Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040263/sj2328sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040263/sj2328Isup2.hkl |
CCDC reference: 660309
3-Chloroperbenzoic acid (77%, 336 mg, 1.50 mmol) was added in small portions to a stirred solution of ethyl 2-(5-methyl-3-methylsulfanyl-1-benzofuran-2-yl)acetate (370 mg, 1.40 mmol) in dichloromethane (30 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 in vacuum. The residue was purified by column chromatography (ethyl acetate) to afford the title compound as a colorless solid [yield 88%, m.p. 426–427 K; Rf = 0.56 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in tetrahydrofuran at room temperature.
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms, 0.98 Å for methyl H atoms and 0.99 Å for methylene H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms and 1.5Ueq(C) for methyl H atoms. The highest peak in the difference map is 1.06 Å from S and the largest hole is 0.52 Å from S.
The crystals were small and weakly diffracting and some of the weak high angle intensities could not be detected. This resulted in a lower than normal data completeness.
As part of our ongoing work on the synthesis and structure of 2-benzofuranacetic acid derivatives, the crystal structures of ethyl [5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(5-ethyl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid (Seo et al., 2007) have been described previously. Herein we report the molecular and crystal structure of the title compound (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.007 Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between adjacent benzene units. The Cg···Cgiii distance is 3.641 (3) Å (Cg is the centroid of the C2—C7 benzene ring; symmetry code as in Fig. 2). The molecular packing is further stabilized by two kinds of C—H···O hydrogen bonds between the oxygen of the S═O group and hydrogen atoms on the benzene ring and of the benzylic methylene group respectively (Table 1 and Fig. 2).
For crystal structures of isomers of the title compound, see: Choi et al. (2006); Seo et al. (2007).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C14H16O4S | Z = 2 |
Mr = 280.33 | F(000) = 296 |
Triclinic, P1 | Dx = 1.350 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1499 (8) Å | Cell parameters from 2164 reflections |
b = 9.4958 (9) Å | θ = 2.8–28.2° |
c = 10.283 (1) Å | µ = 0.24 mm−1 |
α = 73.216 (2)° | T = 173 K |
β = 79.023 (2)° | Block, colorless |
γ = 65.188 (2)° | 0.40 × 0.20 × 0.10 mm |
V = 689.37 (12) Å3 |
Bruker SMART CCD diffractometer | 2020 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 25.5°, θmin = 2.1° |
Detector resolution: 10.00 pixels mm-1 | h = −9→9 |
φ and ω scans | k = −11→9 |
3639 measured reflections | l = −12→12 |
2416 independent 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0258P)2 + 0.6897P] where P = (Fo2 + 2Fc2)/3 |
2416 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C14H16O4S | γ = 65.188 (2)° |
