2,5,7-Trimethyl-3-phenyl­sulfinyl-1-benzo­furan

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

doi:10.1107/S1600536808019302

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1395

doi:10.1107/S1600536808019302

Open

access

2,5,7-Trimethyl-3-phenylsulfinyl-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 6 June 2008; accepted 25 June 2008; online 5 July 2008)

The title compound, C₁₇H₁₆O₂S, was prepared by the oxidation of 2,5,7-trimethyl-3-phenylsulfanyl-1-benzofuran with 3-chloroperoxybenzoic acid. The O atom and the phenyl group of the phenylsulfinyl substituent lie on opposite sides of the plane of the benzofuran fragment. The phenyl ring is nearly perpendicular to the plane of the benzofuran unit [88.30 (9)°] and is tilted slightly towards it. No π–π or C—H⋯π interactions are observed between neighbouring molecules in the crystal structure because of steric hindrance induced by the three methyl groups.

Related literature

For the crystal structures of similar 3-phenylsulfinyl-1-benzofuran derivatives, see: Choi et al. (2007 , 2008 ).

Experimental

Crystal data

C₁₇H₁₆O₂S
M_r = 284.36
Monoclinic, P 2₁ /c
a = 18.393 (2) Å
b = 6.1515 (6) Å
c = 13.054 (1) Å
β = 93.024 (2)°
V = 1474.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
8615 measured reflections
3215 independent reflections
1611 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.163
S = 1.01
3215 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.20 e Å⁻³

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/S1600536808019302/rn2045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019302/rn2045Isup2.hkl

checkCIF report

Comment top

This work is related to the our communications on the synthesis and structures of 3-phenylsulfinyl-1-benzofuran analogues, viz. 2,5-dimethyl-3-phenylsulfinyl-1-benzofuran (Choi et al., 2007) and 2,4,6,7-tetramethyl-3-phenylsulfinyl-1-benzofuran (Choi et al., 2008). Here we report the crystal structure of the title compound, 2,5,7-trimethyl-3-phenylsulfinyl-1-benzofuran (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 phenyl ring (C9—C14) is almost perpendicular to the plane of the benzofuran ring system [88.30 (9)°] and is tilted slightly towards it. In the crystal structure, π—π or C—H···π interactions between adjacent molecules are prevented by the steric influence of the three methyl groups in the molecule.

Related literature top

For the crystal structures of similar 3-phenylsulfinyl-1-benzofuran derivatives, see: Choi et al. (2007, 2008).

Experimental top

77% 3-chloroperoxybenzoic acid (247 mg, 1.1 mmol) was added in small portions to a stirred solution of 2,5,7-trimethyl-3-phenylsulfanyl-1-benzofuran (268 mg, 1.0 mmol) in dichloromethane (20 ml) at 273 K. After being stirred at room temperature for 2 h, 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, 1:1 v/v) to afford the title compound as a colorless solid [yield 82%, m.p. 393–394 K; R_f = 0.65 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in acetone at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.22 (s, 3H), 2.41 (s, 3H), 2.75 (s, 3H), 6.84 (d, J = 6.96 Hz, 2H), 7.43–7.51 (m, 3H), 7.67 (d, J = 6.60 Hz, 2H); EI—MS 284 [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 ellipsoides drawn at the 30% probability level.

2,5,7-Trimethyl-3-phenylsulfinyl-1-benzofuran top

Crystal data top

C₁₇H₁₆O₂S	F(000) = 600
M_r = 284.36	D_x = 1.281 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P_2ybc	Cell parameters from 1802 reflections
a = 18.393 (2) Å	θ = 3.1–24.3°
b = 6.1515 (6) Å	µ = 0.22 mm⁻¹
c = 13.054 (1) Å	T = 298 K
β = 93.024 (2)°	Block, colorless
V = 1474.9 (2) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1611 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.066
Graphite monochromator	θ_max = 27.0°, θ_min = 1.1°
Detector resolution: 10.0 pixels mm^-1	h = −18→23
ϕ and ω scans	k = −6→7
8615 measured reflections	l = −16→13
3215 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0668P)² + 0.2115P] where P = (F_o² + 2F_c²)/3
3215 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₇H₁₆O₂S	V = 1474.9 (2) Å³
M_r = 284.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.393 (2) Å	µ = 0.22 mm⁻¹
b = 6.1515 (6) Å	T = 298 K
c = 13.054 (1) Å	0.20 × 0.10 × 0.10 mm
β = 93.024 (2)°

