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The title compound, C13H13IO4S, was prepared by the oxidation of ethyl 2-(5-iodo-3-methyl­sulfanyl-1-benzofuran-2-yl)­acetate using 3-chloro­perbenzoic acid. The O atom and the methyl group of the methyl­sulfinyl substituent lie on opposite sides of the plane of the benzofuran system. The crystal structure is stabilized by inter­molecular aromatic π–π inter­actions, with a centroid–centroid distance of 3.591 (3) Å between the benzene rings of neighboring mol­ecules, and by three inter­molecular C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044583/cf2138sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044583/cf2138Isup2.hkl
Contains datablock I

CCDC reference: 663784

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](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

Comment top

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 SO unit, i.e. C3—H3···O2iv, a second between a methylene—H and the SO 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).

Related literature top

For the crystal structures of isomers of the title compound, see: Choi et al. (2007a,b).

Experimental top

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.

Refinement top

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.

Structure description top

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 SO unit, i.e. C3—H3···O2iv, a second between a methylene—H and the SO 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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. π···π interactions and C—H···O hydrogen bonds (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry code: (i) 1 - x, 2 - y, 1 - z; (ii) 2 - x, 2 - y, 1 - z; (iii) 2 - x, 2 - y, -z; (iv) 1 - x, 2 - y, -z.]
Ethyl 2-(5-iodo-3-methylsulfinyl-1-benzofuran-2-yl)acetate top
Crystal data top
C13H13IO4SZ = 2
Mr = 392.19F(000) = 384
Triclinic, P1Dx = 1.835 Mg m3
Hall symbol: -p_1Mo Kα radiation, λ = 0.71073 Å
a = 8.4311 (4) ÅCell parameters from 5167 reflections
b = 9.8128 (5) Åθ = 2.4–28.3°
c = 10.0299 (5) ŵ = 2.41 mm1
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
Data collection top
Bruker SMART CCD
diffractometer
3053 independent reflections
Radiation source: fine-focus sealed tube2900 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
Detector resolution: 10.0 pixels mm-1θmax = 27.0°, θmin = 2.2°
φ and ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
k = 1212
Tmin = 0.561, Tmax = 0.790l = 1212
6175 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H-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 parametersΔρmax = 1.08 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
C13H13IO4Sγ = 65.370 (1)°
Mr = 392.19V = 709.92 (6) Å3
Triclinic, P1Z = 2
a = 8.4311 (4) ÅMo Kα radiation
b = 9.8128 (5) ŵ = 2.41 mm1
c = 10.0299 (5) ÅT = 173 K
α = 70.629 (1)°0.30 × 0.20 × 0.10 mm
β = 78.623 (1)°
Data collection top
Bruker SMART CCD
diffractometer
