3-(2-Fluoro­phenyl­sulfin­yl)-2,5,7-tri­methyl-1-benzo­furan

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

doi:10.1107/S1600536813011495

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o821

doi:10.1107/S1600536813011495

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3-(2-Fluorophenylsulfinyl)-2,5,7-trimethyl-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 28 March 2013; accepted 27 April 2013; online 4 May 2013)

In the title compound, C₁₇H₁₅FO₂S, the benzofuran ring system, being essentially planar, with an r.m.s. deviation from the least-squares plane of 0.009 (2) Å, makes a dihedral angle of 79.02 (5)° with the plane of the 2-fluorophenyl group. In the crystal, molecules are linked by pairs of weak C—H⋯O hydrogen bonds into centrosymmetric dimers.

Related literature

For background information and the crystal structures of related compounds, see: Choi et al. (2010 , 2011 ).

Experimental

Crystal data

C₁₇H₁₅FO₂S
M_r = 302.35
Triclinic, $[P \overline 1]$
a = 6.0969 (10) Å
b = 10.9279 (16) Å
c = 11.2209 (16) Å
α = 78.167 (10)°
β = 83.72 (1)°
γ = 79.722 (11)°
V = 717.92 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 173 K
0.22 × 0.13 × 0.12 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.640, T_max = 0.746
10389 measured reflections
2533 independent reflections
2028 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.099
S = 1.05
2533 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O2ⁱ	0.95	2.47	3.308 (3)	148
Symmetry code: (i) -x+2, -y, -z.

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 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813011495/yk2091sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813011495/yk2091Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813011495/yk2091Isup3.cml

checkCIF report

Comment top

As a part of our continuing study of 2,5,7-trimethyl-1-benzofuran derivatives containing 4-fluorophenylsulfinyl (Choi et al., 2010) and 3-fluorophenylsulfinyl (Choi et al., 2011) substituents in 3-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 0.009 (2) Å from the least-squares plane defined by the nine constituent atoms. The dihedral angle between the 2-fluorophenyl ring and the mean plane of the benzofuran ring is 79.02 (5)°. In the crystal structure, molecules are connected by pairs of weak C—H..O hydrogen bonds into centrosymmetric dimers (Table 1).

Related literature top

For background information and the crystal structures of related compounds, see: Choi et al. (2010, 2011).

Experimental top

3-Chloroperoxybenzoic acid (77%, 269 mg, 1.2 mmol) was added in small portions to a stirred solution of 3-(2-fluorophenylsulfanyl)-2,5,7-trimethyl-1-benzofuran (315 mg, 1.1 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 76%, m.p. 394–395 K; R_f = 0.46 (benzene)]. 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 for Windows (Farrugia, 2012) 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 small spheres of arbitrary radius.

