Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044583/cf2138sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044583/cf2138Isup2.hkl |
CCDC reference: 663784
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.004 Å
- R factor = 0.020
- wR factor = 0.055
- Data-to-parameter ratio = 17.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.96 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
3-Chloroperbenzoic acid (77%, 247 mg, 1.10 mmol) was added in small portions to a stirred solution of ethyl 2-(5-iodo-3-methylsulfanyl-1-benzofuran-2-yl)acetate (376 mg, 1.0 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 (hexane-ethyl acetate, 1:2, v/v) to afford the title compound as a colorless solid [yield 79%, m.p. 446–447 K; Rf = 0.74 (hexane-ethyl acetate, 1:2, v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in chloroform at room temperature.
All H atoms were geometrically located in ideal positions 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, 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 1.36 Å from S.
As part of our continuing studies on the synthesis and structure of ethyl 2-benzofuranacetate analogues, we have recently described the crystal structures of ethyl 2-(5-chloro-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007a) and ethyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007b). Here we report the crystal structure of the title compound, ethyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (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···Cgi distance is 3.591 (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 C—H···O hydrogen bonds (Table 1 and Fig. 2); one between a benzene-H and the S═O unit, i.e. C3—H3···O2iv, a second between a methylene—H and the S═O unit, i.e. C9—H9A···O2iii, and a third between the second methylene—H and the furan—O, i.e. C9—H9B···O1ii, respectively (symmetry codes as in Fig. 2).
For the crystal structures of isomers of the title compound, see: Choi et al. (2007a,b).
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).
C13H13IO4S | Z = 2 |
Mr = 392.19 | F(000) = 384 |
Triclinic, P1 | Dx = 1.835 Mg m−3 |
Hall symbol: -p_1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4311 (4) Å | Cell parameters from 5167 reflections |
b = 9.8128 (5) Å | θ = 2.4–28.3° |
c = 10.0299 (5) Å | µ = 2.41 mm−1 |
α = 70.629 (1)° | T = 173 K |
β = 78.623 (1)° | Block, colorless |
γ = 65.370 (1)° | 0.30 × 0.20 × 0.10 mm |
V = 709.92 (6) Å3 |
Bruker SMART CCD diffractometer | 3053 independent reflections |
Radiation source: fine-focus sealed tube | 2900 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 = 0.561, Tmax = 0.790 | l = −12→12 |
6175 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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0287P)2 + 0.5008P] where P = (Fo2 + 2Fc2)/3 |
3053 reflections | (Δ/σ)max < 0.001 |
172 parameters | Δρmax = 1.08 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C13H13IO4S | γ = 65.370 (1)° |
Mr = 392.19 | V = 709.92 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4311 (4) Å | Mo Kα radiation |
b = 9.8128 (5) Å | µ = 2.41 mm−1 |
c = 10.0299 (5) Å | T = 173 K |
α = 70.629 (1)° | 0.30 × 0.20 × 0.10 mm |
β = 78.623 (1)° |
Bruker SMART CCD diffractometer | 3053 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | 2900 reflections with I > 2σ(I) |
Tmin = 0.561, Tmax = 0.790 | Rint = 0.016 |
6175 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.08 | Δρmax = 1.08 e Å−3 |
3053 reflections | Δρmin = −0.54 e Å−3 |
172 parameters |
Experimental. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz) δ 1.28 (t, J = 7.48 Hz, 3H), 3.06 (s, 3H), 4.04 (s, 2H), 4.20 (q, J = 7.48 Hz, 2H), 7.28 (d, J = 8.72 Hz 1H), 7.65 (dd, J = 8.72 Hz and J = 1.64 Hz, 1H), 8.27 (d, J = 1.68 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.11, 33.40, 40.97, 62.08, 87.69, 113.85, 119.94, 126.34, 128.92, 134.43, 152.04, 153.75, 167.74; EI—MS 392[M+]. |
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 | ||
I | 0.295210 (19) | 0.698038 (17) | 0.404232 (16) | 0.02686 (6) | |
S | 0.72966 (7) | 1.11343 (7) | 0.02831 (6) | 0.02383 (12) | |
O1 | 0.83624 (19) | 0.96021 (18) | 0.43043 (16) | 0.0205 (3) | |
O2 | 0.7316 (2) | 0.9883 (2) | −0.02664 (18) | 0.0334 (4) | |
O3 | 0.9768 (2) | 1.37474 (19) | 0.22152 (19) | 0.0291 (4) | |
O4 | 0.7275 (2) | 1.3768 (2) | 0.1722 (2) | 0.0348 (4) | |
C1 | 0.7421 (3) | 1.0328 (3) | 0.2133 (2) | 0.0196 (4) | |
C2 | 0.6560 (3) | 0.9327 (2) | 0.3072 (2) | 0.0191 (4) | |
C3 | 0.5323 (3) | 0.8778 (2) | 0.2951 (2) | 0.0204 (4) | |
H3 | 0.4844 | 0.9051 | 0.2073 | 0.024* | |
C4 | 0.4828 (3) | 0.7819 (2) | 0.4166 (2) | 0.0210 (4) | |
C5 | 0.5511 (3) | 0.7389 (3) | 0.5482 (2) | 0.0225 (4) | |
H5 | 0.5138 | 0.6717 | 0.6285 | 0.027* | |
C6 | 0.6727 (3) | 0.7940 (3) | 0.5611 (2) | 0.0220 (4) | |
H6 | 0.7205 | 0.7667 | 0.6489 | 0.026* | |
C7 | 0.7207 (3) | 0.8910 (2) | 0.4392 (2) | 0.0187 (4) | |
C8 | 0.8475 (3) | 1.0452 (2) | 0.2905 (2) | 0.0192 (4) | |
C9 | 0.9667 (3) | 1.1309 (3) | 0.2571 (2) | 0.0218 (4) | |
H9A | 1.0536 | 1.0992 | 0.1798 | 0.026* | |
H9B | 1.0311 | 1.1005 | 0.3415 | 0.026* | |
C10 | 0.8723 (3) | 1.3066 (3) | 0.2128 (2) | 0.0224 (4) | |
C11 | 0.9013 (4) | 1.5457 (3) | 0.1832 (3) | 0.0363 (6) | |
H11A | 0.7912 | 1.5824 | 0.2414 | 0.044* | |
H11B | 0.8755 | 1.5891 | 0.0821 | 0.044* | |
C13 | 0.5088 (3) | 1.2521 (3) | 0.0257 (3) | 0.0330 (5) | |
H13A | 0.4795 | 1.3090 | −0.0726 | 0.049* | |
H13B | 0.4963 | 1.3260 | 0.0768 | 0.049* | |
H13C | 0.4296 | 1.1973 | 0.0715 | 0.049* | |
C12 | 1.0325 (4) | 1.5972 (4) | 0.2098 (5) | 0.0556 (9) | |
H12A | 1.1409 | 1.5599 | 0.1518 | 0.067* | |
H12B | 1.0565 | 1.5540 | 0.3102 | 0.067* | |
H12C | 0.9864 | 1.7115 | 0.1848 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I | 0.02609 (9) | 0.02369 (9) | 0.03565 (10) | −0.01374 (6) | −0.00606 (6) | −0.00646 (6) |
S | 0.0260 (3) | 0.0284 (3) | 0.0183 (2) | −0.0125 (2) | −0.0041 (2) | −0.0038 (2) |
O1 | 0.0213 (7) | 0.0214 (7) | 0.0207 (7) | −0.0097 (6) | −0.0058 (6) | −0.0037 (6) |
O2 | 0.0392 (10) | 0.0396 (10) | 0.0262 (9) | −0.0137 (8) | −0.0050 (7) | −0.0150 (8) |
O3 | 0.0268 (8) | 0.0214 (8) | 0.0423 (10) | −0.0115 (7) | −0.0099 (7) | −0.0055 (7) |
O4 | 0.0282 (9) | 0.0256 (9) | 0.0497 (11) | −0.0111 (7) | −0.0158 (8) | −0.0006 (8) |
C1 | 0.0198 (10) | 0.0193 (10) | 0.0200 (10) | −0.0072 (8) | −0.0028 (8) | −0.0053 (8) |
C2 | 0.0202 (10) | 0.0169 (10) | 0.0197 (10) | −0.0045 (8) | −0.0034 (8) | −0.0066 (8) |
C3 | 0.0219 (10) | 0.0199 (10) | 0.0215 (10) | −0.0066 (8) | −0.0055 (8) | −0.0081 (8) |
C4 | 0.0203 (10) | 0.0168 (10) | 0.0289 (11) | −0.0069 (8) | −0.0037 (8) | −0.0090 (8) |
C5 | 0.0244 (11) | 0.0171 (10) | 0.0239 (10) | −0.0079 (8) | −0.0014 (8) | −0.0034 (8) |
C6 | 0.0249 (11) | 0.0188 (10) | 0.0211 (10) | −0.0062 (9) | −0.0061 (8) | −0.0044 (8) |
C7 | 0.0170 (9) | 0.0171 (10) | 0.0233 (10) | −0.0052 (8) | −0.0053 (8) | −0.0066 (8) |
C8 | 0.0203 (10) | 0.0164 (10) | 0.0206 (10) | −0.0062 (8) | −0.0032 (8) | −0.0048 (8) |
C9 | 0.0205 (10) | 0.0221 (10) | 0.0255 (11) | −0.0093 (8) | −0.0048 (8) | −0.0066 (9) |
C10 | 0.0257 (11) | 0.0239 (11) | 0.0207 (10) | −0.0127 (9) | −0.0037 (8) | −0.0045 (8) |
C11 | 0.0343 (13) | 0.0203 (12) | 0.0544 (17) | −0.0102 (10) | −0.0101 (12) | −0.0070 (11) |
C13 | 0.0313 (13) | 0.0332 (13) | 0.0307 (13) | −0.0072 (11) | −0.0113 (10) | −0.0056 (10) |
C12 | 0.0454 (17) | 0.0285 (15) | 0.100 (3) | −0.0157 (13) | −0.0198 (18) | −0.0168 (16) |
I—C4 | 2.104 (2) | C5—H5 | 0.950 |
S—O2 | 1.4973 (19) | C6—C7 | 1.385 (3) |
S—C1 | 1.765 (2) | C6—H6 | 0.950 |
S—C13 | 1.790 (3) | C8—C9 | 1.488 (3) |
O1—C7 | 1.377 (3) | C9—C10 | 1.514 (3) |
O1—C8 | 1.382 (3) | C9—H9A | 0.990 |
O3—C10 | 1.338 (3) | C9—H9B | 0.990 |
O3—C11 | 1.465 (3) | C11—C12 | 1.490 (4) |
O4—C10 | 1.200 (3) | C11—H11A | 0.990 |
C1—C8 | 1.352 (3) | C11—H11B | 0.990 |
C1—C2 | 1.445 (3) | C13—H13A | 0.980 |
C2—C3 | 1.399 (3) | C13—H13B | 0.980 |
C2—C7 | 1.400 (3) | C13—H13C | 0.980 |
C3—C4 | 1.382 (3) | C12—H12A | 0.980 |
C3—H3 | 0.950 | C12—H12B | 0.980 |
C4—C5 | 1.407 (3) | C12—H12C | 0.980 |
C5—C6 | 1.386 (3) | ||
O2—S—C1 | 105.94 (10) | O1—C8—C9 | 115.37 (18) |
O2—S—C13 | 106.48 (12) | C8—C9—C10 | 113.32 (18) |
C1—S—C13 | 98.80 (11) | C8—C9—H9A | 108.9 |
C7—O1—C8 | 106.37 (16) | C10—C9—H9A | 108.9 |
C10—O3—C11 | 115.76 (18) | C8—C9—H9B | 108.9 |
C8—C1—C2 | 107.76 (18) | C10—C9—H9B | 108.9 |
C8—C1—S | 124.73 (17) | H9A—C9—H9B | 107.7 |
C2—C1—S | 127.32 (16) | O4—C10—O3 | 124.1 (2) |
C3—C2—C7 | 119.4 (2) | O4—C10—C9 | 126.1 (2) |
C3—C2—C1 | 136.1 (2) | O3—C10—C9 | 109.77 (18) |
C7—C2—C1 | 104.50 (18) | O3—C11—C12 | 107.2 (2) |
C4—C3—C2 | 116.94 (19) | O3—C11—H11A | 110.3 |
C4—C3—H3 | 121.5 | C12—C11—H11A | 110.3 |
C2—C3—H3 | 121.5 | O3—C11—H11B | 110.3 |
C3—C4—C5 | 123.1 (2) | C12—C11—H11B | 110.3 |
C3—C4—I | 118.37 (15) | H11A—C11—H11B | 108.5 |
C5—C4—I | 118.54 (16) | S—C13—H13A | 109.5 |
C6—C5—C4 | 120.2 (2) | S—C13—H13B | 109.5 |
C6—C5—H5 | 119.9 | H13A—C13—H13B | 109.5 |
C4—C5—H5 | 119.9 | S—C13—H13C | 109.5 |
C7—C6—C5 | 116.4 (2) | H13A—C13—H13C | 109.5 |
C7—C6—H6 | 121.8 | H13B—C13—H13C | 109.5 |
C5—C6—H6 | 121.8 | C11—C12—H12A | 109.5 |
O1—C7—C6 | 125.41 (19) | C11—C12—H12B | 109.5 |
