Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704041X/tk2188sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704041X/tk2188Isup2.hkl |
CCDC reference: 660318
3-Chloroperbenzoic acid (77%, 359 mg, 1.60 mmol) was added in small portions to a stirred solution of ethyl 2-(5-bromo-3-methylsulfanyl-1-benzofuran-2-yl)acetate (494 mg, 1.50 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 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 (I) as a colorless solid [yield 86%, m.p. 453–454 K; Rf = 0.73 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute chloroform solution of (I) held at room temperature.
All the H atoms were included in the riding-model approximation, with C—H = 0.95–0.99, and with Uiso(H) = 1.2 or 1.5Ueq(C).
As part of our on-going studies on the synthesis and structure of 2-benzofuranacetic acid derivatives, we have recently described the crystal structures of ethyl [5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(3-methyllsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007). Herein, we report the molecular and crystal structure of the title compound, ethyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (I, Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.010 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···Cgiv distance is 3.592 (2) Å (Cg is the centroid of the C2–C7 ring; symmetry code as in Fig. 2). The molecular packing is further stabilized by C—H···O interactions (Table 1 and Fig. 2): one between a benzene-H and the S═O unit, i.e. C3—H3···O2i, a second between a methylene-H and the S═O unit, i.e. C9—H9B···O2ii, and a third between the second methylene-H the furan-O, i.e. C9—H9A···O1iii.
For the crystal structures of isomers of the title compound, see: Choi et al. (2006, 2007).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.
C13H13BrO4S | Z = 2 |
Mr = 345.20 | F(000) = 348 |
Triclinic, P1 | Dx = 1.666 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3557 (4) Å | Cell parameters from 4506 reflections |
b = 9.5625 (5) Å | θ = 2.2–28.3° |
c = 10.0192 (5) Å | µ = 3.14 mm−1 |
α = 71.644 (1)° | T = 173 K |
β = 78.619 (1)° | Block, colourless |
γ = 65.304 (1)° | 0.40 × 0.40 × 0.20 mm |
V = 688.31 (6) Å3 |
Bruker SMART CCD area-detector diffractometer | 2961 independent reflections |
Radiation source: fine-focus sealed tube | 2772 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.0°, θmin = 2.2° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | k = −12→12 |
Tmin = 0.321, Tmax = 0.541 | l = −12→12 |
5994 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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.031P)2 + 0.3245P] where P = (Fo2 + 2Fc2)/3 |
2961 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C13H13BrO4S | γ = 65.304 (1)° |
Mr = 345.20 | V = 688.31 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3557 (4) Å | Mo Kα radiation |
b = 9.5625 (5) Å | µ = 3.14 mm−1 |
c = 10.0192 (5) Å | T = 173 K |
