Methyl 2-(5-methyl-3-methyl­sulfinyl-1-benzofuran-2-yl)acetate

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

doi:10.1107/S1600536808024689

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1711

doi:10.1107/S1600536808024689

Open

access

Methyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate

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 27 July 2008; accepted 1 August 2008; online 6 August 2008)

The title compound, C₁₃H₁₄O₄S, was prepared by oxidation of methyl 2-(5-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate with 3-chloroperoxybenzoic acid. The O atom and methyl group of the methylsulfinyl substituent lie on opposite sides of the plane of the benzofuran system. The crystal structure is stabilized by intermolecular aromatic π–π interactions between the benzene rings of neighbouring molecules, with a centroid–centroid separation of 3.841 (3) Å.

Related literature

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

Experimental

Crystal data

C₁₃H₁₄O₄S
M_r = 266.30
Triclinic, $[P \overline 1]$
a = 7.9331 (6) Å
b = 8.1097 (6) Å
c = 10.7017 (8) Å
α = 71.601 (1)°
β = 81.107 (1)°
γ = 84.303 (1)°
V = 644.51 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 (2) K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
3414 measured reflections
2237 independent reflections
1788 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.123
S = 1.03
2237 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.35 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/S1600536808024689/bh2186sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024689/bh2186Isup2.hkl

checkCIF report

Comment top

This work is related to our previous communications on the synthesis and structures of ethyl 2-(3-methylsulfinyl-1-benzofuran-2-yl)acetate analogues, viz. ethyl 2-(5-chloro-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007a) and ethyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007b). Here we report the crystal structure of the title compound, methyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate (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 packing structure is stabilized by aromatic π–π stacking interactions between adjacent benzene units, with a Cg···Cgⁱ distance is 3.841 (3) Å (Fig. 2).

Related literature top

For the crystal structures of similar ethyl 2-(3-methylsulfinyl-1-benzofuran-2-yl)acetate derivatives, 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 methyl 2-(5-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate (375 mg, 1.5 mmol) in dichloromethane (30 ml) at 273 K. After being stirred for 3 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 (ethyl acetate) to afford the title compound as a colorless solid [yield 79%, m.p. 380–381 K; R_f = 0.58 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in ethyl acetate at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) δ 2.45 (s, 3H), 3.07 (s, 3H), 3.74 (s, 3H), 4.04 (s, 2H), 7.17 (dd, J = 8.44 Hz and J = 1.08 Hz, 1H), 7.38 (d, J = 8.40 Hz, 1H), 7.71 (s, 1H); EI–MS 266 [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 30% probability level.
	Fig. 2. Intermolecular π–π interactions (dotted lines) in the title compound. Cg denotes ring centroid. Symmetry code: (i) 1-x, 2-y, -z.

Methyl 2-(5-methyl-3-methylsulfinyl-1-benzofuran-2-yl)acetate top

Crystal data top

C₁₃H₁₄O₄S	Z = 2
M_r = 266.30	F(000) = 280
Triclinic, P1	D_x = 1.372 Mg m⁻³
Hall symbol: -P 1	Melting point = 380–381 K
a = 7.9331 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1097 (6) Å	Cell parameters from 1817 reflections
c = 10.7017 (8) Å	θ = 2.6–27.3°
α = 71.601 (1)°	µ = 0.26 mm⁻¹
β = 81.107 (1)°	T = 298 K
γ = 84.303 (1)°	Block, colorless
V = 644.51 (8) Å³	0.40 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	1788 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
Detector resolution: 10.0 pixels mm^-1	h = −9→9
ϕ and ω scans	k = −9→9
3414 measured reflections	l = −9→12
2237 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0647P)² + 0.1924P] where P = (F_o² + 2F_c²)/3
2237 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₃H₁₄O₄S	γ = 84.303 (1)°
M_r = 266.30	V = 644.51 (8) Å³
Triclinic, P1	Z = 2
a = 7.9331 (6) Å	Mo Kα radiation
b = 8.1097 (6) Å	µ = 0.26 mm⁻¹
c = 10.7017 (8) Å	T = 298 K
α = 71.601 (1)°	0.40 × 0.20 × 0.20 mm
β = 81.107 (1)°

