2-(5-Fluoro-7-methyl-3-methyl­sulfanyl-1-benzofuran-2-yl)acetic acid

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

doi:10.1107/S1600536811026729

organic compounds

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Volume 67| Part 8| August 2011| Page o1978

doi:10.1107/S1600536811026729

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2-(5-Fluoro-7-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid

Pil Ja Seo,^a Hong Dae Choi,^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 4 July 2011; accepted 5 July 2011; online 9 July 2011)

The title compound, C₁₂H₁₁FO₃S, was prepared by alkaline hydrolysis of ethyl 2-(5-fluoro-7-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate. In the crystal, the carboxyl groups are involved in intermolecular O—H⋯O hydrogen bonds, which link the molecules into centrosymmetric dimers.

Related literature

For the pharmacological activity of benzofuran compounds, see: Aslam et al. (2009 ); Galal et al. (2009 ); Khan et al. (2005 ). For natural products with benzofuran rings, see: Akgul & Anil (2003 ); Soekamto et al. (2003 ). For structural studies of related 2-(5-halo-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives, see: Choi et al. (2009a ,b ).

Experimental

Crystal data

C₁₂H₁₁FO₃S
M_r = 254.27
Monoclinic, P 2₁ /c
a = 16.1747 (9) Å
b = 4.9242 (3) Å
c = 14.4572 (7) Å
β = 91.701 (3)°
V = 1150.97 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.42 × 0.19 × 0.09 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.889, T_max = 0.975
10241 measured reflections
2873 independent reflections
2114 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.153
S = 1.05
2873 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.38 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
O2—H2⋯O3ⁱ	0.84	1.87	2.706 (2)	177
Symmetry code: (i) -x, -y+1, -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 (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/S1600536811026729/xu5266sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026729/xu5266Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026729/xu5266Isup3.cml

checkCIF report

Comment top

Recently, many compounds involving a benzofuran moiety have drawn much attention due to their valuable pharmacological properties such as antibacterial and antifungal, antitumor and antiviral, and antimicrobial activities (Aslam et al., 2009, Galal et al., 2009, Khan et al., 2005). These benzofuran derivatives occur in a wide range of natural products (Akgul & Anil, 2003; Soekamto et al., 2003). As a part of our ongoing study of the substituent effect on the solid state structures of 2-(5-halo-3-methylsulfanyl-1-benzofuran-2-yl) acetic acid analogues (Choi et al., 2009a,b), 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 0.005 (1) Å from the least-squares plane defined by the nine constituent atoms. The carboxyl groups are involved in intermolecular O—H···O hydrogen bonds (Table 1), which link the molecules into centrosymmetric dimers.

Related literature top

For the pharmacological activity of benzofuran compounds, see: Aslam et al. (2009); Galal et al. (2009); Khan et al. (2005). For natural products with benzofuran rings, see: Akgul & Anil (2003); Soekamto et al. (2003). For structural studies of related 2-(5-halo-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives, see: Choi et al. (2009a,b).

Experimental top

Ethyl 2-(5-fluoro-7-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate (338 mg, 1.2 mmol) was added to a solution of potassium hydroxide (337 mg, 6 mmol) in water (10 ml) and methanol (10 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 at reduced pressure. The residue was purified by column chromatography (ethyl acetate) to afford the title compound as a colorless solid [yield 82%, m.p. 436–437 K; R_f = 0.65 (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.

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 (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 with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

2-(5-Fluoro-7-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid top

Crystal data top

C₁₂H₁₁FO₃S	F(000) = 528
M_r = 254.27	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3638 reflections
a = 16.1747 (9) Å	θ = 2.5–27.9°
b = 4.9242 (3) Å	µ = 0.29 mm⁻¹
c = 14.4572 (7) Å	T = 173 K
β = 91.701 (3)°	Block, colourless
V = 1150.97 (11) Å³	0.42 × 0.19 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	2873 independent reflections
Radiation source: rotating anode	2114 reflections with I > 2σ(I)
Graphite multilayer monochromator	R_int = 0.050
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.4°, θ_min = 2.5°
ϕ and ω scans	h = −19→21
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −6→6
T_min = 0.889, T_max = 0.975	l = −19→19
10241 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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F²) = 0.153	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0891P)² + 0.0162P] where P = (F_o² + 2F_c²)/3
2873 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₂H₁₁FO₃S	V = 1150.97 (11) Å³
M_r = 254.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.1747 (9) Å	µ = 0.29 mm⁻¹
b = 4.9242 (3) Å	T = 173 K
c = 14.4572 (7) Å	0.42 × 0.19 × 0.09 mm
β = 91.701 (3)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2873 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2114 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.975	R_int = 0.050
10241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.05	Δρ_max = 0.38 e Å⁻³
2873 reflections	Δρ_min = −0.27 e Å⁻³
156 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	0.15190 (3)	0.70323 (12)	0.30067 (3)	0.0375 (2)
F1	0.38947 (9)	−0.1018 (3)	0.42507 (7)	0.0606 (5)
O1	0.29563 (7)	0.4092 (3)	0.10941 (7)	0.0292 (3)
O2	0.10398 (10)	0.3674 (3)	0.03782 (12)	0.0558 (5)
H2	0.0565	0.3189	0.0195	0.084*
O3	0.05132 (8)	0.7769 (3)	0.01681 (10)	0.0438 (4)
C1	0.22446 (10)	0.5379 (4)	0.23383 (11)	0.0273 (4)
C2	0.28406 (10)	0.3388 (4)	0.26357 (10)	0.0255 (4)
C3	0.30513 (12)	0.2144 (4)	0.34788 (11)	0.0324 (5)
H3	0.2782	0.2579	0.4035	0.039*
C4	0.36662 (11)	0.0275 (5)	0.34518 (11)	0.0355 (5)
C5	0.40838 (11)	−0.0469 (4)	0.26625 (11)	0.0337 (5)
H5	0.4506	−0.1811	0.2700	0.040*
C6	0.38838 (10)	0.0749 (4)	0.18228 (11)	0.0291 (4)
C7	0.32623 (11)	0.2652 (4)	0.18496 (10)	0.0257 (4)
C8	0.23433 (10)	0.5719 (4)	0.14195 (11)	0.0286 (4)
C9	0.43079 (12)	0.0035 (5)	0.09414 (12)	0.0402 (5)
H9A	0.3896	−0.0592	0.0479	0.060*
H9B	0.4713	−0.1410	0.1065	0.060*
H9C	0.4591	0.1642	0.0707	0.060*
C10	0.18996 (12)	0.7432 (5)	0.07219 (13)	0.0358 (5)
H10A	0.2252	0.7646	0.0179	0.043*
H10B	0.1815	0.9259	0.0989	0.043*
C11	0.10771 (11)	0.6315 (4)	0.04024 (11)	0.0292 (4)
C12	0.07261 (13)	0.4483 (5)	0.30180 (15)	0.0471 (6)
H12A	0.0508	0.4187	0.2386	0.071*
H12B	0.0278	0.5087	0.3411	0.071*
H12C	0.0959	0.2782	0.3263	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0334 (3)	0.0289 (4)	0.0506 (3)	0.0038 (2)	0.0054 (2)	−0.0077 (2)
F1	0.0761 (9)	0.0696 (12)	0.0360 (6)	0.0303 (8)	−0.0012 (5)	0.0216 (6)
O1	0.0293 (6)	0.0322 (8)	0.0258 (5)	0.0010 (6)	−0.0025 (4)	0.0047 (5)
O2	0.0470 (9)	0.0267 (9)	0.0917 (11)	−0.0022 (8)	−0.0345 (8)	0.0036 (9)
O3	0.0319 (8)	0.0305 (9)	0.0680 (9)	0.0070 (7)	−0.0143 (7)	0.0012 (7)
C1	0.0244 (8)	0.0239 (10)	0.0335 (8)	−0.0010 (8)	−0.0007 (6)	−0.0001 (8)
C2	0.0238 (8)	0.0249 (10)	0.0279 (7)	−0.0015 (8)	0.0001 (6)	−0.0010 (7)
C3	0.0373 (10)	0.0343 (12)	0.0258 (7)	0.0002 (9)	0.0020 (7)	0.0027 (8)
C4	0.0401 (10)	0.0375 (13)	0.0286 (8)	0.0040 (10)	−0.0042 (7)	0.0097 (8)
C5	0.0296 (9)	0.0306 (12)	0.0406 (9)	0.0063 (9)	−0.0022 (7)	0.0001 (9)
C6	0.0246 (8)	0.0307 (12)	0.0321 (8)	−0.0019 (8)	0.0007 (6)	−0.0042 (8)
C7	0.0247 (8)	0.0278 (11)	0.0243 (7)	−0.0033 (8)	−0.0032 (6)	0.0021 (7)
C8	0.0240 (8)	0.0251 (11)	0.0362 (8)	−0.0015 (8)	−0.0052 (6)	0.0024 (8)
C9	0.0342 (10)	0.0504 (15)	0.0362 (9)	0.0065 (10)	0.0058 (7)	−0.0090 (9)
C10	0.0359 (10)	0.0290 (11)	0.0420 (9)	−0.0021 (9)	−0.0099 (8)	0.0080 (9)
C11	0.0324 (9)	0.0257 (11)	0.0291 (7)	−0.0007 (9)	−0.0042 (6)	0.0034 (8)
C12	0.0375 (11)	0.0407 (15)	0.0637 (12)	−0.0032 (11)	0.0121 (9)	−0.0064 (11)

Geometric parameters (Å, º) top

S1—C1	1.7440 (17)	C5—C6	1.384 (2)
S1—C12	1.795 (2)	C5—H5	0.9500
F1—C4	1.3605 (19)	C6—C7	1.376 (3)
O1—C8	1.369 (2)	C6—C9	1.507 (2)
O1—C7	1.382 (2)	C8—C10	1.484 (3)
O2—C11	1.303 (2)	C9—H9A	0.9800
O2—H2	0.8400	C9—H9B	0.9800
O3—C11	1.200 (2)	C9—H9C	0.9800
C1—C8	1.353 (2)	C10—C11	1.500 (3)
C1—C2	1.432 (3)	C10—H10A	0.9900
C2—C7	1.391 (2)	C10—H10B	0.9900
C2—C3	1.397 (2)	C12—H12A	0.9800
C3—C4	1.356 (3)	C12—H12B	0.9800
C3—H3	0.9500	C12—H12C	0.9800
C4—C5	1.392 (2)

C1—S1—C12	99.86 (10)	C1—C8—O1	111.87 (15)
C8—O1—C7	105.96 (12)	C1—C8—C10	131.99 (18)
C11—O2—H2	109.5	O1—C8—C10	116.10 (15)
C8—C1—C2	106.36 (15)	C6—C9—H9A	109.5
C8—C1—S1	125.95 (15)	C6—C9—H9B	109.5
C2—C1—S1	127.69 (12)	H9A—C9—H9B	109.5
C7—C2—C3	119.05 (17)	C6—C9—H9C	109.5
C7—C2—C1	105.98 (14)	H9A—C9—H9C	109.5
C3—C2—C1	134.97 (16)	H9B—C9—H9C	109.5
C4—C3—C2	115.62 (15)	C8—C10—C11	114.05 (16)
C4—C3—H3	122.2	C8—C10—H10A	108.7
C2—C3—H3	122.2	C11—C10—H10A	108.7
C3—C4—F1	118.29 (15)	C8—C10—H10B	108.7
C3—C4—C5	125.18 (16)	C11—C10—H10B	108.7
F1—C4—C5	116.52 (18)	H10A—C10—H10B	107.6
C6—C5—C4	119.90 (18)	O3—C11—O2	123.63 (18)
C6—C5—H5	120.0	O3—C11—C10	121.85 (19)
C4—C5—H5	120.0	O2—C11—C10	114.49 (17)
C7—C6—C5	115.00 (15)	S1—C12—H12A	109.5
C7—C6—C9	122.29 (16)	S1—C12—H12B	109.5
C5—C6—C9	122.71 (17)	H12A—C12—H12B	109.5
C6—C7—O1	124.91 (14)	S1—C12—H12C	109.5
C6—C7—C2	125.25 (16)	H12A—C12—H12C	109.5
O1—C7—C2	109.83 (16)	H12B—C12—H12C	109.5

C12—S1—C1—C8	97.22 (19)	C9—C6—C7—C2	179.39 (18)
C12—S1—C1—C2	−81.79 (19)	C8—O1—C7—C6	179.17 (18)
C8—C1—C2—C7	−0.3 (2)	C8—O1—C7—C2	−0.02 (19)
S1—C1—C2—C7	178.89 (14)	C3—C2—C7—C6	0.3 (3)
C8—C1—C2—C3	−179.4 (2)	C1—C2—C7—C6	−179.00 (18)
S1—C1—C2—C3	−0.2 (3)	C3—C2—C7—O1	179.47 (16)
C7—C2—C3—C4	0.0 (3)	C1—C2—C7—O1	0.2 (2)
C1—C2—C3—C4	179.0 (2)	C2—C1—C8—O1	0.3 (2)
C2—C3—C4—F1	−179.57 (17)	S1—C1—C8—O1	−178.91 (13)
C2—C3—C4—C5	−0.3 (3)	C2—C1—C8—C10	178.18 (19)
C3—C4—C5—C6	0.5 (3)	S1—C1—C8—C10	−1.0 (3)
F1—C4—C5—C6	179.75 (17)	C7—O1—C8—C1	−0.2 (2)
C4—C5—C6—C7	−0.3 (3)	C7—O1—C8—C10	−178.42 (15)
C4—C5—C6—C9	−179.8 (2)	C1—C8—C10—C11	−77.6 (3)
C5—C6—C7—O1	−179.19 (16)	O1—C8—C10—C11	100.2 (2)
C9—C6—C7—O1	0.3 (3)	C8—C10—C11—O3	148.89 (18)
C5—C6—C7—C2	−0.1 (3)	C8—C10—C11—O2	−32.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.84	1.87	2.706 (2)	177

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁FO₃S
M_r	254.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	16.1747 (9), 4.9242 (3), 14.4572 (7)
β (°)	91.701 (3)
V (Å³)	1150.97 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.42 × 0.19 × 0.09

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.889, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	10241, 2873, 2114
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.153, 1.05
No. of reflections	2873
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.27

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
O2—H2···O3ⁱ	0.84	1.87	2.706 (2)	177

Symmetry code: (i) −x, −y+1, −z.

References

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