ = 0.25 mm⁻¹
b = 6.1223 (3) Å	T = 173 K
c = 19.6899 (9) Å	0.30 × 0.30 × 0.21 mm
β = 100.155 (2)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3115 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2830 reflections with I > 2σ(I)
T_min = 0.645, T_max = 0.746	R_int = 0.032
22996 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.07	Δρ_max = 0.30 e Å⁻³
3115 reflections	Δρ_min = −0.32 e Å⁻³
183 parameters

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

	x	y	z	U_iso*/U_eq
S	0.93298 (3)	0.31885 (6)	0.605178 (18)	0.03074 (12)
F1	0.72777 (10)	0.51180 (19)	0.31715 (5)	0.0556 (3)
O1	0.68994 (9)	0.46191 (17)	0.71689 (5)	0.0346 (2)
O2	0.96804 (10)	0.08380 (18)	0.60734 (6)	0.0410 (3)
C1	0.80592 (12)	0.3425 (2)	0.64361 (7)	0.0277 (3)
C2	0.70234 (11)	0.2027 (2)	0.63519 (7)	0.0262 (3)
C3	0.66200 (12)	0.0220 (2)	0.59513 (7)	0.0299 (3)
H3	0.7071	−0.0342	0.5628	0.036*
C4	0.55514 (12)	−0.0758 (2)	0.60278 (7)	0.0320 (3)
C5	0.48975 (13)	0.0120 (3)	0.65052 (7)	0.0358 (3)
H5	0.4167	−0.0556	0.6554	0.043*
C6	0.52732 (13)	0.1926 (3)	0.69067 (8)	0.0369 (3)
H6	0.4820	0.2508	0.7225	0.044*
C7	0.63433 (12)	0.2835 (2)	0.68184 (7)	0.0291 (3)
C8	0.79456 (12)	0.4921 (2)	0.69286 (7)	0.0310 (3)
C9	0.51060 (15)	−0.2747 (3)	0.56091 (9)	0.0433 (4)
H9A	0.5564	−0.2937	0.5236	0.065*
H9B	0.4260	−0.2558	0.5412	0.065*
H9C	0.5204	−0.4041	0.5907	0.065*
C10	0.87069 (16)	0.6753 (3)	0.72348 (8)	0.0419 (4)
H10A	0.9421	0.6830	0.7022	0.063*
H10B	0.8942	0.6518	0.7733	0.063*
H10C	0.8262	0.8126	0.7153	0.063*
C11	0.86493 (11)	0.3744 (2)	0.51764 (7)	0.0266 (3)
C12	0.86759 (12)	0.2162 (2)	0.46786 (7)	0.0305 (3)
H12	0.9008	0.0765	0.4804	0.037*
C13	0.82143 (13)	0.2629 (3)	0.39942 (8)	0.0355 (3)