Data collection top

Bruker SMART CCD diffractometer	1611 reflections with I > 2σ(I)
8615 measured reflections	R_int = 0.066
3215 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
3215 reflections	Δρ_min = −0.20 e Å⁻³
184 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	0.33491 (5)	0.75793 (15)	0.41600 (7)	0.0730 (3)
O1	0.12972 (11)	0.7187 (3)	0.31945 (14)	0.0536 (5)
O2	0.34960 (15)	0.7328 (5)	0.52790 (19)	0.1133 (11)
C1	0.24341 (15)	0.6884 (5)	0.3874 (2)	0.0481 (7)
C2	0.20160 (15)	0.5094 (4)	0.42636 (19)	0.0438 (7)
C3	0.21511 (17)	0.3364 (5)	0.4936 (2)	0.0517 (7)
H3	0.2611	0.3158	0.5251	0.062*
C4	0.15868 (19)	0.1960 (5)	0.5125 (2)	0.0577 (8)
C5	0.09051 (19)	0.2308 (5)	0.4641 (2)	0.0653 (9)
H5	0.0534	0.1338	0.4775	0.078*
C6	0.07447 (16)	0.4016 (5)	0.3972 (2)	0.0571 (8)
C7	0.13246 (15)	0.5374 (4)	0.38166 (19)	0.0450 (7)
C8	0.19788 (17)	0.8067 (5)	0.3253 (2)	0.0517 (7)
C9	0.37498 (15)	0.5292 (5)	0.3559 (2)	0.0552 (8)
C10	0.36512 (17)	0.5067 (6)	0.2517 (3)	0.0727 (10)
H10	0.3375	0.6073	0.2134	0.087*
C11	0.3964 (2)	0.3347 (9)	0.2050 (3)	0.0974 (14)
H11	0.3891	0.3161	0.1345	0.117*
C12	0.4385 (2)	0.1893 (8)	0.2609 (5)	0.1024 (14)
H12	0.4588	0.0715	0.2281	0.123*
C13	0.4510 (2)	0.2152 (7)	0.3637 (4)	0.0973 (14)
H13	0.4807	0.1179	0.4009	0.117*
C14	0.41888 (19)	0.3882 (7)	0.4128 (3)	0.0779 (11)
H14	0.4270	0.4084	0.4831	0.094*
C15	0.1696 (2)	0.0106 (6)	0.5874 (3)	0.0864 (11)
H15A	0.2207	−0.0077	0.6043	0.130*
H15B	0.1503	−0.1207	0.5569	0.130*
H15C	0.1449	0.0422	0.6486	0.130*
C16	0.00061 (18)	0.4398 (7)	0.3461 (3)	0.0873 (12)
H16A	−0.0161	0.5825	0.3631	0.131*
H16B	−0.0329	0.3332	0.3695	0.131*
H16C	0.0035	0.4280	0.2731	0.131*
C17	0.2083 (2)	1.0024 (5)	0.2620 (2)	0.0760 (10)
H17A	0.2548	1.0662	0.2803	0.114*
H17B	0.1704	1.1056	0.2737	0.114*
H17C	0.2063	0.9624	0.1908	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0663 (6)	0.0763 (7)	0.0762 (6)	−0.0265 (5)	0.0011 (4)	−0.0218 (5)
O1	0.0570 (13)	0.0537 (13)	0.0496 (12)	0.0046 (10)	−0.0005 (9)	−0.0029 (10)
O2	0.0903 (18)	0.178 (3)	0.0700 (17)	−0.0144 (18)	−0.0154 (14)	−0.0556 (17)
C1	0.0577 (18)	0.0457 (17)	0.0409 (16)	−0.0104 (14)	0.0017 (13)	−0.0058 (12)
C2	0.0541 (17)	0.0419 (16)	0.0356 (14)	−0.0058 (13)	0.0054 (12)	−0.0090 (12)
C3	0.067 (2)	0.0490 (17)	0.0387 (16)	0.0014 (15)	0.0030 (14)	−0.0008 (13)
C4	0.082 (2)	0.0468 (19)	0.0457 (18)	−0.0085 (16)	0.0177 (16)	−0.0021 (13)
C5	0.073 (2)	0.061 (2)	0.064 (2)	−0.0234 (18)	0.0229 (17)	−0.0057 (17)
C6	0.0527 (19)	0.064 (2)	0.0554 (19)	−0.0108 (16)	0.0085 (15)	−0.0140 (16)
C7	0.0528 (18)	0.0443 (17)	0.0379 (15)	−0.0011 (14)	0.0025 (13)	−0.0060 (13)
C8	0.069 (2)	0.0433 (18)	0.0434 (16)	−0.0031 (15)	0.0072 (14)	−0.0056 (13)
C9	0.0415 (17)	0.072 (2)	0.0522 (18)	−0.0146 (15)	0.0024 (14)	0.0029 (16)
C10	0.051 (2)	0.108 (3)	0.058 (2)	0.0070 (19)	−0.0011 (16)	−0.012 (2)
C11	0.061 (2)	0.144 (4)	0.088 (3)	0.006 (3)	0.006 (2)	−0.033 (3)
C12	0.082 (3)	0.096 (3)	0.132 (4)	−0.004 (3)	0.038 (3)	−0.022 (3)
C13	0.074 (3)	0.089 (3)	0.131 (4)	0.008 (2)	0.023 (3)	0.033 (3)
C14	0.067 (2)	0.100 (3)	0.067 (2)	−0.013 (2)	0.0089 (19)	0.018 (2)
C15	0.132 (3)	0.063 (2)	0.066 (2)	−0.006 (2)	0.026 (2)	0.0133 (18)
C16	0.054 (2)	0.107 (3)	0.100 (3)	−0.014 (2)	0.001 (2)	−0.017 (2)
C17	0.112 (3)	0.052 (2)	0.065 (2)	−0.0031 (19)	0.015 (2)	0.0073 (16)

