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ISSN: 2056-9890

2-(5,7-Di­methyl-3-methyl­sulfanyl-1-benzo­furan-2-yl)acetic acid

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 14 July 2008; accepted 22 July 2008; online 26 July 2008)

The title compound, C13H14O3S, was prepared by alkaline hydrolysis of ethyl 2-(5,7-dimethyl-3-methyl­sulfanyl-1-benzofuran-2-yl)acetate. In the crystal structure, the carboxyl groups are involved in inter­molecular O—H⋯O hydrogen bonds, which link the mol­ecules into centrosymmetric dimers. These dimers are further packed into stacks along the a axis by weak C—H⋯π inter­actions.

Related literature

For the crystal structures of similar 2-(3-methyl­sulfanyl-1-benzofuran-2-yl)acetic acid derivatives, see: Choi et al. (2007[Choi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o3468.]); Seo et al. (2007[Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o2048-o2049.]).

[Scheme 1]

Experimental

Crystal data
  • C13H14O3S

  • Mr = 250.30

  • Triclinic, [P \overline 1]

  • a = 4.7225 (9) Å

  • b = 7.476 (2) Å

  • c = 17.687 (3) Å

  • α = 80.91 (3)°

  • β = 89.86 (3)°

  • γ = 80.67 (3)°

  • V = 608.3 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.26 mm−1

  • T = 293 (2) K

  • 0.40 × 0.40 × 0.20 mm

Data collection
  • Bruker SMART CCD diffractometer

  • Absorption correction: none

  • 4707 measured reflections

  • 2344 independent reflections

  • 2156 reflections with I > 2σ(I)

  • Rint = 0.059

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.144

  • S = 1.24

  • 2344 reflections

  • 161 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.41 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3O⋯O2i 0.73 (4) 1.95 (4) 2.680 (3) 177 (4)
C9—H9ACgii 0.96 2.72 3.621 (4) 156
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x+1, y, z.

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 1998[Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

As a part of our ongoing studies on the synthesis and structures of 2-(3-methylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives, we have described 2-(5-ethyl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid (Seo et al., 2007) and 2-(3-methylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007). Here we report the crystal structure of the title compound, (I) (Fig. 1).

In (I), the benzofuran unit is essentially planar, with a mean deviation of 0.004 (2) Å from the least-squares plane defined by the nine constituent atoms. The crystal packing (Fig. 2) is stabilized by classical inversion-related O—H···O hydrogen bonds (Table 1) and C—H···π interactions between a methyl H atom and the ring C2–C7 (Cg is its centroid) of a neighbouring molecule (Table 1).

Related literature top

For the crystal structures of similar 2-(3-methylsulfanyl-1-benzofuran-2-yl) acetic acid derivatives, see: Choi et al. (2007); Seo et al. (2007).

Experimental top

Ethyl 2-(5,7-dimethyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate (417 mg, 1.50 mmol) was added to a solution of potassium hydroxide (505 mg, 9.0 mmol) in water (25 ml) and methanol (25 ml), and the mixture was refluxed for 5 h, then cooled. Water was added, and the solution was extracted with dichloromethane. The aqueous layer was acidified to pH 1 with concentrated hydrochloric acid and then extracted with chloroform, 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 82%, m.p. 420–421 K; Rf = 0.66 (ethyl acetate)]. 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 2.32 (s, 3H), 2.43 (s, 3H), 2.45 (s, 3H), 4.03 (s, 2H), 6.93 (s, 1H), 7.25 (s, 1H), 10.10 (s, 1H); EI—MS 250 [M+].

Refinement top

Atom H3O of the hydroxy group was found in a difference Fourier map and refined isotropically. The other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms, 0.97 Å for methylene H atoms and 0.96 Å for methyl H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms and 1.5Ueq(C) for methyl H atoms.