Mr = 280.33 | V = 689.37 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1499 (8) Å | Mo Kα radiation |
b = 9.4958 (9) Å | µ = 0.24 mm−1 |
c = 10.283 (1) Å | T = 173 K |
α = 73.216 (2)° | 0.40 × 0.20 × 0.10 mm |
β = 79.023 (2)° |
Bruker SMART CCD diffractometer | 2020 reflections with I > 2σ(I) |
3639 measured reflections | Rint = 0.044 |
2416 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.37 e Å−3 |
2416 reflections | Δρmin = −0.25 e Å−3 |
173 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S | 0.77608 (9) | 0.37116 (9) | 0.95947 (6) | 0.0313 (2) | |
O1 | 0.6542 (2) | 0.54093 (19) | 0.57810 (16) | 0.0239 (4) | |
O2 | 0.7583 (3) | 0.4964 (3) | 1.0281 (2) | 0.0471 (6) | |
O3 | 0.5072 (2) | 0.1180 (2) | 0.7741 (2) | 0.0371 (5) | |
O4 | 0.7751 (3) | 0.1114 (2) | 0.8028 (2) | 0.0426 (5) | |
C1 | 0.7611 (3) | 0.4609 (3) | 0.7840 (2) | 0.0227 (5) | |
C2 | 0.8480 (3) | 0.5637 (3) | 0.6972 (2) | 0.0223 (5) | |
C3 | 0.9769 (3) | 0.6190 (3) | 0.7105 (3) | 0.0255 (6) | |
H3 | 1.0284 | 0.5886 | 0.7948 | 0.031* | |
C4 | 1.0282 (3) | 0.7195 (3) | 0.5981 (3) | 0.0281 (6) | |
C5 | 0.9505 (3) | 0.7637 (3) | 0.4743 (3) | 0.0293 (6) | |
H5 | 0.9867 | 0.8329 | 0.3987 | 0.035* | |
C6 | 0.8229 (3) | 0.7102 (3) | 0.4582 (3) | 0.0280 (6) | |
H6 | 0.7711 | 0.7404 | 0.3741 | 0.034* | |
C7 | 0.7755 (3) | 0.6100 (3) | 0.5722 (2) | 0.0233 (5) | |
C8 | 0.6482 (3) | 0.4513 (3) | 0.7094 (2) | 0.0225 (5) | |
C9 | 0.5246 (3) | 0.3651 (3) | 0.7405 (3) | 0.0258 (6) | |
H9A | 0.4543 | 0.3977 | 0.6608 | 0.031* | |
H9B | 0.4375 | 0.3979 | 0.8181 | 0.031* | |
C10 | 0.6202 (3) | 0.1852 (3) | 0.7753 (2) | 0.0264 (6) | |
C11 | 0.5784 (4) | −0.0565 (3) | 0.8073 (4) | 0.0482 (8) | |
H11A | 0.6075 | −0.0994 | 0.9037 | 0.058* | |
H11B | 0.6907 | −0.0987 | 0.7490 | 0.058* | |
C12 | 0.4391 (5) | −0.1053 (4) | 0.7841 (5) | 0.0621 (11) | |
H12A | 0.4842 | −0.2221 | 0.8058 | 0.093* | |
H12B | 0.4116 | −0.0628 | 0.6883 | 0.093* | |
H12C | 0.3288 | −0.0635 | 0.8426 | 0.093* | |
C13 | 1.1675 (4) | 0.7805 (4) | 0.6083 (3) | 0.0399 (7) | |
H13A | 1.1795 | 0.7681 | 0.7045 | 0.060* | |
H13B | 1.1290 | 0.8936 | 0.5614 | 0.060* | |
H13C | 1.2846 | 0.7195 | 0.5658 | 0.060* | |
C14 | 1.0112 (4) | 0.2413 (4) | 0.9549 (3) | 0.0397 (7) | |
H14A | 1.0434 | 0.1802 | 1.0475 | 0.060* | |
H14B | 1.0852 | 0.3049 | 0.9173 | 0.060* | |
H14C | 1.0335 | 0.1677 | 0.8975 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0308 (4) | 0.0403 (4) | 0.0203 (3) | −0.0133 (3) | −0.0046 (3) | −0.0026 (3) |
O1 | 0.0259 (9) | 0.0238 (9) | 0.0226 (8) | −0.0109 (8) | −0.0074 (7) | −0.0011 (7) |
O2 | 0.0454 (12) | 0.0636 (15) | 0.0336 (11) | −0.0129 (11) | −0.0062 (9) | −0.0239 (10) |
O3 | 0.0294 (10) | 0.0217 (10) | 0.0614 (13) | −0.0105 (8) | −0.0105 (9) | −0.0062 (9) |
O4 | 0.0308 (11) | 0.0278 (11) | 0.0640 (14) | −0.0097 (9) | −0.0166 (10) | 0.0028 (10) |
C1 | 0.0242 (12) | 0.0212 (13) | 0.0210 (12) | −0.0063 (10) | −0.0033 (10) | −0.0053 (10) |
C2 | 0.0226 (12) | 0.0193 (13) | 0.0236 (12) | −0.0041 (10) | −0.0034 (10) | −0.0079 (10) |
C3 | 0.0246 (13) | 0.0242 (14) | 0.0302 (13) | −0.0079 (11) | −0.0054 (11) | −0.0103 (11) |
C4 | 0.0235 (13) | 0.0203 (14) | 0.0421 (15) | −0.0054 (11) | −0.0039 (11) | −0.0138 (11) |
C5 | 0.0291 (14) | 0.0212 (14) | 0.0347 (14) | −0.0097 (11) | −0.0001 (11) | −0.0038 (11) |
C6 | 0.0292 (13) | 0.0253 (14) | 0.0258 (13) | −0.0074 (11) | −0.0058 (11) | −0.0033 (11) |
C7 | 0.0216 (12) | 0.0191 (13) | 0.0286 (13) | −0.0059 (10) | −0.0048 (10) | −0.0061 (10) |
C8 | 0.0233 (12) | 0.0188 (13) | 0.0219 (12) | −0.0053 (10) | −0.0019 (10) | −0.0041 (9) |
C9 | 0.0236 (13) | 0.0267 (14) | 0.0270 (13) | −0.0103 (11) | −0.0028 (10) | −0.0047 (10) |
C10 | 0.0272 (14) | 0.0271 (14) | 0.0249 (12) | −0.0121 (12) | −0.0036 (10) | −0.0028 (10) |
C11 | 0.0380 (17) | 0.0211 (16) | 0.081 (2) | −0.0065 (13) | −0.0117 (16) | −0.0084 (15) |
C12 | 0.046 (2) | 0.0267 (18) | 0.114 (3) | −0.0151 (15) | −0.010 (2) | −0.0145 (19) |
C13 | 0.0368 (16) | 0.0348 (17) | 0.0541 (18) | −0.0197 (14) | −0.0066 (14) | −0.0082 (14) |
C14 | 0.0374 (16) | 0.0379 (17) | 0.0356 (15) | −0.0065 (13) | −0.0157 (13) | −0.0009 (13) |
S—O2 | 1.495 (2) | C6—C7 | 1.386 (4) |
S—C1 | 1.763 (2) | C6—H6 | 0.9500 |
S—C14 | 1.792 (3) | C8—C9 | 1.485 (3) |
O1—C8 | 1.377 (3) | C9—C10 | 1.513 (4) |
O1—C7 | 1.382 (3) | C9—H9A | 0.9900 |
O3—C10 | 1.326 (3) | C9—H9B | 0.9900 |
O3—C11 | 1.463 (3) | C11—C12 | 1.473 (4) |
O4—C10 | 1.202 (3) | C11—H11A | 0.9900 |
C1—C8 | 1.350 (3) | C11—H11B | 0.9900 |
C1—C2 | 1.444 (3) | C12—H12A | 0.9800 |
C2—C7 | 1.393 (3) | C12—H12B | 0.9800 |
C2—C3 | 1.399 (3) | C12—H12C | 0.9800 |
C3—C4 | 1.391 (4) | C13—H13A | 0.9800 |
C3—H3 | 0.9500 | C13—H13B | 0.9800 |
C4—C5 | 1.405 (4) | C13—H13C | 0.9800 |
C4—C13 | 1.506 (4) | C14—H14A | 0.9800 |
C5—C6 | 1.388 (4) | C14—H14B | 0.9800 |
C5—H5 | 0.9500 | C14—H14C | 0.9800 |
O2—S—C1 | 106.9 (1) | C10—C9—H9A | 108.7 |
O2—S—C14 | 106.4 (1) | C8—C9—H9B | 108.7 |
C1—S—C14 | 98.7 (1) | C10—C9—H9B | 108.7 |
C8—O1—C7 | 106.2 (2) | H9A—C9—H9B | 107.6 |
C10—O3—C11 | 117.2 (2) | O4—C10—O3 | 123.9 (2) |
C8—C1—C2 | 107.9 (2) | O4—C10—C9 | 125.8 (2) |
C8—C1—S | 122.7 (2) | O3—C10—C9 | 110.3 (2) |
C2—C1—S | 129.2 (2) | O3—C11—C12 | 108.2 (2) |
C7—C2—C3 | 119.2 (2) | O3—C11—H11A | 110.1 |
C7—C2—C1 | 104.3 (2) | C12—C11—H11A | 110.1 |
C3—C2—C1 | 136.4 (2) | O3—C11—H11B | 110.1 |
C4—C3—C2 | 118.8 (2) | C12—C11—H11B | 110.1 |
C4—C3—H3 | 120.6 | H11A—C11—H11B | 108.4 |
C2—C3—H3 | 120.6 | C11—C12—H12A | 109.5 |
C3—C4—C5 | 119.9 (2) | C11—C12—H12B | 109.5 |
C3—C4—C13 | 120.3 (2) | H12A—C12—H12B | 109.5 |
C5—C4—C13 | 119.8 (2) | C11—C12—H12C | 109.5 |
C6—C5—C4 | 122.5 (2) | H12A—C12—H12C | 109.5 |
C6—C5—H5 | 118.8 | H12B—C12—H12C | 109.5 |
C4—C5—H5 | 118.8 | C4—C13—H13A | 109.5 |
C7—C6—C5 | 116.0 (2) | C4—C13—H13B | 109.5 |
C7—C6—H6 | 122.0 | H13A—C13—H13B | 109.5 |
C5—C6—H6 | 122.0 | C4—C13—H13C | 109.5 |
O1—C7—C6 | 125.6 (2) | H13A—C13—H13C | 109.5 |
O1—C7—C2 | 110.8 (2) | H13B—C13—H13C | 109.5 |
C6—C7—C2 | 123.6 (2) | S—C14—H14A | 109.5 |
C1—C8—O1 | 110.8 (2) | S—C14—H14B | 109.5 |
C1—C8—C9 | 133.3 (2) | H14A—C14—H14B | 109.5 |
O1—C8—C9 | 115.9 (2) | S—C14—H14C | 109.5 |
C8—C9—C10 | 114.1 (2) | H14A—C14—H14C | 109.5 |
C8—C9—H9A | 108.7 | H14B—C14—H14C | 109.5 |
O2—S—C1—C8 | −129.7 (2) | C5—C6—C7—C2 | 0.2 (4) |
C14—S—C1—C8 | 120.2 (2) | C3—C2—C7—O1 | 178.7 (2) |
O2—S—C1—C2 | 45.0 (3) | C1—C2—C7—O1 | −0.7 (3) |
C14—S—C1—C2 | −65.1 (3) | C3—C2—C7—C6 | −0.4 (4) |
C8—C1—C2—C7 | 0.4 (3) | C1—C2—C7—C6 | −179.8 (2) |
S—C1—C2—C7 | −174.91 (19) | C2—C1—C8—O1 | 0.1 (3) |
C8—C1—C2—C3 | −178.9 (3) | S—C1—C8—O1 | 175.77 (16) |
S—C1—C2—C3 | 5.8 (4) | C2—C1—C8—C9 | 179.6 (3) |
C7—C2—C3—C4 | 0.2 (4) | S—C1—C8—C9 | −4.7 (4) |
C1—C2—C3—C4 | 179.4 (3) | C7—O1—C8—C1 | −0.6 (3) |
C2—C3—C4—C5 | 0.1 (4) | C7—O1—C8—C9 | 179.8 (2) |
C2—C3—C4—C13 | −179.6 (2) | C1—C8—C9—C10 | −64.4 (4) |
C3—C4—C5—C6 | −0.3 (4) | O1—C8—C9—C10 | 115.1 (2) |
C13—C4—C5—C6 | 179.4 (2) | C11—O3—C10—O4 | −0.6 (4) |
C4—C5—C6—C7 | 0.1 (4) | C11—O3—C10—C9 | −179.3 (2) |
C8—O1—C7—C6 | 179.9 (2) | C8—C9—C10—O4 | 14.1 (4) |
C8—O1—C7—C2 | 0.8 (3) | C8—C9—C10—O3 | −167.2 (2) |
C5—C6—C7—O1 | −178.7 (2) | C10—O3—C11—C12 | −173.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2i | 0.95 | 2.48 | 3.407 (3) | 164 |
C9—H9B···O2ii | 0.99 | 2.16 | 3.143 (3) | 172 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C14H16O4S |
Mr | 280.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.1499 (8), 9.4958 (9), 10.283 (1) |
α, β, γ (°) | 73.216 (2), 79.023 (2), 65.188 (2) |
V (Å3) | 689.37 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.40 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3639, 2416, 2020 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.110, 1.13 |
No. of reflections | 2416 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.25 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2i | 0.95 | 2.48 | 3.407 (3) | 163.8 |
C9—H9B···O2ii | 0.99 | 2.16 | 3.143 (3) | 171.9 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+2. |
As part of our ongoing work on the synthesis and structure of 2-benzofuranacetic acid derivatives, the crystal structures of ethyl [5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(5-ethyl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid (Seo et al., 2007) have been described previously. Herein we report the molecular and crystal structure of the title compound (Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.007 Å from the least-squares plane defined by the nine constituent atoms. The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between adjacent benzene units. The Cg···Cgiii distance is 3.641 (3) Å (Cg is the centroid of the C2—C7 benzene ring; symmetry code as in Fig. 2). The molecular packing is further stabilized by two kinds of C—H···O hydrogen bonds between the oxygen of the S═O group and hydrogen atoms on the benzene ring and of the benzylic methylene group respectively (Table 1 and Fig. 2).