3053 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
2900 reflections with I > 2σ(I)
Tmin = 0.561, Tmax = 0.790Rint = 0.016
6175 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.055H-atom parameters constrained
S = 1.08Δρmax = 1.08 e Å3
3053 reflectionsΔρmin = 0.54 e Å3
172 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I0.295210 (19)0.698038 (17)0.404232 (16)0.02686 (6)
S0.72966 (7)1.11343 (7)0.02831 (6)0.02383 (12)
O10.83624 (19)0.96021 (18)0.43043 (16)0.0205 (3)
O20.7316 (2)0.9883 (2)0.02664 (18)0.0334 (4)
O30.9768 (2)1.37474 (19)0.22152 (19)0.0291 (4)
O40.7275 (2)1.3768 (2)0.1722 (2)0.0348 (4)
C10.7421 (3)1.0328 (3)0.2133 (2)0.0196 (4)
C20.6560 (3)0.9327 (2)0.3072 (2)0.0191 (4)
C30.5323 (3)0.8778 (2)0.2951 (2)0.0204 (4)
H30.48440.90510.20730.024*
C40.4828 (3)0.7819 (2)0.4166 (2)0.0210 (4)
C50.5511 (3)0.7389 (3)0.5482 (2)0.0225 (4)
H50.51380.67170.62850.027*
C60.6727 (3)0.7940 (3)0.5611 (2)0.0220 (4)
H60.72050.76670.64890.026*
C70.7207 (3)0.8910 (2)0.4392 (2)0.0187 (4)
C80.8475 (3)1.0452 (2)0.2905 (2)0.0192 (4)
C90.9667 (3)1.1309 (3)0.2571 (2)0.0218 (4)
H9A1.05361.09920.17980.026*
H9B1.03111.10050.34150.026*
C100.8723 (3)1.3066 (3)0.2128 (2)0.0224 (4)
C110.9013 (4)1.5457 (3)0.1832 (3)0.0363 (6)
H11A0.79121.58240.24140.044*
H11B0.87551.58910.08210.044*
C130.5088 (3)1.2521 (3)0.0257 (3)0.0330 (5)
H13A0.47951.30900.07260.049*
H13B0.49631.32600.07680.049*
H13C0.42961.19730.07150.049*
C121.0325 (4)1.5972 (4)0.2098 (5)0.0556 (9)
H12A1.14091.55990.15180.067*
H12B1.05651.55400.31020.067*
H12C0.98641.71150.18480.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I0.02609 (9)0.02369 (9)0.03565 (10)0.01374 (6)0.00606 (6)0.00646 (6)
S0.0260 (3)0.0284 (3)0.0183 (2)0.0125 (2)0.0041 (2)0.0038 (2)
O10.0213 (7)0.0214 (7)0.0207 (7)0.0097 (6)0.0058 (6)0.0037 (6)
O20.0392 (10)0.0396 (10)0.0262 (9)0.0137 (8)0.0050 (7)0.0150 (8)
O30.0268 (8)0.0214 (8)0.0423 (10)0.0115 (7)0.0099 (7)0.0055 (7)
O40.0282 (9)0.0256 (9)0.0497 (11)0.0111 (7)0.0158 (8)0.0006 (8)
C10.0198 (10)0.0193 (10)0.0200 (10)0.0072 (8)0.0028 (8)0.0053 (8)
C20.0202 (10)0.0169 (10)0.0197 (10)0.0045 (8)0.0034 (8)0.0066 (8)
C30.0219 (10)0.0199 (10)0.0215 (10)0.0066 (8)0.0055 (8)0.0081 (8)
C40.0203 (10)0.0168 (10)0.0289 (11)0.0069 (8)0.0037 (8)0.0090 (8)
C50.0244 (11)0.0171 (10)0.0239 (10)0.0079 (8)0.0014 (8)0.0034 (8)
C60.0249 (11)0.0188 (10)0.0211 (10)0.0062 (9)0.0061 (8)0.0044 (8)
C70.0170 (9)0.0171 (10)0.0233 (10)0.0052 (8)0.0053 (8)0.0066 (8)
C80.0203 (10)0.0164 (10)0.0206 (10)0.0062 (8)0.0032 (8)0.0048 (8)
C90.0205 (10)0.0221 (10)0.0255 (11)0.0093 (8)0.0048 (8)0.0066 (9)
C100.0257 (11)0.0239 (11)0.0207 (10)0.0127 (9)0.0037 (8)0.0045 (8)
C110.0343 (13)0.0203 (12)0.0544 (17)0.0102 (10)0.0101 (12)0.0070 (11)
C130.0313 (13)0.0332 (13)0.0307 (13)0.0072 (11)0.0113 (10)0.0056 (10)
C120.0454 (17)0.0285 (15)0.100 (3)0.0157 (13)0.0198 (18)0.0168 (16)
Geometric parameters (Å, º) top
I—C42.104 (2)C5—H50.950
S—O21.4973 (19)C6—C71.385 (3)
S—C11.765 (2)C6—H60.950
S—C131.790 (3)C8—C91.488 (3)