3-(2-Fluorophenylsulfinyl)-2,5,7-trimethyl-1-benzofuran top

Crystal data top

C₁₇H₁₅FO₂S	Z = 2
M_r = 302.35	F(000) = 316
Triclinic, P1	D_x = 1.399 Mg m⁻³
Hall symbol: -P 1	Melting point = 394–395 K
a = 6.0969 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9279 (16) Å	Cell parameters from 3261 reflections
c = 11.2209 (16) Å	θ = 2.4–26.4°
α = 78.167 (10)°	µ = 0.24 mm⁻¹
β = 83.72 (1)°	T = 173 K
γ = 79.722 (11)°	Block, colourless
V = 717.92 (19) Å³	0.22 × 0.13 × 0.12 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2533 independent reflections
Radiation source: rotating anode	2028 reflections with I > 2σ(I)
Graphite multilayer monochromator	R_int = 0.042
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −12→12
T_min = 0.640, T_max = 0.746	l = −13→13
10389 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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F²) = 0.099	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0383P)² + 0.4211P] where P = (F_o² + 2F_c²)/3
2533 reflections	(Δ/σ)_max < 0.001
193 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₇H₁₅FO₂S	γ = 79.722 (11)°
M_r = 302.35	V = 717.92 (19) Å³
Triclinic, P1	Z = 2
a = 6.0969 (10) Å	Mo Kα radiation
b = 10.9279 (16) Å	µ = 0.24 mm⁻¹
c = 11.2209 (16) Å	T = 173 K
α = 78.167 (10)°	0.22 × 0.13 × 0.12 mm
β = 83.72 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2533 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2028 reflections with I > 2σ(I)
T_min = 0.640, T_max = 0.746	R_int = 0.042
10389 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
2533 reflections	Δρ_min = −0.27 e Å⁻³
193 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	0.53792 (10)	0.04652 (5)	0.12189 (5)	0.03178 (17)
F1	0.1918 (2)	0.28030 (14)	0.06722 (13)	0.0503 (4)
O1	0.2735 (2)	0.11435 (14)	0.43943 (13)	0.0326 (4)
O2	0.7672 (3)	−0.02603 (15)	0.12725 (15)	0.0427 (4)
C1	0.4627 (4)	0.10282 (19)	0.25824 (19)	0.0281 (5)
C2	0.5593 (3)	0.18749 (19)	0.31335 (19)	0.0271 (5)
C3	0.7316 (4)	0.2583 (2)	0.2813 (2)	0.0304 (5)
H3	0.8194	0.2568	0.2061	0.037*
C4	0.7730 (4)	0.3311 (2)	0.3611 (2)	0.0336 (5)
C5	0.6391 (4)	0.3330 (2)	0.4711 (2)	0.0368 (6)
H5	0.6688	0.3845	0.5241	0.044*
C6	0.4664 (4)	0.2636 (2)	0.5060 (2)	0.0346 (5)
C7	0.4356 (4)	0.19125 (19)	0.42355 (19)	0.0288 (5)
C8	0.2952 (4)	0.0620 (2)	0.33726 (19)	0.0299 (5)
C9	0.9605 (4)	0.4073 (2)	0.3309 (2)	0.0440 (6)
H9A	1.0749	0.3683	0.2756	0.066*
H9B	1.0265	0.4094	0.4061	0.066*