Geometric parameters (Å, º) top

S—O2	1.480 (3)	C9—C14	1.376 (4)
S—C1	1.757 (3)	C10—C11	1.364 (5)
S—C9	1.789 (3)	C10—H10	0.9300
O1—C8	1.364 (3)	C11—C12	1.368 (6)
O1—C7	1.379 (3)	C11—H11	0.9300
C1—C8	1.347 (4)	C12—C13	1.360 (6)
C1—C2	1.450 (4)	C12—H12	0.9300
C2—C7	1.382 (4)	C13—C14	1.390 (6)
C2—C3	1.393 (4)	C13—H13	0.9300
C3—C4	1.383 (4)	C14—H14	0.9300
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.390 (5)	C15—H15B	0.9600
C4—C15	1.509 (4)	C15—H15C	0.9600
C5—C6	1.388 (4)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C6—C7	1.378 (4)	C16—H16C	0.9600
C6—C16	1.500 (4)	C17—H17A	0.9600
C8—C17	1.479 (4)	C17—H17B	0.9600
C9—C10	1.369 (4)	C17—H17C	0.9600

O2—S—C1	107.90 (15)	C11—C10—H10	120.5
O2—S—C9	107.03 (16)	C9—C10—H10	120.5
C1—S—C9	97.32 (13)	C10—C11—C12	120.6 (4)
C8—O1—C7	106.4 (2)	C10—C11—H11	119.7
C8—C1—C2	107.3 (2)	C12—C11—H11	119.7
C8—C1—S	123.7 (2)	C13—C12—C11	120.8 (4)
C2—C1—S	129.0 (2)	C13—C12—H12	119.6
C7—C2—C3	119.4 (3)	C11—C12—H12	119.6
C7—C2—C1	104.5 (2)	C12—C13—C14	119.4 (4)
C3—C2—C1	136.1 (3)	C12—C13—H13	120.3
C4—C3—C2	118.6 (3)	C14—C13—H13	120.3
C4—C3—H3	120.7	C9—C14—C13	119.0 (4)
C2—C3—H3	120.7	C9—C14—H14	120.5
C3—C4—C5	119.4 (3)	C13—C14—H14	120.5
C3—C4—C15	120.8 (3)	C4—C15—H15A	109.5
C5—C4—C15	119.8 (3)	C4—C15—H15B	109.5
C6—C5—C4	124.0 (3)	H15A—C15—H15B	109.5
C6—C5—H5	118.0	C4—C15—H15C	109.5
C4—C5—H5	118.0	H15A—C15—H15C	109.5
C7—C6—C5	114.3 (3)	H15B—C15—H15C	109.5
C7—C6—C16	122.0 (3)	C6—C16—H16A	109.5
C5—C6—C16	123.7 (3)	C6—C16—H16B	109.5
C6—C7—O1	124.9 (3)	H16A—C16—H16B	109.5
C6—C7—C2	124.4 (3)	C6—C16—H16C	109.5
O1—C7—C2	110.7 (2)	H16A—C16—H16C	109.5
C1—C8—O1	111.1 (2)	H16B—C16—H16C	109.5
C1—C8—C17	132.9 (3)	C8—C17—H17A	109.5
O1—C8—C17	115.9 (3)	C8—C17—H17B	109.5
C10—C9—C14	121.1 (3)	H17A—C17—H17B	109.5
C10—C9—S	118.6 (3)	C8—C17—H17C	109.5
C14—C9—S	120.2 (3)	H17A—C17—H17C	109.5
C11—C10—C9	119.1 (4)	H17B—C17—H17C	109.5

O2—S—C1—C8	134.5 (3)	C3—C2—C7—C6	−1.3 (4)
C9—S—C1—C8	−114.9 (3)	C1—C2—C7—C6	179.7 (3)
O2—S—C1—C2	−42.3 (3)	C3—C2—C7—O1	178.9 (2)
C9—S—C1—C2	68.3 (3)	C1—C2—C7—O1	−0.1 (3)
C8—C1—C2—C7	0.5 (3)	C2—C1—C8—O1	−0.6 (3)
S—C1—C2—C7	177.7 (2)	S—C1—C8—O1	−178.05 (18)
C8—C1—C2—C3	−178.3 (3)	C2—C1—C8—C17	−178.2 (3)
S—C1—C2—C3	−1.1 (5)	S—C1—C8—C17	4.4 (5)
C7—C2—C3—C4	0.8 (4)	C7—O1—C8—C1	0.6 (3)
C1—C2—C3—C4	179.4 (3)	C7—O1—C8—C17	178.6 (2)
C2—C3—C4—C5	0.1 (4)	O2—S—C9—C10	176.0 (2)
C2—C3—C4—C15	−177.9 (3)	C1—S—C9—C10	64.7 (3)
C3—C4—C5—C6	−0.5 (5)	O2—S—C9—C14	−8.4 (3)
C15—C4—C5—C6	177.5 (3)	C1—S—C9—C14	−119.7 (3)
C4—C5—C6—C7	0.0 (4)	C14—C9—C10—C11	3.5 (5)
C4—C5—C6—C16	−179.3 (3)	S—C9—C10—C11	179.0 (3)
C5—C6—C7—O1	−179.3 (2)	C9—C10—C11—C12	−1.5 (6)
C16—C6—C7—O1	0.0 (4)	C10—C11—C12—C13	−1.1 (7)
C5—C6—C7—C2	0.9 (4)	C11—C12—C13—C14	1.8 (6)
C16—C6—C7—C2	−179.8 (3)	C10—C9—C14—C13	−2.8 (5)
C8—O1—C7—C6	180.0 (3)	S—C9—C14—C13	−178.2 (3)
C8—O1—C7—C2	−0.2 (3)	C12—C13—C14—C9	0.2 (6)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₆O₂S
M_r	284.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	18.393 (2), 6.1515 (6), 13.054 (1)
β (°)	93.024 (2)
V (Å³)	1474.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8615, 3215, 1611
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.163, 1.01
No. of reflections	3215
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.20

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).

References

Brandenburg, K. (1998). DIAMOND. Version 2.1. University of 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. (2007). Acta Cryst. E63, o4042. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2008). Acta Cryst. E64, o1143. 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