supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

is2285 scheme

Acta Cryst. (2008). E64, o864    [ doi:10.1107/S1600536808010064 ]

(S)-(-)-Methyl 2-(p-tolylsulfonyloxy)propanoate

W. Chen, S. Liu, Q.-Y. Chu, W. Luo and H.-J. Zhu

Abstract top

In the title compound, C11H14O5S, there is an intramolecular C-H...O hydrogen bond, for which the C-C-S-O torsion angle involving the acceptor and donor atoms is 2.4 (4)°. The dihedral angle between the benzene ring and the methoxycarbonyl plane is 52.7 (4)°. In the crystal structure, molecules are linked via intermolecular C-H...O hydrogen bonds, forming a molecular chain along the b axis.

Comment top

(S)-(-)-methyl 2-(p-toluenesulfonyloxy)propanoate is an important fine chemical, which can be used for many fields such as chiral pesticide, organometallic chemistry, etc. (Talbert et al., 1974). The bond lengths and angles of the title compound are within normal ranges (Allen et al., 1987). In the crystal structure, molecules are linked via intermolecular C—H···O hydrogen bonds, which with intramolecular C—H···O hydrogen bonds seem to be effective in the stabilization of the crystal. As can be seen from the packing diagram (Fig. 2), the molecules are stacked along the a axis.

Related literature top

For related literature, see: Allen et al. (1987); Chan et al. (1975); Talbert et al. (1974).

Experimental top

The title compound was prepared according to the literature method (Chan et al., 1975). The crystals were obtained by dissolving the title compound (500 mg, 2 mmol) in ethyl acetate (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Refinement top

H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A drawing of the title molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is shown by dashed line.
[Figure 2] Fig. 2. A packing diagram of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.
(S)-(-)-Methyl 2-(p-tolylsulfonyloxy)propanoate top
Crystal data top
C11H14O5SF000 = 544
Mr = 258.28Dx = 1.300 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 7.4890 (15) Åθ = 9–14º
b = 10.150 (2) ŵ = 0.25 mm−1
c = 17.362 (4) ÅT = 298 (2) K
V = 1319.7 (5) Å3Block, colorless
Z = 40.40 × 0.20 × 0.20 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.063
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 2.3º
T = 298(2) Kh = −9→9
ω/2θ scansk = 0→12
Absorption correction: ψ scan
(North et al., 1968)		l = 0→21
Tmin = 0.906, Tmax = 0.9513 standard reflections
2933 measured reflections every 200 reflections
2581 independent reflections intensity decay: none
1703 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.063  w = 1/[σ2(Fo2) + (0.06P)2 + P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.154(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.31 e Å−3
2581 reflectionsΔρmin = −0.29 e Å−3
154 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1073 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.20 (16)
Crystal data top
C11H14O5SV = 1319.7 (5) Å3
Mr = 258.28Z = 4
Orthorhombic, P212121Mo Kα
a = 7.4890 (15) ŵ = 0.25 mm−1
b = 10.150 (2) ÅT = 298 (2) K
c = 17.362 (4) Å0.40 × 0.20 × 0.20 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1703 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.063
Tmin = 0.906, Tmax = 0.9513 standard reflections
2933 measured reflections every 200 reflections
2581 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.154Δρmax = 0.31 e Å−3
S = 1.01Δρmin = −0.29 e Å−3
2581 reflectionsAbsolute structure: Flack (1983), 1073 Friedel pairs
154 parametersFlack parameter: 0.20 (16)
Special details top