H9C	0.9026	0.4939	0.2912	0.066*
C10	0.3234 (5)	0.2640 (3)	0.6234 (2)	0.0492 (7)
H10A	0.1691	0.3010	0.6057	0.074*
H10B	0.3800	0.3144	0.6725	0.074*
H10C	0.3277	0.1769	0.6687	0.074*
C11	0.1356 (4)	−0.0245 (2)	0.3341 (2)	0.0366 (6)
H11A	0.1604	−0.0540	0.2562	0.055*
H11B	−0.0176	0.0206	0.3426	0.055*
H11C	0.1584	−0.0973	0.4014	0.055*
C12	0.5649 (4)	0.1939 (2)	0.02030 (19)	0.0294 (5)
C13	0.3881 (4)	0.2921 (2)	0.0008 (2)	0.0346 (5)
C14	0.4049 (4)	0.4017 (2)	−0.0821 (2)	0.0423 (6)
H14	0.2817	0.4687	−0.0925	0.051*
C15	0.6056 (5)	0.4119 (2)	−0.1500 (2)	0.0446 (6)
H15	0.6211	0.4867	−0.2085	0.053*
C16	0.7835 (4)	0.3147 (2)	−0.1339 (2)	0.0440 (6)
H16	0.9206	0.3227	−0.1817	0.053*
C17	0.7641 (4)	0.2053 (2)	−0.0484 (2)	0.0357 (5)
H17	0.8876	0.1385	−0.0372	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0403 (3)	0.0285 (3)	0.0280 (3)	−0.0103 (2)	0.0039 (2)	−0.0080 (2)
F1	0.0343 (8)	0.0617 (10)	0.0483 (9)	−0.0033 (7)	0.0032 (7)	−0.0023 (7)
O1	0.0354 (9)	0.0332 (8)	0.0275 (8)	−0.0073 (7)	0.0059 (7)	−0.0048 (7)
O2	0.0483 (10)	0.0361 (9)	0.0379 (9)	0.0035 (8)	0.0052 (8)	−0.0067 (8)
C1	0.0319 (12)	0.0261 (11)	0.0257 (11)	−0.0066 (9)	0.0011 (9)	−0.0037 (9)
C2	0.0319 (12)	0.0233 (11)	0.0245 (11)	−0.0028 (9)	−0.0011 (9)	−0.0027 (9)
C3	0.0317 (12)	0.0270 (11)	0.0307 (12)	−0.0039 (9)	0.0004 (9)	−0.0033 (9)
C4	0.0373 (13)	0.0235 (11)	0.0391 (13)	−0.0023 (10)	−0.0096 (11)	−0.0024 (10)
C5	0.0505 (15)	0.0259 (12)	0.0358 (13)	−0.0007 (11)	−0.0128 (11)	−0.0097 (10)
C6	0.0440 (14)	0.0291 (12)	0.0276 (12)	0.0012 (10)	−0.0051 (10)	−0.0030 (10)
C7	0.0327 (12)	0.0240 (11)	0.0278 (12)	−0.0032 (9)	−0.0008 (9)	−0.0025 (9)
C8	0.0342 (12)	0.0277 (11)	0.0270 (11)	−0.0043 (9)	−0.0013 (9)	−0.0047 (9)
C9	0.0496 (15)	0.0326 (13)	0.0524 (16)	−0.0118 (11)	−0.0112 (12)	−0.0057 (12)
C10	0.0671 (18)	0.0478 (15)	0.0320 (14)	−0.0038 (13)	0.0026 (12)	−0.0138 (12)
C11	0.0349 (13)	0.0336 (12)	0.0411 (14)	−0.0109 (10)	0.0023 (11)	−0.0047 (11)
C12	0.0374 (12)	0.0309 (11)	0.0232 (11)	−0.0120 (10)	0.0001 (9)	−0.0080 (9)
C13	0.0356 (13)	0.0423 (14)	0.0280 (12)	−0.0100 (11)	−0.0009 (10)	−0.0087 (10)
C14	0.0545 (16)	0.0352 (13)	0.0369 (14)	−0.0031 (12)	−0.0116 (12)	−0.0055 (11)
C15	0.0632 (18)	0.0378 (14)	0.0334 (14)	−0.0194 (13)	−0.0013 (12)	0.0003 (11)
C16	0.0510 (16)	0.0504 (15)	0.0334 (13)	−0.0245 (13)	0.0090 (12)	−0.0067 (12)
C17	0.0386 (13)	0.0374 (13)	0.0329 (13)	−0.0105 (11)	0.0038 (10)	−0.0103 (10)

