5-Fluoro-2-(4-methyl­phen­yl)-3-methyl­sulfinyl-1-benzofuran

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

doi:10.1107/S1600536812044844

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3338

doi:10.1107/S1600536812044844

Open

access

5-Fluoro-2-(4-methylphenyl)-3-methylsulfinyl-1-benzofuran

Hong Dae Choi,^a Pil Ja Seo ^a and Uk Lee ^b ^*

^aDepartment of Chemistry, Dongeui University, San 24 Kaya-dong, Busanjin-gu, Busan 614-714, Republic of Korea, and ^bDepartment of Chemistry, Pukyong National University, 599-1 Daeyeon 3-dong, Nam-gu, Busan 608-737, Republic of Korea
^*Correspondence e-mail: uklee@pknu.ac.kr

(Received 29 October 2012; accepted 30 October 2012; online 14 November 2012)

In the title compound, C₁₆H₁₃FO₂S, the 4-methylphenyl ring makes a dihedral angle of 29.53 (4)° with the mean plane of the benzofuran fragment [r.m.s. deviation = 0.004 (1) Å]. In the crystal, molecules are linked by pairs of weak C—H⋯O hydrogen bonds, forming inversion dimers that stack along the a axis.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2009a ,b ).

Experimental

Crystal data

C₁₆H₁₃FO₂S
M_r = 288.32
Triclinic, $[P \overline 1]$
a = 8.0407 (2) Å
b = 8.0838 (2) Å
c = 11.3517 (2) Å
α = 80.126 (1)°
β = 85.091 (1)°
γ = 66.773 (1)°
V = 667.88 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 173 K
0.53 × 0.40 × 0.24 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.701, T_max = 0.746
12234 measured reflections
3307 independent reflections
3095 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.091
S = 1.09
3307 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O2ⁱ	0.95	2.54	3.4138 (16)	154
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812044844/su2522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044844/su2522Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812044844/su2522Isup3.cml

checkCIF report

Comment top

As a part of our ongoing study of 5-fluoro-3-methylsulfinyl-1-benzofuran derivatives with various substituents in the 2-position, such as 4-bromophenyl (Choi et al., 2009a) or 4-iodophenyl (Choi et al., 2009b), 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 0.004 (1) Å from the mean plane defined by the nine constituent atoms. The dihedral angle between the 4-methylphenyl ring and the mean plane of the benzofuran ring is 29.53 (4)°.

In the crystal, molecules are connected by a pair of weak C—H···O hydrogen bonds, forming inversion dimers that stack along the a axis (Table 1).

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2009a,b).

Experimental top

3-Chloroperoxybenzoic acid (77%, 269 mg, 1.2 mmol) was added in small portions to a stirred solution of 5-fluoro-2-(4-methylphenyl)-3-methylsulfanyl-1-benzofuran (326 mg, 1.1 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 73%, m.p. 417–418 K; R_f = 0.45 (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.

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 molecule, with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level.