H13	0.8227	0.1568	0.3644	0.043*
C14	0.77397 (13)	0.4659 (3)	0.38377 (8)	0.0364 (3)
C15	0.77240 (14)	0.6277 (3)	0.43241 (9)	0.0391 (3)
H15	0.7392	0.7672	0.4196	0.047*
C16	0.82041 (13)	0.5810 (2)	0.50024 (8)	0.0348 (3)
H16	0.8228	0.6901	0.5348	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.02162 (18)	0.0348 (2)	0.0361 (2)	0.00162 (12)	0.00577 (13)	−0.00400 (13)
F1	0.0606 (6)	0.0669 (7)	0.0382 (5)	0.0008 (5)	0.0062 (5)	0.0120 (5)
O1	0.0392 (5)	0.0384 (5)	0.0284 (5)	−0.0003 (4)	0.0118 (4)	−0.0062 (4)
O2	0.0384 (6)	0.0412 (6)	0.0443 (6)	0.0170 (5)	0.0095 (5)	0.0035 (5)
C1	0.0259 (6)	0.0283 (6)	0.0291 (6)	0.0017 (5)	0.0055 (5)	−0.0020 (5)
C2	0.0242 (6)	0.0276 (6)	0.0271 (6)	0.0043 (5)	0.0051 (5)	0.0031 (5)
C3	0.0277 (6)	0.0284 (6)	0.0341 (7)	0.0034 (5)	0.0072 (5)	−0.0016 (5)
C4	0.0297 (7)	0.0301 (7)	0.0348 (7)	0.0004 (5)	0.0021 (5)	0.0047 (5)
C5	0.0285 (7)	0.0438 (8)	0.0358 (7)	−0.0036 (6)	0.0076 (6)	0.0081 (6)
C6	0.0342 (8)	0.0477 (9)	0.0319 (7)	0.0024 (6)	0.0140 (6)	0.0021 (6)
C7	0.0319 (7)	0.0316 (7)	0.0245 (6)	0.0029 (5)	0.0064 (5)	0.0007 (5)
C8	0.0327 (7)	0.0332 (7)	0.0270 (6)	0.0017 (5)	0.0045 (5)	−0.0007 (5)
C9	0.0394 (8)	0.0358 (8)	0.0532 (9)	−0.0082 (6)	0.0044 (7)	−0.0019 (7)
C10	0.0495 (9)	0.0397 (8)	0.0359 (8)	−0.0069 (7)	0.0057 (7)	−0.0108 (6)
C11	0.0204 (6)	0.0265 (6)	0.0350 (7)	−0.0017 (5)	0.0106 (5)	−0.0012 (5)
C12	0.0256 (6)	0.0258 (6)	0.0414 (7)	0.0004 (5)	0.0090 (5)	−0.0041 (5)
C13	0.0312 (7)	0.0388 (7)	0.0381 (8)	−0.0038 (6)	0.0110 (6)	−0.0091 (6)
C14	0.0309 (7)	0.0432 (8)	0.0364 (7)	−0.0050 (6)	0.0097 (6)	0.0058 (6)
C15	0.0397 (8)	0.0295 (7)	0.0497 (9)	0.0032 (6)	0.0125 (7)	0.0077 (6)
C16	0.0362 (7)	0.0269 (7)	0.0436 (8)	0.0026 (5)	0.0135 (6)	−0.0036 (6)