Geometric parameters (Å, º) top

S1—O2	1.4800 (17)	C9—H9A	0.9800
S1—C1	1.750 (2)	C9—H9B	0.9800
S1—C12	1.794 (2)	C9—H9C	0.9800
F1—C13	1.351 (3)	C10—H10A	0.9800
O1—C8	1.367 (3)	C10—H10B	0.9800
O1—C7	1.382 (3)	C10—H10C	0.9800
C1—C8	1.353 (3)	C11—H11A	0.9800
C1—C2	1.447 (3)	C11—H11B	0.9800
C2—C7	1.380 (3)	C11—H11C	0.9800
C2—C3	1.388 (3)	C12—C17	1.376 (3)
C3—C4	1.383 (3)	C12—C13	1.380 (3)
C3—H3	0.9500	C13—C14	1.370 (3)
C4—C5	1.405 (3)	C14—C15	1.378 (4)
C4—C9	1.501 (3)	C14—H14	0.9500
C5—C6	1.383 (3)	C15—C16	1.374 (4)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.381 (3)	C16—C17	1.386 (3)
C6—C10	1.498 (3)	C16—H16	0.9500
C8—C11	1.480 (3)	C17—H17	0.9500

O2—S1—C1	108.67 (10)	H9A—C9—H9C	109.5
O2—S1—C12	105.39 (10)	H9B—C9—H9C	109.5
C1—S1—C12	99.10 (10)	C6—C10—H10A	109.5
C8—O1—C7	106.29 (16)	C6—C10—H10B	109.5
C8—C1—C2	107.28 (18)	H10A—C10—H10B	109.5
C8—C1—S1	121.35 (17)	C6—C10—H10C	109.5
C2—C1—S1	131.27 (16)	H10A—C10—H10C	109.5
C7—C2—C3	119.3 (2)	H10B—C10—H10C	109.5
C7—C2—C1	104.71 (18)	C8—C11—H11A	109.5
C3—C2—C1	136.0 (2)	C8—C11—H11B	109.5
C4—C3—C2	118.6 (2)	H11A—C11—H11B	109.5
C4—C3—H3	120.7	C8—C11—H11C	109.5
C2—C3—H3	120.7	H11A—C11—H11C	109.5
C3—C4—C5	119.6 (2)	H11B—C11—H11C	109.5
C3—C4—C9	120.3 (2)	C17—C12—C13	118.7 (2)
C5—C4—C9	120.1 (2)	C17—C12—S1	118.60 (18)
C6—C5—C4	123.4 (2)	C13—C12—S1	122.49 (17)
C6—C5—H5	118.3	F1—C13—C14	118.8 (2)
C4—C5—H5	118.3	F1—C13—C12	118.7 (2)
C7—C6—C5	114.3 (2)	C14—C13—C12	122.5 (2)
C7—C6—C10	121.8 (2)	C13—C14—C15	118.1 (2)
C5—C6—C10	123.9 (2)	C13—C14—H14	120.9
C2—C7—C6	124.8 (2)	C15—C14—H14	120.9
C2—C7—O1	110.78 (18)	C16—C15—C14	120.6 (2)
C6—C7—O1	124.4 (2)	C16—C15—H15	119.7
C1—C8—O1	110.95 (19)	C14—C15—H15	119.7
C1—C8—C11	133.3 (2)	C15—C16—C17	120.4 (2)
O1—C8—C11	115.71 (19)	C15—C16—H16	119.8
C4—C9—H9A	109.5	C17—C16—H16	119.8
C4—C9—H9B	109.5	C12—C17—C16	119.6 (2)
H9A—C9—H9B	109.5	C12—C17—H17	120.2
C4—C9—H9C	109.5	C16—C17—H17	120.2

O2—S1—C1—C8	−114.62 (19)	C8—O1—C7—C2	−0.3 (2)
C12—S1—C1—C8	135.63 (19)	C8—O1—C7—C6	178.7 (2)
O2—S1—C1—C2	61.2 (2)	C2—C1—C8—O1	0.5 (2)
C12—S1—C1—C2	−48.6 (2)	S1—C1—C8—O1	177.20 (14)
C8—C1—C2—C7	−0.7 (2)	C2—C1—C8—C11	180.0 (2)
S1—C1—C2—C7	−176.90 (17)	S1—C1—C8—C11	−3.3 (4)
C8—C1—C2—C3	179.6 (2)	C7—O1—C8—C1	−0.2 (2)
S1—C1—C2—C3	3.3 (4)	C7—O1—C8—C11	−179.71 (18)
C7—C2—C3—C4	−0.3 (3)	O2—S1—C12—C17	11.7 (2)
C1—C2—C3—C4	179.4 (2)	C1—S1—C12—C17	124.08 (18)
C2—C3—C4—C5	−0.8 (3)	O2—S1—C12—C13	−173.87 (18)
C2—C3—C4—C9	178.9 (2)	C1—S1—C12—C13	−61.5 (2)
C3—C4—C5—C6	0.9 (3)	C17—C12—C13—F1	179.23 (19)
C9—C4—C5—C6	−178.8 (2)	S1—C12—C13—F1	4.8 (3)
C4—C5—C6—C7	0.1 (3)	C17—C12—C13—C14	−1.6 (3)
C4—C5—C6—C10	179.6 (2)	S1—C12—C13—C14	−175.97 (18)
C3—C2—C7—C6	1.4 (3)	F1—C13—C14—C15	−179.4 (2)
C1—C2—C7—C6	−178.4 (2)	C12—C13—C14—C15	1.4 (4)
C3—C2—C7—O1	−179.60 (18)	C13—C14—C15—C16	−0.4 (4)
C1—C2—C7—O1	0.6 (2)	C14—C15—C16—C17	−0.4 (4)
C5—C6—C7—C2	−1.3 (3)	C13—C12—C17—C16	0.7 (3)
C10—C6—C7—C2	179.2 (2)	S1—C12—C17—C16	175.30 (18)
C5—C6—C7—O1	179.88 (19)	C15—C16—C17—C12	0.3 (4)
C10—C6—C7—O1	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O2ⁱ	0.95	2.47	3.308 (3)	148

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅FO₂S
M_r	302.35
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.0969 (10), 10.9279 (16), 11.2209 (16)
α, β, γ (°)	78.167 (10), 83.72 (1), 79.722 (11)
V (Å³)	717.92 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.22 × 0.13 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.640, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	10389, 2533, 2028
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.099, 1.05
No. of reflections	2533
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.27

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O2ⁱ	0.95	2.47	3.308 (3)	147.7

Symmetry code: (i) −x+2, −y, −z.

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.

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