O1—C7—C2 | 110.65 (18) | H12A—C12—H12B | 109.5 |
C6—C7—C2 | 123.9 (2) | C11—C12—H12C | 109.5 |
C1—C8—O1 | 110.72 (19) | H12A—C12—H12C | 109.5 |
C1—C8—C9 | 133.9 (2) | H12B—C12—H12C | 109.5 |
O2—S—C1—C8 | 135.0 (2) | C5—C6—C7—C2 | −1.0 (3) |
C13—S—C1—C8 | −115.0 (2) | C3—C2—C7—O1 | −178.10 (18) |
O2—S—C1—C2 | −39.3 (2) | C1—C2—C7—O1 | 0.7 (2) |
C13—S—C1—C2 | 70.7 (2) | C3—C2—C7—C6 | 1.6 (3) |
C8—C1—C2—C3 | 178.3 (2) | C1—C2—C7—C6 | −179.7 (2) |
S—C1—C2—C3 | −6.6 (4) | C2—C1—C8—O1 | −0.4 (2) |
C8—C1—C2—C7 | −0.2 (2) | S—C1—C8—O1 | −175.65 (15) |
S—C1—C2—C7 | 174.93 (16) | C2—C1—C8—C9 | −179.2 (2) |
C7—C2—C3—C4 | −0.9 (3) | S—C1—C8—C9 | 5.6 (4) |
C1—C2—C3—C4 | −179.2 (2) | C7—O1—C8—C1 | 0.8 (2) |
C2—C3—C4—C5 | −0.1 (3) | C7—O1—C8—C9 | 179.83 (17) |
C2—C3—C4—I | 179.42 (15) | C1—C8—C9—C10 | 64.6 (3) |
C3—C4—C5—C6 | 0.7 (3) | O1—C8—C9—C10 | −114.1 (2) |
I—C4—C5—C6 | −178.86 (16) | C11—O3—C10—O4 | 2.4 (3) |
C4—C5—C6—C7 | −0.1 (3) | C11—O3—C10—C9 | −179.3 (2) |
C8—O1—C7—C6 | 179.4 (2) | C8—C9—C10—O4 | −18.3 (3) |
C8—O1—C7—C2 | −0.9 (2) | C8—C9—C10—O3 | 163.43 (19) |
C5—C6—C7—O1 | 178.62 (19) | C10—O3—C11—C12 | 176.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O1i | 0.99 | 2.53 | 3.513 (3) | 174 |
C9—H9A···O2ii | 0.99 | 2.20 | 3.190 (3) | 174 |
C3—H3···O2iii | 0.95 | 2.48 | 3.391 (3) | 161 |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C13H13IO4S |
Mr | 392.19 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.4311 (4), 9.8128 (5), 10.0299 (5) |
α, β, γ (°) | 70.629 (1), 78.623 (1), 65.370 (1) |
V (Å3) | 709.92 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.41 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1999) |
Tmin, Tmax | 0.561, 0.790 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6175, 3053, 2900 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.055, 1.08 |
No. of reflections | 3053 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.08, −0.54 |
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 |
C9—H9B···O1i | 0.99 | 2.53 | 3.513 (3) | 173.7 |
C9—H9A···O2ii | 0.99 | 2.20 | 3.190 (3) | 173.5 |
C3—H3···O2iii | 0.95 | 2.48 | 3.391 (3) | 160.7 |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+2, −z. |
As part of our continuing studies on the synthesis and structure of ethyl 2-benzofuranacetate analogues, we have recently described the crystal structures of ethyl 2-(5-chloro-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007a) and ethyl 2-(5-bromo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (Choi et al., 2007b). Here we report the crystal structure of the title compound, ethyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate (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···Cgi distance is 3.591 (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 C—H···O hydrogen bonds (Table 1 and Fig. 2); one between a benzene-H and the S═O unit, i.e. C3—H3···O2iv, a second between a methylene—H and the S═O unit, i.e. C9—H9A···O2iii, and a third between the second methylene—H and the furan—O, i.e. C9—H9B···O1ii, respectively (symmetry codes as in Fig. 2).