5-Fluoro-2-(4-methylphenyl)-3-methylsulfinyl-1-benzofuran top

Crystal data top

C₁₆H₁₃FO₂S	Z = 2
M_r = 288.32	F(000) = 300
Triclinic, P1	D_x = 1.434 Mg m⁻³
Hall symbol: -P 1	Melting point < 418 K
a = 8.0407 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0838 (2) Å	Cell parameters from 7852 reflections
c = 11.3517 (2) Å	θ = 2.8–28.3°
α = 80.126 (1)°	µ = 0.25 mm⁻¹
β = 85.091 (1)°	T = 173 K
γ = 66.773 (1)°	Block, colourless
V = 667.88 (3) Å³	0.53 × 0.40 × 0.24 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3307 independent reflections
Radiation source: rotating anode	3095 reflections with I > 2σ(I)
Graphite multilayer monochromator	R_int = 0.020
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.3°, θ_min = 1.8°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −10→10
T_min = 0.701, T_max = 0.746	l = −15→15
12234 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)] = 0.034	Hydrogen site location: difference Fourier map
wR(F²) = 0.091	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0463P)² + 0.2225P] where P = (F_o² + 2F_c²)/3
3307 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₆H₁₃FO₂S	γ = 66.773 (1)°
M_r = 288.32	V = 667.88 (3) Å³
Triclinic, P1	Z = 2
a = 8.0407 (2) Å	Mo Kα radiation
b = 8.0838 (2) Å	µ = 0.25 mm⁻¹
c = 11.3517 (2) Å	T = 173 K
α = 80.126 (1)°	0.53 × 0.40 × 0.24 mm
β = 85.091 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3307 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3095 reflections with I > 2σ(I)
T_min = 0.701, T_max = 0.746	R_int = 0.020
12234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.09	Δρ_max = 0.24 e Å⁻³
3307 reflections	Δρ_min = −0.38 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
S1	0.33118 (4)	0.20343 (4)	0.41621 (3)	0.02410 (10)
O1	0.15249 (12)	0.70005 (11)	0.50374 (7)	0.02400 (18)
F1	−0.01539 (13)	0.79204 (12)	0.03932 (7)	0.0428 (2)
O2	0.21524 (13)	0.17958 (13)	0.33018 (10)	0.0378 (2)
C1	0.24601 (16)	0.43759 (15)	0.42709 (10)	0.0221 (2)
C9	0.30709 (16)	0.43979 (16)	0.64794 (10)	0.0223 (2)
C8	0.23981 (16)	0.51353 (15)	0.52688 (10)	0.0221 (2)
C7	0.10062 (16)	0.74208 (16)	0.38628 (10)	0.0226 (2)
C10	0.46136 (17)	0.28077 (17)	0.67089 (11)	0.0260 (2)
H10	0.5246	0.2185	0.6068	0.031*
C2	0.15628 (16)	0.58455 (15)	0.33364 (10)	0.0221 (2)
C14	0.21693 (17)	0.53140 (17)	0.74329 (11)	0.0260 (2)
H14	0.1117	0.6401	0.7292	0.031*
