organic compounds
2-(5-Fluoro-3-isopropylsulfanyl-7-methyl-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
The title compound, C14H15FO3S, was prepared by alkaline hydrolysis of ethyl 2-(5-fluoro-3-isopropylsulfanyl-7-methyl-1-benzofuran-2-yl)acetate. In the crystal, molecules are linked via pairs of O—H⋯O hydrogen bonds, forming inversion dimers. These dimers are connected by weak C—H⋯O hydrogen bonds.
Related literature
For background information and the crystal structures of related compounds, see: Seo et al. (2011, 2012).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536812008240/ld2050sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812008240/ld2050Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812008240/ld2050Isup3.cml
Ethyl 2-(5-fluoro-3-isopropylsulfanyl-7-methyl-1-benzofuran-2-yl)acetate (372 mg, 1.2 mmol) was added to a solution of potassium hydroxide (336 mg, 6 mmol) in water (10 ml) and methanol (10 ml), and the mixture was refluxed for 6h, 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. The organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by
(ethyl acetate) to afford the title compound as a colorless solid [yield 87%, m.p. 436-437 K; Rf = 0.44 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in diisopropyl ether at room temperature.H atom in the carboxyl group is found in a different Fourier map and refined freely. The other H atoms of C atoms were positioned geometrically and refined using a riding model, with C–H = 0.95 Å for aryl, 1.0 Å for methine, 0.99 Å for methylene and 0.98 Å for methyl H atoms, respectively. Uiso(H) =1.2Ueq(C) for aryl, methine, and methylene, and 1.5Ueq(C) for methyl H atoms. The positions of methyl hydrogens were optimized rotationally. The split of C13 atom was ignored because the disordered ellipsoids also split into two.
As a part of our continuing study of 2-(5-halo-3-isopropylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives containing 5-fluoro (Seo et al. , 2011) and 5-bromo (Seo et al. , 2012) substituents, we report herein the
of the title compound.In the title molecule (Fig. 1), the benzofuran unit is essentially planar, with a mean deviation of 0.010 (1) Å from the least-squares plane defined by the nine constituent atoms. In the
the carboxyl groups are involved in intermolecular O–H···O hydrogen bonds (Fig. 2 & Table 1), which link the molecules into centrosymmetric dimers. These dimers are stuck by weak intermolecular C–H···O hydrogen bonds (Fig. 2 & Table 1).For background information and the crystal structures of related compounds, see: Seo et al. (2011, 2012).
Data collection: APEX2 (Bruker, 2009); cell
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).C14H15FO3S | Z = 2 |
Mr = 282.32 | F(000) = 296 |
Triclinic, P1 | Dx = 1.352 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4365 (2) Å | Cell parameters from 5886 reflections |
b = 9.2771 (2) Å | θ = 2.4–28.4° |
c = 9.7956 (2) Å | µ = 0.25 mm−1 |
α = 91.404 (1)° | T = 173 K |
β = 91.2710 (1)° | Block, colourless |
γ = 115.111 (1)° | 0.35 × 0.32 × 0.28 mm |
V = 693.55 (3) Å3 |
Bruker SMART APEXII CCD diffractometer | 3467 independent reflections |
Radiation source: rotating anode | 2946 reflections with I > 2σ(I) |
Graphite multilayer monochromator | Rint = 0.028 |
Detector resolution: 10.0 pixels mm-1 | θmax = 28.4°, θmin = 2.1° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −11→12 |
Tmin = 0.919, Tmax = 0.934 | l = −13→13 |
12921 measured reflections |
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)] = 0.051 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0853P)2 + 0.3723P] where P = (Fo2 + 2Fc2)/3 |
3467 reflections | (Δ/σ)max < 0.001 |
179 parameters | Δρmax = 0.93 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C14H15FO3S | γ = 115.111 (1)° |
Mr = 282.32 | V = 693.55 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4365 (2) Å | Mo Kα radiation |
b = 9.2771 (2) Å | µ = 0.25 mm−1 |
c = 9.7956 (2) Å | T = 173 K |
α = 91.404 (1)° | 0.35 × 0.32 × 0.28 mm |
β = 91.2710 (1)° |
Bruker SMART APEXII CCD diffractometer | 3467 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2946 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.934 | Rint = 0.028 |
12921 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.93 e Å−3 |
3467 reflections | Δρmin = −0.44 e Å−3 |
179 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.64151 (7) | 0.31790 (6) | 0.28518 (5) | 0.03564 (17) | |
F1 | 0.78061 (17) | 0.98655 (14) | 0.35845 (16) | 0.0503 (4) | |
O1 | 0.23013 (17) | 0.40794 (15) | 0.34150 (13) | 0.0310 (3) | |
O2 | 0.1261 (3) | 0.16845 (17) | 0.07988 (16) | 0.0552 (5) | |
O3 | 0.0331 (2) | −0.07438 (16) | 0.15984 (16) | 0.0434 (4) | |
H3O | −0.022 (5) | −0.102 (5) | 0.082 (4) | 0.097 (13)* | |
C1 | 0.4901 (2) | 0.3980 (2) | 0.30894 (17) | 0.0273 (4) | |
C2 | 0.5220 (2) | 0.5633 (2) | 0.32776 (16) | 0.0261 (3) | |
C3 | 0.6709 (2) | 0.7080 (2) | 0.33113 (19) | 0.0309 (4) | |
H3 | 0.7852 | 0.7141 | 0.3203 | 0.037* | |
C4 | 0.6403 (3) | 0.8411 (2) | 0.3512 (2) | 0.0343 (4) | |
C5 | 0.4765 (3) | 0.8394 (2) | 0.3669 (2) | 0.0348 (4) | |
H5 | 0.4664 | 0.9371 | 0.3791 | 0.042* | |
C6 | 0.3272 (3) | 0.6965 (2) | 0.36477 (18) | 0.0312 (4) | |
C7 | 0.3583 (2) | 0.5618 (2) | 0.34579 (17) | 0.0273 (4) | |
C8 | 0.3153 (2) | 0.3132 (2) | 0.31893 (17) | 0.0287 (4) | |
C9 | 0.1464 (3) | 0.6865 (3) | 0.3815 (2) | 0.0426 (5) | |
H9A | 0.0604 | 0.5752 | 0.3705 | 0.064* | |
H9B | 0.1222 | 0.7497 | 0.3122 | 0.064* | |
H9C | 0.1386 | 0.7283 | 0.4728 | 0.064* | |
C10 | 0.2049 (3) | 0.1387 (2) | 0.30994 (19) | 0.0349 (4) | |
H10A | 0.1139 | 0.1115 | 0.3792 | 0.042* | |
H10B | 0.2789 | 0.0828 | 0.3322 | 0.042* | |
C11 | 0.1170 (3) | 0.0792 (2) | 0.17141 (19) | 0.0317 (4) | |
C12 | 0.6510 (5) | 0.3118 (4) | 0.0971 (3) | 0.0624 (8) | |
H12 | 0.5284 | 0.2565 | 0.0581 | 0.075* | |
C13 | 0.7450 (8) | 0.2152 (6) | 0.0605 (5) | 0.124 (2) | |
H13A | 0.7367 | 0.1960 | −0.0388 | 0.186* | |
H13B | 0.6925 | 0.1132 | 0.1055 | 0.186* | |
H13C | 0.8683 | 0.2722 | 0.0904 | 0.186* | |
C14 | 0.7333 (5) | 0.4753 (4) | 0.0408 (3) | 0.0766 (10) | |
H14A | 0.8535 | 0.5318 | 0.0783 | 0.115* | |
H14B | 0.6652 | 0.5344 | 0.0663 | 0.115* | |
H14C | 0.7351 | 0.4665 | −0.0590 | 0.115* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0454 (3) | 0.0356 (3) | 0.0327 (3) | 0.0233 (2) | 0.0074 (2) | 0.00516 (18) |
F1 | 0.0421 (7) | 0.0235 (6) | 0.0731 (9) | 0.0025 (5) | 0.0028 (6) | −0.0043 (6) |
O1 | 0.0274 (6) | 0.0274 (6) | 0.0340 (7) | 0.0077 (5) | −0.0037 (5) | 0.0021 (5) |
O2 | 0.0785 (12) | 0.0260 (7) | 0.0413 (8) | 0.0041 (7) | −0.0244 (8) | 0.0048 (6) |
O3 | 0.0606 (10) | 0.0224 (6) | 0.0362 (8) | 0.0077 (6) | −0.0109 (7) | 0.0002 (5) |
C1 | 0.0329 (9) | 0.0237 (8) | 0.0232 (7) | 0.0103 (7) | −0.0018 (6) | −0.0003 (6) |
C2 | 0.0304 (9) | 0.0243 (8) | 0.0217 (7) | 0.0101 (7) | −0.0009 (6) | −0.0001 (6) |
C3 | 0.0278 (9) | 0.0277 (8) | 0.0334 (9) | 0.0082 (7) | 0.0014 (7) | −0.0006 (7) |
C4 | 0.0365 (10) | 0.0232 (8) | 0.0354 (9) | 0.0056 (7) | −0.0011 (7) | −0.0015 (7) |
C5 | 0.0436 (11) | 0.0269 (8) | 0.0353 (9) | 0.0164 (8) | 0.0006 (8) | −0.0004 (7) |
C6 | 0.0342 (10) | 0.0329 (9) | 0.0287 (8) | 0.0164 (8) | −0.0014 (7) | 0.0023 (7) |
C7 | 0.0285 (8) | 0.0261 (8) | 0.0244 (8) | 0.0091 (7) | −0.0034 (6) | 0.0013 (6) |
C8 | 0.0324 (9) | 0.0243 (8) | 0.0259 (8) | 0.0088 (7) | −0.0038 (6) | 0.0012 (6) |
C9 | 0.0393 (11) | 0.0434 (11) | 0.0521 (12) | 0.0240 (9) | 0.0007 (9) | 0.0072 (9) |
C10 | 0.0392 (10) | 0.0245 (8) | 0.0326 (9) | 0.0057 (7) | −0.0070 (8) | 0.0034 (7) |
C11 | 0.0328 (9) | 0.0229 (8) | 0.0332 (9) | 0.0061 (7) | −0.0037 (7) | 0.0015 (6) |
C12 | 0.097 (2) | 0.0646 (16) | 0.0406 (12) | 0.0479 (16) | 0.0232 (13) | 0.0050 (11) |
C13 | 0.202 (6) | 0.151 (4) | 0.086 (3) | 0.135 (5) | 0.063 (3) | 0.026 (3) |
C14 | 0.116 (3) | 0.076 (2) | 0.0474 (15) | 0.048 (2) | 0.0261 (16) | 0.0178 (14) |
S1—C1 | 1.7464 (19) | C6—C9 | 1.502 (3) |
S1—C12 | 1.847 (3) | C8—C10 | 1.485 (2) |
F1—C4 | 1.365 (2) | C9—H9A | 0.9800 |
O1—C8 | 1.368 (2) | C9—H9B | 0.9800 |
O1—C7 | 1.376 (2) | C9—H9C | 0.9800 |
O2—C11 | 1.217 (2) | C10—C11 | 1.506 (3) |
O3—C11 | 1.295 (2) | C10—H10A | 0.9900 |
O3—H3O | 0.86 (4) | C10—H10B | 0.9900 |
C1—C8 | 1.352 (3) | C12—C13 | 1.469 (4) |
C1—C2 | 1.446 (2) | C12—C14 | 1.501 (4) |
C2—C7 | 1.390 (3) | C12—H12 | 1.0000 |
C2—C3 | 1.395 (2) | C13—H13A | 0.9800 |
C3—C4 | 1.375 (3) | C13—H13B | 0.9800 |
C3—H3 | 0.9500 | C13—H13C | 0.9800 |
C4—C5 | 1.387 (3) | C14—H14A | 0.9800 |
C5—C6 | 1.387 (3) | C14—H14B | 0.9800 |
C5—H5 | 0.9500 | C14—H14C | 0.9800 |
C6—C7 | 1.390 (3) | ||
C1—S1—C12 | 101.58 (11) | C6—C9—H9C | 109.5 |
C8—O1—C7 | 105.60 (14) | H9A—C9—H9C | 109.5 |
C11—O3—H3O | 110 (3) | H9B—C9—H9C | 109.5 |
C8—C1—C2 | 105.76 (16) | C8—C10—C11 | 113.50 (15) |
C8—C1—S1 | 125.54 (14) | C8—C10—H10A | 108.9 |
C2—C1—S1 | 128.66 (14) | C11—C10—H10A | 108.9 |
C7—C2—C3 | 119.79 (16) | C8—C10—H10B | 108.9 |
C7—C2—C1 | 105.53 (15) | C11—C10—H10B | 108.9 |
C3—C2—C1 | 134.68 (17) | H10A—C10—H10B | 107.7 |
C4—C3—C2 | 115.14 (17) | O2—C11—O3 | 123.96 (17) |
C4—C3—H3 | 122.4 | O2—C11—C10 | 122.48 (16) |
C2—C3—H3 | 122.4 | O3—C11—C10 | 113.55 (16) |
F1—C4—C3 | 118.24 (18) | C13—C12—C14 | 112.4 (3) |
F1—C4—C5 | 116.81 (17) | C13—C12—S1 | 107.5 (2) |
C3—C4—C5 | 124.94 (17) | C14—C12—S1 | 112.2 (2) |
C4—C5—C6 | 120.63 (17) | C13—C12—H12 | 108.2 |
C4—C5—H5 | 119.7 | C14—C12—H12 | 108.2 |
C6—C5—H5 | 119.7 | S1—C12—H12 | 108.2 |
C5—C6—C7 | 114.44 (17) | C12—C13—H13A | 109.5 |
C5—C6—C9 | 123.24 (18) | C12—C13—H13B | 109.5 |
C7—C6—C9 | 122.32 (18) | H13A—C13—H13B | 109.5 |
O1—C7—C2 | 110.54 (15) | C12—C13—H13C | 109.5 |
O1—C7—C6 | 124.41 (17) | H13A—C13—H13C | 109.5 |
C2—C7—C6 | 125.04 (17) | H13B—C13—H13C | 109.5 |
C1—C8—O1 | 112.56 (15) | C12—C14—H14A | 109.5 |
C1—C8—C10 | 130.95 (18) | C12—C14—H14B | 109.5 |
O1—C8—C10 | 116.49 (16) | H14A—C14—H14B | 109.5 |
C6—C9—H9A | 109.5 | C12—C14—H14C | 109.5 |
C6—C9—H9B | 109.5 | H14A—C14—H14C | 109.5 |
H9A—C9—H9B | 109.5 | H14B—C14—H14C | 109.5 |
C12—S1—C1—C8 | 91.91 (19) | C3—C2—C7—C6 | 1.5 (3) |
C12—S1—C1—C2 | −91.00 (18) | C1—C2—C7—C6 | −178.68 (16) |
C8—C1—C2—C7 | −0.86 (19) | C5—C6—C7—O1 | 179.41 (16) |
S1—C1—C2—C7 | −178.39 (13) | C9—C6—C7—O1 | −0.6 (3) |
C8—C1—C2—C3 | 178.94 (19) | C5—C6—C7—C2 | −1.0 (3) |
S1—C1—C2—C3 | 1.4 (3) | C9—C6—C7—C2 | 179.04 (18) |
C7—C2—C3—C4 | −0.7 (3) | C2—C1—C8—O1 | 0.5 (2) |
C1—C2—C3—C4 | 179.49 (18) | S1—C1—C8—O1 | 178.10 (12) |
C2—C3—C4—F1 | 178.68 (16) | C2—C1—C8—C10 | −179.33 (17) |
C2—C3—C4—C5 | −0.4 (3) | S1—C1—C8—C10 | −1.7 (3) |
F1—C4—C5—C6 | −178.20 (17) | C7—O1—C8—C1 | 0.13 (19) |
C3—C4—C5—C6 | 0.9 (3) | C7—O1—C8—C10 | 179.95 (14) |
C4—C5—C6—C7 | −0.2 (3) | C1—C8—C10—C11 | −98.2 (2) |
C4—C5—C6—C9 | 179.80 (19) | O1—C8—C10—C11 | 82.0 (2) |
C8—O1—C7—C2 | −0.71 (18) | C8—C10—C11—O2 | −5.3 (3) |
C8—O1—C7—C6 | 178.95 (16) | C8—C10—C11—O3 | 174.37 (18) |
C3—C2—C7—O1 | −178.85 (15) | C1—S1—C12—C13 | −168.1 (3) |
C1—C2—C7—O1 | 0.98 (19) | C1—S1—C12—C14 | 67.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O2i | 0.86 (4) | 1.76 (4) | 2.616 (2) | 176 (4) |
C9—H9B···O3ii | 0.98 | 2.56 | 3.534 (3) | 171 |
Symmetry codes: (i) −x, −y, −z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H15FO3S |
Mr | 282.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.4365 (2), 9.2771 (2), 9.7956 (2) |
α, β, γ (°) | 91.404 (1), 91.2710 (1), 115.111 (1) |
V (Å3) | 693.55 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.35 × 0.32 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.919, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12921, 3467, 2946 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.155, 1.06 |
No. of reflections | 3467 |
No. of parameters | 179 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.93, −0.44 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O2i | 0.86 (4) | 1.76 (4) | 2.616 (2) | 176 (4) |
C9—H9B···O3ii | 0.98 | 2.56 | 3.534 (3) | 171.1 |
Symmetry codes: (i) −x, −y, −z; (ii) x, y+1, z. |
References
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2011). Acta Cryst. E67, o3112. Web of Science CSD CrossRef IUCr Journals Google Scholar
Seo, P. J., Choi, H. D., Son, B. W. & Lee, U. (2012). Acta Cryst. E68, o58. Web of Science CSD 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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As a part of our continuing study of 2-(5-halo-3-isopropylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives containing 5-fluoro (Seo et al. , 2011) and 5-bromo (Seo et al. , 2012) substituents, 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 0.010 (1) Å from the least-squares plane defined by the nine constituent atoms. In the crystal structure, the carboxyl groups are involved in intermolecular O–H···O hydrogen bonds (Fig. 2 & Table 1), which link the molecules into centrosymmetric dimers. These dimers are stuck by weak intermolecular C–H···O hydrogen bonds (Fig. 2 & Table 1).