O1—C71.377 (3)C9—C101.514 (3)
O1—C81.382 (3)C9—H9A0.990
O3—C101.338 (3)C9—H9B0.990
O3—C111.465 (3)C11—C121.490 (4)
O4—C101.200 (3)C11—H11A0.990
C1—C81.352 (3)C11—H11B0.990
C1—C21.445 (3)C13—H13A0.980
C2—C31.399 (3)C13—H13B0.980
C2—C71.400 (3)C13—H13C0.980
C3—C41.382 (3)C12—H12A0.980
C3—H30.950C12—H12B0.980
C4—C51.407 (3)C12—H12C0.980
C5—C61.386 (3)
O2—S—C1105.94 (10)O1—C8—C9115.37 (18)
O2—S—C13106.48 (12)C8—C9—C10113.32 (18)
C1—S—C1398.80 (11)C8—C9—H9A108.9
C7—O1—C8106.37 (16)C10—C9—H9A108.9
C10—O3—C11115.76 (18)C8—C9—H9B108.9
C8—C1—C2107.76 (18)C10—C9—H9B108.9
C8—C1—S124.73 (17)H9A—C9—H9B107.7
C2—C1—S127.32 (16)O4—C10—O3124.1 (2)
C3—C2—C7119.4 (2)O4—C10—C9126.1 (2)
C3—C2—C1136.1 (2)O3—C10—C9109.77 (18)
C7—C2—C1104.50 (18)O3—C11—C12107.2 (2)
C4—C3—C2116.94 (19)O3—C11—H11A110.3
C4—C3—H3121.5C12—C11—H11A110.3
C2—C3—H3121.5O3—C11—H11B110.3
C3—C4—C5123.1 (2)C12—C11—H11B110.3
C3—C4—I118.37 (15)H11A—C11—H11B108.5
C5—C4—I118.54 (16)S—C13—H13A109.5
C6—C5—C4120.2 (2)S—C13—H13B109.5
C6—C5—H5119.9H13A—C13—H13B109.5
C4—C5—H5119.9S—C13—H13C109.5
C7—C6—C5116.4 (2)H13A—C13—H13C109.5
C7—C6—H6121.8H13B—C13—H13C109.5
C5—C6—H6121.8C11—C12—H12A109.5
O1—C7—C6125.41 (19)C11—C12—H12B109.5
O1—C7—C2110.65 (18)H12A—C12—H12B109.5
C6—C7—C2123.9 (2)C11—C12—H12C109.5
C1—C8—O1110.72 (19)H12A—C12—H12C109.5
C1—C8—C9133.9 (2)H12B—C12—H12C109.5
O2—S—C1—C8135.0 (2)C5—C6—C7—C21.0 (3)
C13—S—C1—C8115.0 (2)C3—C2—C7—O1178.10 (18)
O2—S—C1—C239.3 (2)C1—C2—C7—O10.7 (2)
C13—S—C1—C270.7 (2)C3—C2—C7—C61.6 (3)
C8—C1—C2—C3178.3 (2)C1—C2—C7—C6179.7 (2)
S—C1—C2—C36.6 (4)C2—C1—C8—O10.4 (2)
C8—C1—C2—C70.2 (2)S—C1—C8—O1175.65 (15)
S—C1—C2—C7174.93 (16)C2—C1—C8—C9179.2 (2)
C7—C2—C3—C40.9 (3)S—C1—C8—C95.6 (4)
C1—C2—C3—C4179.2 (2)C7—O1—C8—C10.8 (2)
C2—C3—C4—C50.1 (3)C7—O1—C8—C9179.83 (17)
C2—C3—C4—I179.42 (15)C1—C8—C9—C1064.6 (3)
C3—C4—C5—C60.7 (3)O1—C8—C9—C10114.1 (2)
I—C4—C5—C6178.86 (16)C11—O3—C10—O42.4 (3)
C4—C5—C6—C70.1 (3)C11—O3—C10—C9179.3 (2)
C8—O1—C7—C6179.4 (2)C8—C9—C10—O418.3 (3)
C8—O1—C7—C20.9 (2)C8—C9—C10—O3163.43 (19)
C5—C6—C7—O1178.62 (19)C10—O3—C11—C12176.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···O1i0.992.533.513 (3)174
C9—H9A···O2ii0.992.203.190 (3)174
C3—H3···O2iii0.952.483.391 (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 formulaC13H13IO4S
Mr392.19
Crystal system, space groupTriclinic, 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)
V3)709.92 (6)
Z2
Radiation typeMo Kα
µ (mm1)2.41
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1999)
Tmin, Tmax0.561, 0.790
No. of measured, independent and
observed [I > 2σ(I)] reflections
6175, 3053, 2900
Rint0.016
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.055, 1.08
No. of reflections3053
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···O1i0.992.533.513 (3)173.7
C9—H9A···O2ii0.992.203.190 (3)173.5
C3—H3···O2iii0.952.483.391 (3)160.7
Symmetry codes: (i) x+2, y+2, z+1; (ii) x+2, y+2, z; (iii) x+1, y+2, z.
 

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