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
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A portion of the crystal packing showing C—H···π interaction and hydrogen bonds (dotted lines). Cg denotes the C2–C7 ring centroid [symmetry codes: (i) x + 1, y, z; (ii) -x + 1, -y + 2, -z + 1; (iii) x - 1, y, z].
2-(5,7-Dimethyl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid top
Crystal data top
C13H14O3SZ = 2
Mr = 250.30F(000) = 264
Triclinic, P1Dx = 1.367 Mg m3
Hall symbol: -P_1Melting point = 420–421 K
a = 4.7225 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.476 (2) ÅCell parameters from 3835 reflections
c = 17.687 (3) Åθ = 2.3–28.3°
α = 80.91 (3)°µ = 0.26 mm1
β = 89.86 (3)°T = 293 K
γ = 80.67 (3)°Block, colourless
V = 608.3 (2) Å30.40 × 0.40 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer
2156 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.059
Graphite monochromatorθmax = 26.0°, θmin = 1.2°
Detector resolution: 10.0 pixels mm-1h = 55
ϕ and ω scansk = 99
4707 measured reflectionsl = 2121
2344 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.24 w = 1/[σ2(Fo2) + (0.063P)2 + 0.3562P]
where P = (Fo2 + 2Fc2)/3
2344 reflections(Δ/σ)max < 0.001
161 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
C13H14O3Sγ = 80.67 (3)°
Mr = 250.30V = 608.3 (2) Å3
Triclinic, P1Z = 2
a = 4.7225 (9) ÅMo Kα radiation
b = 7.476 (2) ŵ = 0.26 mm1
c = 17.687 (3) ÅT = 293 K
α = 80.91 (3)°0.40 × 0.40 × 0.20 mm
β = 89.86 (3)°
Data collection top
Bruker SMART CCD
diffractometer
2156 reflections with I > 2σ(I)
4707 measured reflectionsRint = 0.059
2344 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 1.24Δρmax = 0.38 e Å3
2344 reflectionsΔρmin = 0.41 e Å3
161 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
xyzUiso*/Ueq
S0.85977 (13)0.34264 (8)0.36615 (3)0.0254 (2)
O10.4166 (3)0.8236 (2)0.27417 (9)0.0223 (4)
O20.2357 (4)0.9616 (2)0.44893 (10)0.0272 (4)
O30.6544 (4)0.7728 (2)0.47532 (11)0.0282 (4)
H3O0.685 (8)0.848 (5)0.494 (2)0.049 (11)*
C10.6982 (5)0.5473 (3)0.30908 (14)0.0214 (5)
C20.7803 (5)0.6242 (3)0.23378 (14)0.0232 (5)
C30.9867 (5)0.5690 (3)0.18203 (15)0.0268 (5)
H31.10980.45740.19360.032*
C41.0055 (6)0.6834 (4)0.11284 (15)0.0293 (6)
C50.8179 (6)0.8526 (3)0.09713 (15)0.0306 (6)
H50.83320.92750.05050.037*
C60.6115 (6)0.9133 (3)0.14758 (15)0.0279 (5)
C70.6010 (5)0.7931 (3)0.21521 (14)0.0231 (5)
C80.4821 (5)0.6706 (3)0.32972 (13)0.0211 (5)
C91.2248 (6)0.6283 (4)0.05502 (17)0.0400 (7)
H9A1.41130.64360.07180.060*
H9B1.17620.70430.00630.060*
H9C1.22650.50210.05020.060*
C100.4134 (6)1.0944 (3)0.13076 (17)0.0359 (6)
H10A0.23251.08330.15440.054*
H10B0.38421.12910.07640.054*
H10C0.49721.18640.15080.054*
C110.3130 (5)0.6760 (3)0.40038 (13)0.0225 (5)
H11A0.34820.55620.43240.027*
H11B0.10990.70500.38690.027*
C120.3944 (5)0.8187 (3)0.44444 (13)0.0195 (5)
C130.7336 (6)0.1752 (3)0.31692 (18)0.0360 (6)
H13A0.52770.19200.31760.054*
H13B0.81100.05380.34210.054*
H13C0.79500.19080.26490.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0300 (3)0.0185 (3)0.0271 (3)0.0028 (2)0.0065 (2)0.0025 (2)
O10.0275 (8)0.0163 (7)0.0230 (9)0.0025 (6)0.0001 (6)0.0039 (6)
O20.0275 (9)0.0214 (8)0.0334 (10)0.0003 (7)0.0053 (7)0.0105 (7)
O30.0251 (9)0.0248 (9)0.0370 (10)0.0017 (7)0.0069 (7)0.0140 (8)
C10.0254 (11)0.0162 (10)0.0241 (12)0.0044 (8)0.0027 (9)0.0063 (9)
C20.0256 (12)0.0200 (11)0.0263 (12)0.0079 (9)0.0025 (9)0.0066 (9)
C30.0267 (12)0.0261 (12)0.0297 (13)0.0068 (9)0.0006 (10)0.0084 (10)
C40.0334 (13)0.0314 (13)0.0289 (13)0.0150 (10)0.0057 (10)0.0125 (10)
C50.0418 (15)0.0292 (13)0.0235 (13)0.0155 (11)0.0006 (10)0.0024 (10)
C60.0366 (13)0.0209 (11)0.0281 (13)0.0092 (10)0.0021 (10)0.0051 (10)
C70.0280 (12)0.0209 (11)0.0227 (12)0.0074 (9)0.0006 (9)0.0066 (9)
C80.0256 (11)0.0170 (10)0.0223 (11)0.0066 (8)0.0045 (9)0.0045 (9)
C90.0449 (16)0.0437 (16)0.0368 (15)0.0173 (13)0.0140 (13)0.0125 (13)
C100.0480 (16)0.0247 (13)0.0318 (14)0.0035 (11)0.0049 (12)0.0031 (11)
C110.0252 (11)0.0191 (10)0.0253 (12)0.0074 (9)0.0000 (9)0.0059 (9)
C120.0218 (11)0.0188 (10)0.0193 (11)0.0071 (8)0.0025 (8)0.0035 (8)
C130.0439 (15)0.0200 (11)0.0452 (16)0.0068 (11)0.0132 (12)0.0066 (11)
Geometric parameters (Å, º) top
S—C11.755 (2)C5—H50.9300
S—C131.808 (3)C6—C71.384 (4)
O1—C81.379 (3)C6—C101.503 (4)
O1—C71.380 (3)C8—C111.484 (3)
O2—C121.215 (3)C9—H9A0.9600
O3—C121.316 (3)C9—H9B0.9600
O3—H3O0.73 (4)C9—H9C0.9600
C1—C81.351 (3)C10—H10A0.9600
C1—C21.443 (3)C10—H10B0.9600
C2—C71.393 (3)C10—H10C0.9600
C2—C31.394 (3)C11—C121.514 (3)
C3—C41.389 (4)C11—H11A0.9700
C3—H30.9300C11—H11B0.9700
C4—C51.410 (4)C13—H13A0.9600
C4—C91.509 (4)C13—H13B0.9600
C5—C61.390 (4)C13—H13C0.9600
C1—S—C13100.58 (12)C4—C9—H9A109.5
C8—O1—C7105.62 (18)C4—C9—H9B109.5
C12—O3—H3O109 (3)H9A—C9—H9B109.5
C8—C1—C2106.3 (2)C4—C9—H9C109.5
C8—C1—S126.10 (19)H9A—C9—H9C109.5
C2—C1—S127.50 (18)H9B—C9—H9C109.5
C7—C2—C3119.3 (2)C6—C10—H10A109.5
C7—C2—C1105.7 (2)C6—C10—H10B109.5
C3—C2—C1135.1 (2)H10A—C10—H10B109.5
C4—C3—C2118.9 (2)C6—C10—H10C109.5
C4—C3—H3120.6H10A—C10—H10C109.5
C2—C3—H3120.6H10B—C10—H10C109.5
C3—C4—C5119.3 (2)C8—C11—C12110.56 (18)
C3—C4—C9120.6 (3)C8—C11—H11A109.5
C5—C4—C9120.1 (2)C12—C11—H11A109.5
C6—C5—C4123.5 (2)C8—C11—H11B109.5
C6—C5—H5118.3C12—C11—H11B109.5
C4—C5—H5118.3H11A—C11—H11B108.1
C7—C6—C5114.6 (2)O2—C12—O3124.3 (2)
C7—C6—C10122.1 (2)O2—C12—C11122.7 (2)
C5—C6—C10123.3 (2)O3—C12—C11112.94 (19)
O1—C7—C6125.3 (2)S—C13—H13A109.5
O1—C7—C2110.3 (2)S—C13—H13B109.5
C6—C7—C2124.4 (2)H13A—C13—H13B109.5
C1—C8—O1112.1 (2)S—C13—H13C109.5
C1—C8—C11132.8 (2)H13A—C13—H13C109.5
O1—C8—C11115.00 (19)H13B—C13—H13C109.5
C13—S—C1—C8110.5 (2)C10—C6—C7—O10.8 (4)
C13—S—C1—C274.3 (2)C5—C6—C7—C20.5 (3)
C8—C1—C2—C70.2 (2)C10—C6—C7—C2179.7 (2)
S—C1—C2—C7175.77 (17)C3—C2—C7—O1178.87 (19)
C8—C1—C2—C3179.0 (2)C1—C2—C7—O10.2 (2)
S—C1—C2—C33.0 (4)C3—C2—C7—C60.1 (3)
C7—C2—C3—C40.7 (3)C1—C2—C7—C6179.1 (2)
C1—C2—C3—C4179.4 (2)C2—C1—C8—O10.5 (2)
C2—C3—C4—C50.6 (3)S—C1—C8—O1175.57 (15)
C2—C3—C4—C9179.7 (2)C2—C1—C8—C11177.8 (2)
C3—C4—C5—C60.0 (4)S—C1—C8—C111.8 (4)
C9—C4—C5—C6179.6 (2)C7—O1—C8—C10.5 (2)
C4—C5—C6—C70.6 (4)C7—O1—C8—C11178.39 (17)
C4—C5—C6—C10179.6 (2)C1—C8—C11—C12108.4 (3)
C8—O1—C7—C6179.4 (2)O1—C8—C11—C1268.9 (2)
C8—O1—C7—C20.4 (2)C8—C11—C12—O2109.1 (2)
C5—C6—C7—O1179.4 (2)C8—C11—C12—O369.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O2i0.73 (4)1.95 (4)2.680 (3)177 (4)
C9—H9A···Cgii0.962.723.621 (4)156
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC13H14O3S
Mr250.30
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)4.7225 (9), 7.476 (2), 17.687 (3)
α, β, γ (°)80.91 (3), 89.86 (3), 80.67 (3)
V3)608.3 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.26
Crystal size (mm)0.40 × 0.40 × 0.20
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4707, 2344, 2156
Rint0.059
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.144, 1.24
No. of reflections2344
No. of parameters161
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.38, 0.41

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···AD—HH···AD···AD—H···A
O3—H3O···O2i0.73 (4)1.95 (4)2.680 (3)177 (4)
C9—H9A···Cgii0.962.723.621 (4)156.4
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y, z.
 

References

First citationBrandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChoi, H. D., Seo, P. J., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o3468.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationSeo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2007). Acta Cryst. E63, o2048–o2049.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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