Geometric parameters (Å, º) top

S—O2	1.4921 (11)	C8—C10	1.480 (2)
S—C1	1.7540 (13)	C9—H9A	0.9800
S—C11	1.7935 (14)	C9—H9B	0.9800
F1—C14	1.3540 (18)	C9—H9C	0.9800
O1—C8	1.3705 (17)	C10—H10A	0.9800
O1—C7	1.3846 (17)	C10—H10B	0.9800
C1—C8	1.3567 (18)	C10—H10C	0.9800
C1—C2	1.4434 (18)	C11—C12	1.3824 (19)
C2—C3	1.3892 (19)	C11—C16	1.3830 (19)
C2—C7	1.3927 (18)	C12—C13	1.387 (2)
C3—C4	1.3886 (19)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.369 (2)
C4—C5	1.405 (2)	C13—H13	0.9500
C4—C9	1.508 (2)	C14—C15	1.380 (2)
C5—C6	1.383 (2)	C15—C16	1.381 (2)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.379 (2)	C16—H16	0.9500
C6—H6	0.9500

O2—S—C1	107.72 (7)	C4—C9—H9B	109.5
O2—S—C11	106.18 (6)	H9A—C9—H9B	109.5
C1—S—C11	98.57 (6)	C4—C9—H9C	109.5
C8—O1—C7	106.49 (10)	H9A—C9—H9C	109.5
C8—C1—C2	107.65 (12)	H9B—C9—H9C	109.5
C8—C1—S	123.65 (11)	C8—C10—H10A	109.5
C2—C1—S	128.47 (10)	C8—C10—H10B	109.5
C3—C2—C7	119.36 (12)	H10A—C10—H10B	109.5
C3—C2—C1	136.00 (12)	C8—C10—H10C	109.5
C7—C2—C1	104.64 (12)	H10A—C10—H10C	109.5
C4—C3—C2	119.37 (12)	H10B—C10—H10C	109.5
C4—C3—H3	120.3	C12—C11—C16	121.21 (13)
C2—C3—H3	120.3	C12—C11—S	119.25 (10)
C3—C4—C5	119.09 (13)	C16—C11—S	119.29 (11)
C3—C4—C9	120.40 (13)	C11—C12—C13	119.50 (13)
C5—C4—C9	120.50 (13)	C11—C12—H12	120.2
C6—C5—C4	122.76 (13)	C13—C12—H12	120.2
C6—C5—H5	118.6	C14—C13—C12	118.22 (13)
C4—C5—H5	118.6	C14—C13—H13	120.9
C7—C6—C5	116.24 (13)	C12—C13—H13	120.9
C7—C6—H6	121.9	F1—C14—C13	118.51 (14)
C5—C6—H6	121.9	F1—C14—C15	118.21 (14)
C6—C7—O1	126.34 (12)	C13—C14—C15	123.27 (14)
C6—C7—C2	123.18 (13)	C14—C15—C16	118.09 (14)
O1—C7—C2	110.48 (12)	C14—C15—H15	121.0
C1—C8—O1	110.74 (12)	C16—C15—H15	121.0
C1—C8—C10	132.86 (14)	C15—C16—C11	119.64 (14)
O1—C8—C10	116.40 (12)	C15—C16—H16	120.2
C4—C9—H9A	109.5	C11—C16—H16	120.2

O2—S—C1—C8	131.07 (12)	C1—C2—C7—O1	0.42 (14)
C11—S—C1—C8	−118.80 (12)	C2—C1—C8—O1	−0.67 (16)
O2—S—C1—C2	−42.67 (14)	S—C1—C8—O1	−175.53 (9)
C11—S—C1—C2	67.46 (13)	C2—C1—C8—C10	−179.96 (15)
C8—C1—C2—C3	−178.80 (15)	S—C1—C8—C10	5.2 (2)
S—C1—C2—C3	−4.3 (2)	C7—O1—C8—C1	0.92 (15)
C8—C1—C2—C7	0.15 (15)	C7—O1—C8—C10	−179.66 (12)
S—C1—C2—C7	174.69 (10)	O2—S—C11—C12	−7.30 (12)
C7—C2—C3—C4	−0.5 (2)	C1—S—C11—C12	−118.67 (11)
C1—C2—C3—C4	178.31 (14)	O2—S—C11—C16	178.43 (11)
C2—C3—C4—C5	0.6 (2)	C1—S—C11—C16	67.07 (12)
C2—C3—C4—C9	−178.81 (13)	C16—C11—C12—C13	−2.0 (2)
C3—C4—C5—C6	−0.1 (2)	S—C11—C12—C13	−176.18 (10)
C9—C4—C5—C6	179.28 (14)	C11—C12—C13—C14	−0.3 (2)
C4—C5—C6—C7	−0.4 (2)	C12—C13—C14—F1	−179.40 (12)
C5—C6—C7—O1	−179.06 (13)	C12—C13—C14—C15	1.6 (2)
C5—C6—C7—C2	0.5 (2)	F1—C14—C15—C16	−179.50 (13)
C8—O1—C7—C6	178.76 (14)	C13—C14—C15—C16	−0.5 (2)
C8—O1—C7—C2	−0.82 (15)	C14—C15—C16—C11	−1.9 (2)
C3—C2—C7—C6	0.0 (2)	C12—C11—C16—C15	3.1 (2)
C1—C2—C7—C6	−179.18 (13)	S—C11—C16—C15	177.30 (11)
C3—C2—C7—O1	179.58 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O2ⁱ	0.98	2.62	3.554 (2)	159

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃FO₂S
M_r	288.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.3951 (5), 6.1223 (3), 19.6899 (9)
β (°)	100.155 (2)
V (Å³)	1352.13 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.30 × 0.30 × 0.21

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.645, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	22996, 3115, 2830
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.099, 1.07
No. of reflections	3115
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).