C3	0.11782 (17)	0.59876 (17)	0.21373 (11)	0.0267 (2)
H3	0.1527	0.4950	0.1745	0.032*
C12	0.43513 (19)	0.30326 (18)	0.88157 (11)	0.0294 (3)
C11	0.52340 (18)	0.21267 (18)	0.78664 (11)	0.0292 (3)
H11	0.6274	0.1029	0.8011	0.035*
C6	0.01006 (17)	0.91590 (17)	0.32716 (11)	0.0274 (3)
H6	−0.0244	1.0202	0.3658	0.033*
C13	0.28174 (19)	0.46301 (18)	0.85797 (11)	0.0299 (3)
H13	0.2203	0.5264	0.9221	0.036*
C5	−0.02757 (18)	0.92941 (18)	0.20837 (12)	0.0303 (3)
H5	−0.0899	1.0452	0.1629	0.036*
C16	0.53640 (17)	0.19025 (18)	0.33560 (12)	0.0293 (3)
H16A	0.5951	0.0708	0.3092	0.044*
H16B	0.6178	0.2069	0.3877	0.044*
H16C	0.5085	0.2859	0.2657	0.044*
C4	0.02649 (18)	0.77212 (19)	0.15608 (11)	0.0297 (3)
C15	0.5046 (2)	0.2319 (2)	1.00707 (13)	0.0438 (4)
H15A	0.6136	0.1200	1.0067	0.066*
H15B	0.4114	0.2057	1.0589	0.066*
H15C	0.5341	0.3235	1.0371	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02488 (16)	0.01864 (15)	0.02810 (16)	−0.00752 (11)	0.00168 (11)	−0.00507 (11)
O1	0.0276 (4)	0.0198 (4)	0.0228 (4)	−0.0066 (3)	−0.0014 (3)	−0.0045 (3)
F1	0.0568 (6)	0.0438 (5)	0.0221 (4)	−0.0142 (4)	−0.0091 (4)	0.0014 (3)
O2	0.0297 (5)	0.0315 (5)	0.0574 (6)	−0.0110 (4)	−0.0052 (4)	−0.0204 (5)
C1	0.0231 (5)	0.0196 (5)	0.0228 (5)	−0.0074 (4)	0.0002 (4)	−0.0038 (4)
C9	0.0237 (5)	0.0230 (5)	0.0216 (5)	−0.0105 (4)	−0.0004 (4)	−0.0035 (4)
C8	0.0218 (5)	0.0197 (5)	0.0238 (5)	−0.0070 (4)	0.0009 (4)	−0.0037 (4)
C7	0.0227 (5)	0.0229 (5)	0.0221 (5)	−0.0087 (4)	−0.0005 (4)	−0.0037 (4)
C10	0.0249 (6)	0.0278 (6)	0.0240 (6)	−0.0082 (5)	0.0001 (4)	−0.0060 (4)
C2	0.0217 (5)	0.0209 (5)	0.0234 (5)	−0.0081 (4)	0.0006 (4)	−0.0031 (4)
C14	0.0275 (6)	0.0244 (6)	0.0260 (6)	−0.0094 (5)	0.0015 (5)	−0.0060 (4)
C3	0.0301 (6)	0.0275 (6)	0.0231 (5)	−0.0115 (5)	−0.0002 (5)	−0.0047 (4)
C12	0.0354 (7)	0.0332 (6)	0.0232 (6)	−0.0173 (5)	−0.0050 (5)	−0.0020 (5)
C11	0.0267 (6)	0.0289 (6)	0.0290 (6)	−0.0077 (5)	−0.0050 (5)	−0.0017 (5)
C6	0.0271 (6)	0.0214 (5)	0.0310 (6)	−0.0069 (5)	−0.0005 (5)	−0.0033 (5)
C13	0.0362 (7)	0.0327 (6)	0.0233 (6)	−0.0150 (6)	0.0024 (5)	−0.0083 (5)
C5	0.0295 (6)	0.0250 (6)	0.0308 (6)	−0.0070 (5)	−0.0031 (5)	0.0031 (5)
C16	0.0263 (6)	0.0314 (6)	0.0305 (6)	−0.0105 (5)	0.0036 (5)	−0.0091 (5)
C4	0.0324 (6)	0.0342 (7)	0.0210 (5)	−0.0125 (5)	−0.0030 (5)	−0.0002 (5)
C15	0.0576 (10)	0.0467 (9)	0.0260 (7)	−0.0186 (8)	−0.0123 (6)	−0.0012 (6)