Data collection top

Bruker SMART CCD diffractometer	1788 reflections with I > 2σ(I)
3414 measured reflections	R_int = 0.052
2237 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 0.34 e Å⁻³
2237 reflections	Δρ_min = −0.36 e Å⁻³
166 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S	0.22227 (8)	0.36975 (8)	0.45695 (6)	0.0430 (2)
O1	0.16435 (19)	0.5432 (2)	0.07927 (16)	0.0392 (4)
O2	−0.1560 (3)	0.0853 (3)	0.3071 (3)	0.0850 (8)
O3	0.1251 (2)	0.0969 (2)	0.2923 (2)	0.0565 (5)
O4	0.2489 (3)	0.5059 (3)	0.51807 (19)	0.0597 (5)
C1	0.2418 (3)	0.4676 (3)	0.2838 (2)	0.0348 (5)
C2	0.3713 (3)	0.5757 (3)	0.1944 (2)	0.0342 (5)
C3	0.5246 (3)	0.6396 (3)	0.2059 (3)	0.0410 (6)
H3	0.5647	0.6111	0.2877	0.049*
C4	0.6143 (3)	0.7457 (3)	0.0930 (3)	0.0445 (6)
C5	0.5523 (3)	0.7870 (3)	−0.0291 (3)	0.0486 (7)
H5	0.6147	0.8592	−0.1038	0.058*
C6	0.4028 (3)	0.7256 (3)	−0.0442 (3)	0.0460 (6)
H6	0.3628	0.7534	−0.1260	0.055*
C7	0.3168 (3)	0.6199 (3)	0.0709 (2)	0.0366 (5)
C8	0.1227 (3)	0.4533 (3)	0.2103 (2)	0.0352 (5)
C9	−0.0416 (3)	0.3635 (3)	0.2452 (3)	0.0404 (6)
H9A	−0.1049	0.4071	0.1697	0.048*
H9B	−0.1081	0.3975	0.3181	0.048*
C10	−0.0307 (3)	0.1679 (3)	0.2841 (3)	0.0447 (6)
C11	0.1449 (4)	−0.0918 (4)	0.3298 (4)	0.0801 (11)
H11A	0.0761	−0.1409	0.4132	0.120*
H11B	0.2627	−0.1280	0.3382	0.120*
H11C	0.1090	−0.1312	0.2629	0.120*
C12	0.7804 (3)	0.8174 (4)	0.1000 (3)	0.0616 (8)
H12A	0.8119	0.7677	0.1878	0.092*
H12B	0.7661	0.9416	0.0797	0.092*
H12C	0.8685	0.7884	0.0369	0.092*
C13	0.4142 (4)	0.2333 (4)	0.4661 (3)	0.0573 (7)
H13A	0.5112	0.3042	0.4396	0.086*
H13B	0.4176	0.1635	0.4080	0.086*
H13C	0.4167	0.1588	0.5556	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0403 (4)	0.0487 (4)	0.0362 (4)	−0.0034 (3)	−0.0055 (3)	−0.0072 (3)
O1	0.0378 (9)	0.0428 (9)	0.0376 (9)	−0.0039 (7)	−0.0099 (7)	−0.0104 (7)
O2	0.0557 (13)	0.0589 (13)	0.135 (2)	−0.0209 (11)	−0.0173 (13)	−0.0150 (14)
O3	0.0415 (10)	0.0357 (9)	0.0832 (14)	−0.0039 (8)	0.0035 (9)	−0.0100 (9)
O4	0.0708 (13)	0.0711 (13)	0.0456 (11)	0.0066 (10)	−0.0141 (10)	−0.0297 (10)
C1	0.0363 (12)	0.0338 (12)	0.0349 (12)	−0.0017 (9)	−0.0056 (10)	−0.0110 (10)
C2	0.0354 (12)	0.0307 (11)	0.0377 (13)	0.0006 (9)	−0.0047 (10)	−0.0128 (10)
C3	0.0376 (13)	0.0413 (13)	0.0482 (15)	−0.0020 (10)	−0.0082 (11)	−0.0182 (12)
C4	0.0369 (13)	0.0363 (13)	0.0611 (17)	−0.0010 (10)	−0.0039 (12)	−0.0175 (12)
C5	0.0433 (14)	0.0415 (14)	0.0517 (16)	−0.0044 (11)	0.0054 (12)	−0.0060 (12)
C6	0.0492 (15)	0.0442 (14)	0.0397 (14)	−0.0006 (12)	−0.0058 (12)	−0.0065 (11)
C7	0.0337 (12)	0.0341 (12)	0.0435 (14)	0.0006 (9)	−0.0065 (10)	−0.0139 (10)
C8	0.0354 (12)	0.0317 (11)	0.0381 (13)	−0.0004 (9)	−0.0038 (10)	−0.0110 (10)
C9	0.0317 (12)	0.0448 (14)	0.0466 (15)	−0.0027 (10)	−0.0082 (11)	−0.0152 (11)
C10	0.0423 (14)	0.0478 (15)	0.0453 (15)	−0.0094 (11)	−0.0040 (11)	−0.0148 (12)
C11	0.070 (2)	0.0385 (16)	0.115 (3)	−0.0043 (15)	0.006 (2)	−0.0086 (17)
C12	0.0427 (15)	0.0532 (16)	0.088 (2)	−0.0115 (12)	−0.0069 (15)	−0.0182 (16)
C13	0.0571 (17)	0.0524 (16)	0.0596 (18)	0.0078 (13)	−0.0169 (14)	−0.0116 (14)

Geometric parameters (Å, º) top

S—O4	1.495 (2)	C5—H5	0.9300
S—C1	1.759 (2)	C6—C7	1.381 (3)
S—C13	1.788 (3)	C6—H6	0.9300
O1—C8	1.366 (3)	C8—C9	1.495 (3)
O1—C7	1.392 (3)	C9—C10	1.505 (3)
O2—C10	1.204 (3)	C9—H9A	0.9700
O3—C10	1.315 (3)	C9—H9B	0.9700
O3—C11	1.453 (3)	C11—H11A	0.9600
C1—C8	1.354 (3)	C11—H11B	0.9600
C1—C2	1.444 (3)	C11—H11C	0.9600
C2—C7	1.382 (3)	C12—H12A	0.9600
C2—C3	1.405 (3)	C12—H12B	0.9600
C3—C4	1.381 (4)	C12—H12C	0.9600
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.397 (4)	C13—H13B	0.9600
C4—C12	1.513 (3)	C13—H13C	0.9600
C5—C6	1.382 (4)

O4—S—C1	107.63 (11)	O1—C8—C9	116.0 (2)
O4—S—C13	105.85 (13)	C8—C9—C10	117.4 (2)
C1—S—C13	98.82 (13)	C8—C9—H9A	108.0
C8—O1—C7	106.00 (17)	C10—C9—H9A	108.0
C10—O3—C11	117.3 (2)	C8—C9—H9B	108.0
C8—C1—C2	107.3 (2)	C10—C9—H9B	108.0
C8—C1—S	122.09 (18)	H9A—C9—H9B	107.2
C2—C1—S	130.59 (18)	O2—C10—O3	123.6 (2)
C7—C2—C3	119.0 (2)	O2—C10—C9	121.9 (2)
C7—C2—C1	104.91 (19)	O3—C10—C9	114.4 (2)
C3—C2—C1	136.1 (2)	O3—C11—H11A	109.5
C4—C3—C2	118.5 (2)	O3—C11—H11B	109.5
C4—C3—H3	120.8	H11A—C11—H11B	109.5
C2—C3—H3	120.8	O3—C11—H11C	109.5
C3—C4—C5	120.0 (2)	H11A—C11—H11C	109.5
C3—C4—C12	120.5 (3)	H11B—C11—H11C	109.5
C5—C4—C12	119.4 (2)	C4—C12—H12A	109.5
C6—C5—C4	123.0 (2)	C4—C12—H12B	109.5
C6—C5—H5	118.5	H12A—C12—H12B	109.5
C4—C5—H5	118.5	C4—C12—H12C	109.5
C7—C6—C5	115.3 (2)	H12A—C12—H12C	109.5
C7—C6—H6	122.4	H12B—C12—H12C	109.5
C5—C6—H6	122.4	S—C13—H13A	109.5
C6—C7—C2	124.2 (2)	S—C13—H13B	109.5
C6—C7—O1	125.2 (2)	H13A—C13—H13B	109.5
C2—C7—O1	110.58 (19)	S—C13—H13C	109.5
C1—C8—O1	111.21 (19)	H13A—C13—H13C	109.5
C1—C8—C9	132.8 (2)	H13B—C13—H13C	109.5

O4—S—C1—C8	−129.6 (2)	C1—C2—C7—C6	179.0 (2)
C13—S—C1—C8	120.6 (2)	C3—C2—C7—O1	179.36 (19)
O4—S—C1—C2	48.5 (2)	C1—C2—C7—O1	−1.1 (2)
C13—S—C1—C2	−61.4 (2)	C8—O1—C7—C6	−178.8 (2)
C8—C1—C2—C7	0.5 (2)	C8—O1—C7—C2	1.2 (2)
S—C1—C2—C7	−177.78 (18)	C2—C1—C8—O1	0.3 (3)
C8—C1—C2—C3	180.0 (3)	S—C1—C8—O1	178.70 (15)
S—C1—C2—C3	1.7 (4)	C2—C1—C8—C9	−178.3 (2)
C7—C2—C3—C4	0.5 (3)	S—C1—C8—C9	0.1 (4)
C1—C2—C3—C4	−178.9 (2)	C7—O1—C8—C1	−0.9 (2)
C2—C3—C4—C5	−0.1 (4)	C7—O1—C8—C9	177.97 (19)
C2—C3—C4—C12	−179.8 (2)	C1—C8—C9—C10	−72.1 (3)
C3—C4—C5—C6	−0.3 (4)	O1—C8—C9—C10	109.3 (2)
C12—C4—C5—C6	179.4 (2)	C11—O3—C10—O2	0.7 (4)
C4—C5—C6—C7	0.3 (4)	C11—O3—C10—C9	179.8 (3)
C5—C6—C7—C2	0.2 (4)	C8—C9—C10—O2	−176.1 (3)
C5—C6—C7—O1	−179.8 (2)	C8—C9—C10—O3	4.8 (3)
C3—C2—C7—C6	−0.6 (3)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄O₄S
M_r	266.30
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.9331 (6), 8.1097 (6), 10.7017 (8)
α, β, γ (°)	71.601 (1), 81.107 (1), 84.303 (1)
V (Å³)	644.51 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3414, 2237, 1788
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.04
No. of reflections	2237
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36

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. 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, o3832. Web of Science CSD CrossRef IUCr Journals Google Scholar
Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007b). Acta Cryst. E63, o3839. 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