α = 71.644 (1)° | 0.40 × 0.40 × 0.20 mm |
β = 78.619 (1)° |
Bruker SMART CCD area-detector diffractometer | 2961 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | 2772 reflections with I > 2σ(I) |
Tmin = 0.321, Tmax = 0.541 | Rint = 0.016 |
5994 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.41 e Å−3 |
2961 reflections | Δρmin = −0.38 e Å−3 |
172 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 | ||
Br | 1.19929 (2) | 0.29496 (2) | 0.09731 (2) | 0.03275 (7) | |
S | 0.77219 (6) | −0.11607 (5) | 0.46784 (4) | 0.02467 (10) | |
O1 | 0.66177 (15) | 0.04723 (13) | 0.06926 (11) | 0.0211 (2) | |
O2 | 0.76708 (18) | 0.01229 (17) | 0.52618 (13) | 0.0339 (3) | |
O3 | 0.51765 (17) | −0.37582 (15) | 0.27271 (15) | 0.0303 (3) | |
O4 | 0.76958 (18) | −0.37966 (16) | 0.32289 (16) | 0.0359 (3) | |
C1 | 0.7622 (2) | −0.03343 (19) | 0.28450 (16) | 0.0198 (3) | |
C2 | 0.8492 (2) | 0.06848 (19) | 0.19260 (16) | 0.0197 (3) | |
C3 | 0.9766 (2) | 0.12143 (19) | 0.20606 (17) | 0.0219 (3) | |
H3 | 1.0273 | 0.0910 | 0.2928 | 0.026* | |
C4 | 1.0248 (2) | 0.2206 (2) | 0.08611 (18) | 0.0231 (3) | |
C5 | 0.9530 (2) | 0.2688 (2) | −0.04359 (18) | 0.0246 (3) | |
H5 | 0.9900 | 0.3382 | −0.1221 | 0.030* | |
C6 | 0.8282 (2) | 0.2155 (2) | −0.05775 (17) | 0.0236 (3) | |
H6 | 0.7778 | 0.2461 | −0.1447 | 0.028* | |
C7 | 0.7807 (2) | 0.11484 (19) | 0.06213 (17) | 0.0200 (3) | |
C8 | 0.6524 (2) | −0.04197 (19) | 0.20650 (16) | 0.0199 (3) | |
C9 | 0.5307 (2) | −0.1276 (2) | 0.23858 (17) | 0.0223 (3) | |
H9A | 0.4667 | −0.0971 | 0.1541 | 0.027* | |
H9B | 0.4421 | −0.0931 | 0.3154 | 0.027* | |
C10 | 0.6233 (2) | −0.3068 (2) | 0.28198 (17) | 0.0232 (3) | |
C11 | 0.5906 (3) | −0.5504 (2) | 0.3129 (3) | 0.0385 (5) | |
H11A | 0.6164 | −0.5916 | 0.4133 | 0.046* | |
H11B | 0.7015 | −0.5917 | 0.2548 | 0.046* | |
C12 | 0.4550 (3) | −0.6019 (3) | 0.2887 (3) | 0.0517 (6) | |
H12A | 0.4308 | −0.5606 | 0.1890 | 0.062* | |
H12B | 0.3459 | −0.5604 | 0.3468 | 0.062* | |
H12C | 0.4993 | −0.7187 | 0.3146 | 0.062* | |
C13 | 0.9969 (3) | −0.2565 (2) | 0.4702 (2) | 0.0339 (4) | |
H13A | 1.0248 | −0.3146 | 0.5679 | 0.051* | |
H13B | 1.0760 | −0.1996 | 0.4271 | 0.051* | |
H13C | 1.0125 | −0.3321 | 0.4169 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.02947 (11) | 0.02946 (11) | 0.04696 (12) | −0.01799 (8) | −0.00698 (8) | −0.00823 (8) |
S | 0.0261 (2) | 0.0304 (2) | 0.01890 (18) | −0.01329 (17) | −0.00469 (15) | −0.00297 (16) |
O1 | 0.0224 (6) | 0.0224 (6) | 0.0211 (5) | −0.0103 (5) | −0.0062 (4) | −0.0038 (4) |
O2 | 0.0364 (7) | 0.0424 (8) | 0.0270 (6) | −0.0134 (6) | −0.0042 (5) | −0.0160 (6) |
O3 | 0.0256 (6) | 0.0204 (6) | 0.0472 (8) | −0.0100 (5) | −0.0100 (5) | −0.0059 (5) |
O4 | 0.0288 (7) | 0.0269 (7) | 0.0513 (8) | −0.0115 (6) | −0.0174 (6) | 0.0009 (6) |
C1 | 0.0208 (7) | 0.0193 (8) | 0.0194 (7) | −0.0071 (6) | −0.0039 (6) | −0.0043 (6) |
C2 | 0.0201 (7) | 0.0176 (7) | 0.0217 (7) | −0.0059 (6) | −0.0032 (6) | −0.0065 (6) |
C3 | 0.0220 (8) | 0.0210 (8) | 0.0256 (8) | −0.0076 (6) | −0.0051 (6) | −0.0086 (6) |
C4 | 0.0193 (7) | 0.0199 (8) | 0.0337 (9) | −0.0087 (6) | −0.0027 (6) | −0.0099 (7) |
C5 | 0.0248 (8) | 0.0181 (8) | 0.0278 (8) | −0.0071 (7) | −0.0015 (7) | −0.0036 (6) |
C6 | 0.0247 (8) | 0.0212 (8) | 0.0232 (8) | −0.0073 (7) | −0.0057 (6) | −0.0032 (6) |
C7 | 0.0187 (7) | 0.0183 (7) | 0.0240 (7) | −0.0059 (6) | −0.0049 (6) | −0.0066 (6) |
C8 | 0.0201 (7) | 0.0177 (7) | 0.0209 (7) | −0.0056 (6) | −0.0039 (6) | −0.0046 (6) |
C9 | 0.0210 (8) | 0.0231 (8) | 0.0253 (8) | −0.0101 (6) | −0.0051 (6) | −0.0051 (6) |
C10 | 0.0234 (8) | 0.0251 (8) | 0.0232 (8) | −0.0114 (7) | −0.0038 (6) | −0.0049 (6) |
C11 | 0.0330 (10) | 0.0197 (9) | 0.0622 (13) | −0.0098 (8) | −0.0116 (9) | −0.0055 (9) |
C12 | 0.0407 (12) | 0.0253 (10) | 0.0935 (19) | −0.0149 (9) | −0.0159 (12) | −0.0114 (11) |
C13 | 0.0318 (10) | 0.0305 (10) | 0.0346 (10) | −0.0057 (8) | −0.0145 (8) | −0.0034 (8) |
Br—C4 | 1.904 (2) | C5—H5 | 0.9500 |
S—O2 | 1.500 (1) | C6—C7 | 1.389 (2) |
S—C1 | 1.760 (2) | C6—H6 | 0.9500 |
S—C13 | 1.794 (2) | C8—C9 | 1.486 (2) |
O1—C7 | 1.375 (2) | C9—C10 | 1.510 (2) |
O1—C8 | 1.378 (2) | C9—H9A | 0.9900 |
O3—C10 | 1.334 (2) | C9—H9B | 0.9900 |
O3—C11 | 1.464 (2) | C11—C12 | 1.495 (3) |
O4—C10 | 1.206 (2) | C11—H11A | 0.9900 |
C1—C8 | 1.358 (2) | C11—H11B | 0.9900 |
C1—C2 | 1.445 (2) | C12—H12A | 0.9800 |
C2—C7 | 1.397 (2) | C12—H12B | 0.9800 |
C2—C3 | 1.399 (2) | C12—H12C | 0.9800 |
C3—C4 | 1.384 (2) | C13—H13A | 0.9800 |
C3—H3 | 0.9500 | C13—H13B | 0.9800 |
C4—C5 | 1.400 (2) | C13—H13C | 0.9800 |
C5—C6 | 1.383 (2) | ||
O2—S—C1 | 105.74 (8) | O1—C8—C9 | 115.7 (1) |
O2—S—C13 | 106.19 (9) | C8—C9—C10 | 113.5 (1) |
C1—S—C13 | 98.98 (8) | C8—C9—H9A | 108.9 |
C7—O1—C8 | 106.3 (1) | C10—C9—H9A | 108.9 |
C10—O3—C11 | 116.1 (1) | C8—C9—H9B | 108.9 |
C8—C1—C2 | 107.4 (1) | C10—C9—H9B | 108.9 |
C8—C1—S | 124.3 (1) | H9A—C9—H9B | 107.7 |
C2—C1—S | 128.0 (1) | O4—C10—O3 | 123.8 (2) |
C7—C2—C3 | 119.6 (2) | O4—C10—C9 | 125.9 (2) |
C7—C2—C1 | 104.6 (1) | O3—C10—C9 | 110.2 (1) |
C3—C2—C1 | 135.9 (2) | O3—C11—C12 | 107.2 (2) |
C4—C3—C2 | 116.4 (2) | O3—C11—H11A | 110.3 |
C4—C3—H3 | 121.8 | C12—C11—H11A | 110.3 |
C2—C3—H3 | 121.8 | O3—C11—H11B | 110.3 |
C3—C4—C5 | 123.6 (2) | C12—C11—H11B | 110.3 |
C3—C4—Br | 118.3 (1) | H11A—C11—H11B | 108.5 |
C5—C4—Br | 118.0 (1) | C11—C12—H12A | 109.5 |
C6—C5—C4 | 120.2 (2) | C11—C12—H12B | 109.5 |
C6—C5—H5 | 119.9 | H12A—C12—H12B | 109.5 |
C4—C5—H5 | 119.9 | C11—C12—H12C | 109.5 |
C5—C6—C7 | 116.3 (2) | H12A—C12—H12C | 109.5 |
C5—C6—H6 | 121.8 | H12B—C12—H12C | 109.5 |
C7—C6—H6 | 121.8 | S—C13—H13A | 109.5 |
O1—C7—C6 | 125.3 (1) | S—C13—H13B | 109.5 |
O1—C7—C2 | 110.9 (1) | H13A—C13—H13B | 109.5 |
C6—C7—C2 | 123.9 (2) | S—C13—H13C | 109.5 |
C1—C8—O1 | 110.8 (1) | H13A—C13—H13C | 109.5 |
C1—C8—C9 | 133.5 (2) | H13B—C13—H13C | 109.5 |
O2—S—C1—C8 | −132.39 (15) | C5—C6—C7—C2 | 1.0 (2) |
C13—S—C1—C8 | 117.86 (15) | C3—C2—C7—O1 | 178.24 (14) |
O2—S—C1—C2 | 40.01 (17) | C1—C2—C7—O1 | −0.64 (17) |
C13—S—C1—C2 | −69.74 (16) | C3—C2—C7—C6 | −1.6 (2) |
C8—C1—C2—C7 | 0.28 (18) | C1—C2—C7—C6 | 179.53 (15) |
S—C1—C2—C7 | −173.14 (12) | C2—C1—C8—O1 | 0.17 (18) |
C8—C1—C2—C3 | −178.31 (18) | S—C1—C8—O1 | 173.89 (11) |
S—C1—C2—C3 | 8.3 (3) | C2—C1—C8—C9 | 179.06 (17) |
C7—C2—C3—C4 | 0.9 (2) | S—C1—C8—C9 | −7.2 (3) |
C1—C2—C3—C4 | 179.38 (17) | C7—O1—C8—C1 | −0.55 (17) |
C2—C3—C4—C5 | 0.2 (2) | C7—O1—C8—C9 | −179.66 (13) |
C2—C3—C4—Br | −179.40 (12) | C1—C8—C9—C10 | −62.5 (2) |
C3—C4—C5—C6 | −0.8 (3) | O1—C8—C9—C10 | 116.37 (15) |
Br—C4—C5—C6 | 178.78 (13) | C11—O3—C10—O4 | −1.3 (3) |
C4—C5—C6—C7 | 0.2 (2) | C11—O3—C10—C9 | −179.58 (16) |
C8—O1—C7—C6 | −179.42 (15) | C8—C9—C10—O4 | 18.2 (2) |
C8—O1—C7—C2 | 0.74 (17) | C8—C9—C10—O3 | −163.55 (14) |
C5—C6—C7—O1 | −178.85 (15) | C10—O3—C11—C12 | −177.56 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2i | 0.95 | 2.43 | 3.352 (2) | 164 |
C9—H9B···O2ii | 0.99 | 2.17 | 3.161 (2) | 176 |
C9—H9A···O1iii | 0.99 | 2.50 | 3.4816 (19) | 173 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C13H13BrO4S |
Mr | 345.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.3557 (4), 9.5625 (5), 10.0192 (5) |
α, β, γ (°) | 71.644 (1), 78.619 (1), 65.304 (1) |
V (Å3) | 688.31 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.14 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1999) |
Tmin, Tmax | 0.321, 0.541 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5994, 2961, 2772 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.059, 1.03 |
No. of reflections | 2961 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.38 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O2i | 0.95 | 2.43 | 3.352 (2) | 164 |
C9—H9B···O2ii | 0.99 | 2.17 | 3.161 (2) | 176 |
C9—H9A···O1iii | 0.99 | 2.50 | 3.4816 (19) | 173 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z. |
As part of our on-going studies on the synthesis and structure of 2-benzofuranacetic acid derivatives, we have recently described the crystal structures of ethyl [5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(3-methyllsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007). Herein, we report the molecular and crystal structure of the title compound, ethyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (I, Fig. 1).
The benzofuran unit is essentially planar, with a mean deviation of 0.010 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···Cgiv distance is 3.592 (2) Å (Cg is the centroid of the C2–C7 ring; symmetry code as in Fig. 2). The molecular packing is further stabilized by C—H···O interactions (Table 1 and Fig. 2): one between a benzene-H and the S═O unit, i.e. C3—H3···O2i, a second between a methylene-H and the S═O unit, i.e. C9—H9B···O2ii, and a third between the second methylene-H the furan-O, i.e. C9—H9A···O1iii.