Geometric parameters (Å, º) top

S1—O2	1.4907 (10)	C3—C4	1.3738 (18)
S1—C1	1.7637 (11)	C3—H3	0.9500
S1—C16	1.7911 (13)	C12—C11	1.3897 (18)
O1—C7	1.3767 (14)	C12—C13	1.3937 (19)
O1—C8	1.3770 (14)	C12—C15	1.5082 (17)
F1—C4	1.3625 (14)	C11—H11	0.9500
C1—C8	1.3665 (16)	C6—C5	1.3839 (18)
C1—C2	1.4422 (16)	C6—H6	0.9500
C9—C10	1.3935 (17)	C13—H13	0.9500
C9—C14	1.4009 (16)	C5—C4	1.3917 (19)
C9—C8	1.4589 (16)	C5—H5	0.9500
C7—C6	1.3814 (16)	C16—H16A	0.9800
C7—C2	1.3945 (16)	C16—H16B	0.9800
C10—C11	1.3878 (17)	C16—H16C	0.9800
C10—H10	0.9500	C15—H15A	0.9800
C2—C3	1.3971 (16)	C15—H15B	0.9800
C14—C13	1.3835 (17)	C15—H15C	0.9800
C14—H14	0.9500

O2—S1—C1	106.91 (6)	C11—C12—C15	120.89 (13)
O2—S1—C16	105.80 (6)	C13—C12—C15	120.67 (12)
C1—S1—C16	97.50 (6)	C10—C11—C12	120.76 (12)
C7—O1—C8	106.64 (9)	C10—C11—H11	119.6
C8—C1—C2	107.14 (10)	C12—C11—H11	119.6
C8—C1—S1	126.89 (9)	C7—C6—C5	116.19 (11)
C2—C1—S1	125.80 (9)	C7—C6—H6	121.9
C10—C9—C14	118.99 (11)	C5—C6—H6	121.9
C10—C9—C8	121.35 (10)	C14—C13—C12	121.48 (12)
C14—C9—C8	119.65 (11)	C14—C13—H13	119.3
C1—C8—O1	110.59 (10)	C12—C13—H13	119.3
C1—C8—C9	133.89 (11)	C6—C5—C4	119.51 (12)
O1—C8—C9	115.52 (10)	C6—C5—H5	120.2
O1—C7—C6	125.11 (11)	C4—C5—H5	120.2
O1—C7—C2	110.54 (10)	S1—C16—H16A	109.5
C6—C7—C2	124.33 (11)	S1—C16—H16B	109.5
C11—C10—C9	120.55 (11)	H16A—C16—H16B	109.5
C11—C10—H10	119.7	S1—C16—H16C	109.5
C9—C10—H10	119.7	H16A—C16—H16C	109.5
C7—C2—C3	119.30 (11)	H16B—C16—H16C	109.5
C7—C2—C1	105.09 (10)	F1—C4—C3	117.81 (12)
C3—C2—C1	135.61 (11)	F1—C4—C5	117.39 (11)
C13—C14—C9	119.77 (12)	C3—C4—C5	124.80 (12)
C13—C14—H14	120.1	C12—C15—H15A	109.5
C9—C14—H14	120.1	C12—C15—H15B	109.5
C4—C3—C2	115.87 (11)	H15A—C15—H15B	109.5
C4—C3—H3	122.1	C12—C15—H15C	109.5
C2—C3—H3	122.1	H15A—C15—H15C	109.5
C11—C12—C13	118.44 (11)	H15B—C15—H15C	109.5

O2—S1—C1—C8	144.62 (11)	C8—C1—C2—C7	−0.31 (13)
C16—S1—C1—C8	−106.28 (12)	S1—C1—C2—C7	175.22 (9)
O2—S1—C1—C2	−30.03 (12)	C8—C1—C2—C3	179.87 (13)
C16—S1—C1—C2	79.07 (11)	S1—C1—C2—C3	−4.6 (2)
C2—C1—C8—O1	−0.23 (13)	C10—C9—C14—C13	−0.10 (18)
S1—C1—C8—O1	−175.69 (8)	C8—C9—C14—C13	−179.19 (11)
C2—C1—C8—C9	−179.10 (12)	C7—C2—C3—C4	0.33 (17)
S1—C1—C8—C9	5.4 (2)	C1—C2—C3—C4	−179.86 (13)
C7—O1—C8—C1	0.68 (13)	C9—C10—C11—C12	−1.2 (2)
C7—O1—C8—C9	179.78 (9)	C13—C12—C11—C10	0.7 (2)
C10—C9—C8—C1	29.5 (2)	C15—C12—C11—C10	−178.63 (13)
C14—C9—C8—C1	−151.45 (13)	O1—C7—C6—C5	179.08 (11)
C10—C9—C8—O1	−149.35 (11)	C2—C7—C6—C5	0.79 (19)
C14—C9—C8—O1	29.72 (15)	C9—C14—C13—C12	−0.41 (19)
C8—O1—C7—C6	−179.38 (11)	C11—C12—C13—C14	0.1 (2)
C8—O1—C7—C2	−0.89 (13)	C15—C12—C13—C14	179.43 (13)
C14—C9—C10—C11	0.90 (18)	C7—C6—C5—C4	−0.17 (19)
C8—C9—C10—C11	179.98 (11)	C2—C3—C4—F1	−179.35 (11)
O1—C7—C2—C3	−179.40 (10)	C2—C3—C4—C5	0.3 (2)
C6—C7—C2—C3	−0.90 (18)	C6—C5—C4—F1	179.26 (12)
O1—C7—C2—C1	0.74 (13)	C6—C5—C4—C3	−0.4 (2)
C6—C7—C2—C1	179.25 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O2ⁱ	0.95	2.54	3.4138 (16)	154

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃FO₂S
M_r	288.32
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.0407 (2), 8.0838 (2), 11.3517 (2)
α, β, γ (°)	80.126 (1), 85.091 (1), 66.773 (1)
V (Å³)	667.88 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.53 × 0.40 × 0.24

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.701, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12234, 3307, 3095
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.09
No. of reflections	3307
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.38

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O2ⁱ	0.95	2.54	3.4138 (16)	154

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

This work was supported by the Blue-Bio Industry Regional Innovation Center (RIC08-06-07) at Dongeui University as an RIC program under the Ministry of Knowledge Economy and Busan City.

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2009a). Acta Cryst. E65, o2084. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2009b). Acta Cryst. E65, o2115. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar