3-Methyl­sulfinyl-2-phenyl-1-benzofuran

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

doi:10.1107/S1600536808024276

organic compounds

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Volume 64| Part 9| September 2008| Page o1687

doi:10.1107/S1600536808024276

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3-Methylsulfinyl-2-phenyl-1-benzofuran

Hong Dae Choi,^a Pil Ja Seo,^a Byeng Wha Son ^b 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 24 July 2008; accepted 30 July 2008; online 6 August 2008)

The title compound, C₁₅H₁₂O₂S, was prepared by the oxidation of 3-methylsulfanyl-2-phenyl-1-benzofuran with 3-chloroperoxybenzoic acid. The phenyl ring makes a dihedral angle of 37.65 (8)° with the plane of the benzofuran fragment. The O atom and the methyl group of the methylsulfinyl substituent lie on opposite sides of the plane of the benzofuran ring system. The crystal structure is stabilized by aromatic π–π interactions between the benzene rings of neighbouring molecules [centroid–centroid distance = 3.549 (2) Å] and by intermolecular C—H⋯O interactions.

Related literature

For the crystal structures of similar 3-methylsulfinyl-2-phenyl-1-benzofuran compounds, see: Choi et al. (2007a ,b ).

Experimental

Crystal data

C₁₅H₁₂O₂S
M_r = 256.32
Triclinic, $[P \overline 1]$
a = 8.0185 (8) Å
b = 9.4381 (9) Å
c = 9.7749 (9) Å
α = 115.574 (2)°
β = 109.179 (2)°
γ = 94.296 (2)°
V = 609.51 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
3185 measured reflections
2120 independent reflections
1878 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.090
S = 1.10
2120 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15C⋯O2ⁱ	0.98	2.34	3.290 (3)	164
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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/S1600536808024276/pk2109sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024276/pk2109Isup2.hkl

checkCIF report

Comment top

This work is related to our previous communications on the synthesis and structure of 3-methylsulfinyl-2-phenyl-1-benzofuran analogues, viz. 5-chloro-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007a) and 5-methyl-3-methylsulfinyl-2-phenyl-1-benzofuran (Choi et al., 2007b). Here we report the crystal structure of 3-methylsulfinyl-2-phenyl-1-benzofuran (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 phenyl ring (C9—C14) makes a dihedral angle of 37.65 (8)° with the plane of the benzofuran fragment. The molecular packing (Fig. 2) is stabilized by aromatic π—π stacking interactions between the benzene rings from the adjacent molecules. The Cg···Cgⁱⁱ distance is 3.549 (2) Å (Cg is the centroid of C2—C7 benzene ring, symmetry code as in Fig. 2). The crystal structure is further stabilized by C—H···O (Fig. 2) interactions between a methyl H atom and the oxygen of the S=O unit, with a C15—H15C···O2ⁱ separation of 2.36 Å (Fig. 2 and Table 1; symmetry code as in Fig. 2).

Related literature top

For the crystal structures of similar 3-methylsulfinyl-2-phenyl-1-benzofuran compounds, see: Choi et al. (2007a,b).

Experimental top

77% 3-Chloroperoxybenzoic acid (359 mg, 1.6 mmol) was added in small portions to a stirred solution of 3-methylsulfanyl-2-phenyl-1-benzofuran (360 mg, 1.5 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 2 h at room temperature, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by column chromatography (hexane-ethyl acetate, 1: 2 v/v) to afford the title compound as a colorless solid [yield 76%, m.p. 408–409 K; R_f = 0.79 (hexane-ethyl acetate, 1:2 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in benzene at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 3.13 (s, 3H), 7.33–7.44 (m, 3H), 7.48–7.54 (m, 2H), 7.59 (d, J = 8.03 Hz, 1H), 7.84 (dd, J = 8.08 Hz and J = 1.48 Hz, 2H), 8.22 (d, J = 7.32 Hz, 1H); EI—MS 256 [M⁺].

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. π—π and C—H···O interactions (dotted lines) in the title compound. Cg denotes ring centroid. [Symmetry code: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y, -z + 1.]

3-Methylsulfinyl-2-phenyl-1-benzofuran top

Crystal data top

C₁₅H₁₂O₂S	Z = 2
M_r = 256.32	F(000) = 268
Triclinic, P1	D_x = 1.397 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0185 (8) Å	Cell parameters from 2383 reflections
b = 9.4381 (9) Å	θ = 2.5–28.2°
c = 9.7749 (9) Å	µ = 0.26 mm⁻¹
α = 115.574 (2)°	T = 173 K
β = 109.179 (2)°	Block, colorless
γ = 94.296 (2)°	0.30 × 0.10 × 0.10 mm
V = 609.51 (10) Å³

Data collection top

Bruker SMART CCD diffractometer	1878 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 25.0°, θ_min = 2.5°
Detector resolution: 10.0 pixels mm^-1	h = −8→9
ϕ and ω scans	k = −11→11
3185 measured reflections	l = −11→5
2120 independent 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0341P)² + 0.3746P] where P = (F_o² + 2F_c²)/3
2120 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₅H₁₂O₂S	γ = 94.296 (2)°
M_r = 256.32	V = 609.51 (10) Å³
Triclinic, P1	Z = 2
a = 8.0185 (8) Å	Mo Kα radiation
b = 9.4381 (9) Å	µ = 0.26 mm⁻¹
c = 9.7749 (9) Å	T = 173 K
α = 115.574 (2)°	0.30 × 0.10 × 0.10 mm
β = 109.179 (2)°

Data collection top

Bruker SMART CCD diffractometer	1878 reflections with I > 2σ(I)
3185 measured reflections	R_int = 0.030
2120 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.10	Δρ_max = 0.32 e Å⁻³
2120 reflections	Δρ_min = −0.24 e Å⁻³
164 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.33893 (6)	0.23694 (6)	0.35764 (6)	0.02368 (16)
O1	−0.05250 (18)	−0.15771 (15)	0.17293 (16)	0.0238 (3)
O2	0.4116 (2)	0.33041 (18)	0.54205 (18)	0.0356 (4)
C1	0.1412 (3)	0.0880 (2)	0.2927 (2)	0.0210 (4)
C2	0.0021 (3)	0.1096 (2)	0.3590 (2)	0.0219 (4)
C3	−0.0353 (3)	0.2390 (3)	0.4755 (3)	0.0280 (5)
H3	0.0420	0.3457	0.5336	0.034*
C4	−0.1883 (3)	0.2063 (3)	0.5031 (3)	0.0321 (5)
H4	−0.2170	0.2928	0.5807	0.039*
C5	−0.3018 (3)	0.0500 (3)	0.4202 (3)	0.0326 (5)
H5	−0.4060	0.0329	0.4425	0.039*
C6	−0.2666 (3)	−0.0807 (3)	0.3064 (3)	0.0291 (5)
H6	−0.3429	−0.1877	0.2500	0.035*
C7	−0.1131 (3)	−0.0453 (2)	0.2802 (2)	0.0226 (4)
C8	0.1044 (2)	−0.0725 (2)	0.1847 (2)	0.0212 (4)
C9	0.1918 (3)	−0.1716 (2)	0.0813 (2)	0.0221 (4)
C10	0.1916 (3)	−0.3292 (2)	0.0565 (3)	0.0299 (5)
H10	0.1393	−0.3695	0.1110	0.036*
C11	0.2669 (3)	−0.4265 (3)	−0.0468 (3)	0.0370 (5)
H11	0.2666	−0.5331	−0.0624	0.044*
C12	0.3428 (3)	−0.3693 (3)	−0.1276 (3)	0.0364 (5)
H12	0.3931	−0.4370	−0.1995	0.044*
C13	0.3451 (3)	−0.2136 (3)	−0.1033 (3)	0.0315 (5)
H13	0.3986	−0.1738	−0.1575	0.038*
C14	0.2695 (3)	−0.1150 (2)	0.0000 (2)	0.0255 (4)
H14	0.2707	−0.0083	0.0154	0.031*
C15	0.2300 (3)	0.3619 (3)	0.2805 (3)	0.0352 (5)
H15A	0.1334	0.3896	0.3203	0.053*
H15B	0.1768	0.3027	0.1592	0.053*
H15C	0.3203	0.4616	0.3200	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0189 (3)	0.0221 (3)	0.0235 (3)	0.00303 (19)	0.0068 (2)	0.0072 (2)
O1	0.0233 (7)	0.0214 (7)	0.0253 (7)	0.0042 (5)	0.0117 (6)	0.0089 (6)
O2	0.0311 (8)	0.0359 (9)	0.0232 (8)	−0.0025 (7)	0.0057 (7)	0.0058 (7)
C1	0.0201 (10)	0.0212 (10)	0.0202 (10)	0.0065 (8)	0.0080 (8)	0.0088 (8)
C2	0.0204 (10)	0.0264 (10)	0.0206 (10)	0.0093 (8)	0.0080 (8)	0.0122 (9)
C3	0.0305 (11)	0.0281 (11)	0.0246 (11)	0.0125 (9)	0.0107 (9)	0.0116 (9)
C4	0.0357 (12)	0.0421 (13)	0.0277 (11)	0.0238 (10)	0.0181 (10)	0.0185 (10)
C5	0.0303 (12)	0.0506 (14)	0.0401 (13)	0.0229 (10)	0.0236 (10)	0.0324 (12)
C6	0.0256 (11)	0.0365 (12)	0.0348 (12)	0.0106 (9)	0.0138 (9)	0.0235 (10)
C7	0.0234 (10)	0.0275 (10)	0.0213 (10)	0.0105 (8)	0.0112 (8)	0.0132 (9)
C8	0.0187 (9)	0.0235 (10)	0.0208 (10)	0.0035 (8)	0.0067 (8)	0.0113 (8)
C9	0.0198 (9)	0.0214 (10)	0.0181 (10)	0.0034 (8)	0.0056 (8)	0.0055 (8)
C10	0.0334 (12)	0.0255 (11)	0.0309 (12)	0.0068 (9)	0.0163 (10)	0.0113 (9)
C11	0.0423 (13)	0.0239 (11)	0.0400 (14)	0.0113 (10)	0.0199 (11)	0.0085 (10)
C12	0.0317 (12)	0.0366 (13)	0.0305 (12)	0.0101 (10)	0.0167 (10)	0.0041 (10)
C13	0.0254 (11)	0.0409 (12)	0.0227 (11)	0.0036 (9)	0.0114 (9)	0.0104 (9)
C14	0.0235 (10)	0.0277 (11)	0.0213 (10)	0.0048 (8)	0.0070 (8)	0.0103 (9)
C15	0.0292 (11)	0.0263 (11)	0.0451 (14)	0.0039 (9)	0.0081 (10)	0.0186 (11)

Geometric parameters (Å, º) top

S—O2	1.492 (2)	C6—H6	0.9500
S—C1	1.769 (2)	C8—C9	1.461 (3)
S—C15	1.792 (2)	C9—C14	1.396 (3)
O1—C7	1.384 (2)	C9—C10	1.400 (3)
O1—C8	1.384 (2)	C10—C11	1.382 (3)
C1—C8	1.358 (3)	C10—H10	0.9500
C1—C2	1.449 (3)	C11—C12	1.386 (3)
C2—C7	1.394 (3)	C11—H11	0.9500
C2—C3	1.398 (3)	C12—C13	1.382 (3)
C3—C4	1.381 (3)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.389 (3)
C4—C5	1.394 (3)	C13—H13	0.9500
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.383 (3)	C15—H15A	0.9800
C5—H5	0.9500	C15—H15B	0.9800
C6—C7	1.383 (3)	C15—H15C	0.9800

O2—S—C1	106.42 (9)	C1—C8—C9	134.62 (17)
O2—S—C15	107.19 (10)	O1—C8—C9	114.80 (16)
C1—S—C15	98.28 (10)	C14—C9—C10	118.74 (18)
C7—O1—C8	106.40 (14)	C14—C9—C8	121.25 (17)
C8—C1—C2	107.57 (17)	C10—C9—C8	119.95 (18)
C8—C1—S	125.35 (15)	C11—C10—C9	120.4 (2)
C2—C1—S	126.67 (14)	C11—C10—H10	119.8
C7—C2—C3	118.79 (18)	C9—C10—H10	119.8
C7—C2—C1	104.81 (16)	C10—C11—C12	120.3 (2)
C3—C2—C1	136.38 (19)	C10—C11—H11	119.8
C4—C3—C2	117.8 (2)	C12—C11—H11	119.8
C4—C3—H3	121.1	C13—C12—C11	119.9 (2)
C2—C3—H3	121.1	C13—C12—H12	120.1
C3—C4—C5	121.8 (2)	C11—C12—H12	120.1
C3—C4—H4	119.1	C12—C13—C14	120.2 (2)
C5—C4—H4	119.1	C12—C13—H13	119.9
C6—C5—C4	121.76 (19)	C14—C13—H13	119.9
C6—C5—H5	119.1	C13—C14—C9	120.40 (19)
C4—C5—H5	119.1	C13—C14—H14	119.8
C7—C6—C5	115.5 (2)	C9—C14—H14	119.8
C7—C6—H6	122.3	S—C15—H15A	109.5
C5—C6—H6	122.3	S—C15—H15B	109.5
C6—C7—O1	125.00 (18)	H15A—C15—H15B	109.5
C6—C7—C2	124.38 (18)	S—C15—H15C	109.5
O1—C7—C2	110.62 (16)	H15A—C15—H15C	109.5
C1—C8—O1	110.58 (16)	H15B—C15—H15C	109.5

O2—S—C1—C8	−130.84 (18)	C1—C2—C7—O1	0.4 (2)
C15—S—C1—C8	118.42 (19)	C2—C1—C8—O1	1.2 (2)
O2—S—C1—C2	40.85 (19)	S—C1—C8—O1	174.25 (13)
C15—S—C1—C2	−69.89 (19)	C2—C1—C8—C9	−178.8 (2)
C8—C1—C2—C7	−1.0 (2)	S—C1—C8—C9	−5.8 (3)
S—C1—C2—C7	−173.87 (15)	C7—O1—C8—C1	−1.0 (2)
C8—C1—C2—C3	177.6 (2)	C7—O1—C8—C9	179.06 (16)
S—C1—C2—C3	4.7 (3)	C1—C8—C9—C14	−38.8 (3)
C7—C2—C3—C4	−1.6 (3)	O1—C8—C9—C14	141.18 (18)
C1—C2—C3—C4	179.9 (2)	C1—C8—C9—C10	144.1 (2)
C2—C3—C4—C5	0.8 (3)	O1—C8—C9—C10	−36.0 (3)
C3—C4—C5—C6	0.3 (3)	C14—C9—C10—C11	0.0 (3)
C4—C5—C6—C7	−0.4 (3)	C8—C9—C10—C11	177.18 (19)
C5—C6—C7—O1	179.56 (18)	C9—C10—C11—C12	−0.3 (3)
C5—C6—C7—C2	−0.5 (3)	C10—C11—C12—C13	0.7 (4)
C8—O1—C7—C6	−179.69 (19)	C11—C12—C13—C14	−0.9 (3)
C8—O1—C7—C2	0.3 (2)	C12—C13—C14—C9	0.5 (3)
C3—C2—C7—C6	1.5 (3)	C10—C9—C14—C13	−0.1 (3)
C1—C2—C7—C6	−179.59 (19)	C8—C9—C14—C13	−177.25 (18)
C3—C2—C7—O1	−178.49 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15C···O2ⁱ	0.98	2.34	3.290 (3)	164

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₂S
M_r	256.32
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.0185 (8), 9.4381 (9), 9.7749 (9)
α, β, γ (°)	115.574 (2), 109.179 (2), 94.296 (2)
V (Å³)	609.51 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3185, 2120, 1878
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.090, 1.10
No. of reflections	2120
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.24

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
C15—H15C···O2ⁱ	0.98	2.34	3.290 (3)	163.6

Symmetry code: (i) −x+1, −y+1, −z+1.

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007a). Acta Cryst. E63, o1291–o1292. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o2922. 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

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doi:10.1107/S1600536808024276

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