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
S0.06641 (15)0.89958 (12)0.71844 (7)0.0628 (3)
O10.1083 (4)0.7829 (3)0.67754 (18)0.0765 (10)
O20.1557 (5)1.0219 (3)0.7003 (2)0.0830 (10)
O3−0.1372 (4)0.9339 (3)0.70538 (18)0.0689 (9)
O4−0.3001 (6)0.8618 (5)0.5745 (2)0.1125 (16)
O5−0.4188 (5)0.6878 (4)0.6310 (2)0.0984 (12)
C10.1382 (8)0.7979 (7)1.0589 (3)0.102 (2)
H1B0.10730.87501.08810.152*
H1C0.25980.77411.06950.152*
H1D0.06080.72661.07320.152*
C20.1173 (7)0.8265 (7)0.9740 (3)0.0853 (17)
C30.1522 (6)0.7282 (5)0.9202 (3)0.0723 (13)
H3A0.18740.64570.93770.087*
C40.1371 (6)0.7478 (4)0.8434 (3)0.0589 (11)
H4A0.16270.68070.80860.071*
C50.0814 (5)0.8730 (4)0.8176 (3)0.0561 (11)
C60.0417 (8)0.9679 (5)0.8676 (3)0.0805 (14)
H6A0.00341.04980.85000.097*
C70.0576 (9)0.9444 (6)0.9464 (3)0.0910 (17)
H7A0.02671.01060.98100.109*
C8−0.2695 (6)0.8272 (5)0.7102 (3)0.0715 (13)
H8A−0.21740.74940.73500.086*
C9−0.4204 (7)0.8807 (6)0.7576 (3)0.0969 (17)
H9A−0.37820.90080.80840.145*
H9B−0.51390.81620.76070.145*
H9C−0.46590.95930.73390.145*
C10−0.3253 (6)0.7955 (6)0.6289 (3)0.0758 (14)
C11−0.5033 (10)0.6511 (7)0.5593 (4)0.124 (3)
H11A−0.57450.57360.56710.186*
H11B−0.41340.63340.52130.186*
H11C−0.57820.72190.54200.186*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0524 (6)0.0593 (6)0.0768 (7)−0.0042 (6)0.0029 (6)0.0051 (6)
O10.077 (2)0.080 (2)0.072 (2)0.0056 (18)−0.0007 (17)−0.0045 (17)
O20.078 (2)0.078 (2)0.093 (3)−0.0125 (18)0.0042 (18)0.0086 (19)
O30.0576 (17)0.0589 (18)0.090 (2)0.0055 (14)−0.0090 (16)0.0238 (16)
O40.142 (4)0.119 (4)0.076 (3)−0.042 (3)−0.004 (2)0.026 (3)
O50.098 (3)0.081 (2)0.116 (3)−0.011 (2)−0.025 (2)0.012 (2)
C10.092 (4)0.137 (6)0.075 (4)−0.009 (4)−0.007 (3)−0.003 (4)
C20.057 (3)0.118 (5)0.081 (4)−0.014 (3)−0.012 (3)−0.005 (4)
C30.058 (3)0.070 (3)0.089 (4)−0.009 (2)−0.017 (2)0.008 (3)
C40.061 (3)0.043 (2)0.072 (3)−0.0061 (19)−0.006 (2)−0.001 (2)
C50.036 (2)0.052 (3)0.080 (3)−0.0096 (19)−0.002 (2)0.001 (2)
C60.090 (4)0.061 (3)0.090 (4)0.011 (3)0.004 (3)−0.005 (3)
C70.087 (4)0.096 (4)0.090 (4)−0.012 (4)0.007 (3)−0.032 (3)
C80.053 (2)0.076 (3)0.085 (4)−0.010 (2)−0.008 (2)0.023 (3)
C90.078 (3)0.114 (4)0.099 (4)−0.010 (4)0.017 (3)0.005 (3)
C100.053 (3)0.085 (4)0.089 (4)−0.005 (3)−0.004 (3)0.021 (3)
C110.140 (7)0.111 (5)0.121 (6)−0.019 (5)−0.036 (4)−0.009 (4)
Geometric parameters (Å, °) top
S—O11.416 (3)C4—C51.411 (6)
S—O21.444 (3)C4—H4A0.9300
S—O31.581 (3)C5—C61.331 (6)
S—C51.746 (5)C6—C71.395 (8)
O3—C81.470 (5)C6—H6A0.9300
O4—C101.174 (6)C7—H7A0.9300
O5—C101.299 (6)C8—C91.500 (7)
O5—C111.444 (7)C8—C101.507 (7)
C1—C21.511 (7)C8—H8A0.9800
C1—H1B0.9600C9—H9A0.9600
C1—H1C0.9600C9—H9B0.9600
C1—H1D0.9600C9—H9C0.9600
C2—C71.364 (8)C11—H11A0.9600
C2—C31.392 (8)C11—H11B0.9600
C3—C41.353 (6)C11—H11C0.9600
C3—H3A0.9300
O1—S—O2120.5 (2)C5—C6—H6A120.1
O1—S—O3109.0 (2)C7—C6—H6A120.1
O2—S—O3103.07 (19)C2—C7—C6121.5 (5)
O1—S—C5110.5 (2)C2—C7—H7A119.3
O2—S—C5108.5 (2)C6—C7—H7A119.3
O3—S—C5103.75 (18)O3—C8—C9105.8 (4)
C8—O3—S118.7 (3)O3—C8—C10106.9 (4)
C10—O5—C11115.4 (5)C9—C8—C10112.5 (4)
C2—C1—H1B109.5O3—C8—H8A110.5
C2—C1—H1C109.5C9—C8—H8A110.5
H1B—C1—H1C109.5C10—C8—H8A110.5
C2—C1—H1D109.5C8—C9—H9A109.5
H1B—C1—H1D109.5C8—C9—H9B109.5
H1C—C1—H1D109.5H9A—C9—H9B109.5
C7—C2—C3117.0 (5)C8—C9—H9C109.5
C7—C2—C1123.0 (6)H9A—C9—H9C109.5
C3—C2—C1119.9 (6)H9B—C9—H9C109.5
C4—C3—C2122.8 (5)O4—C10—O5126.3 (6)
C4—C3—H3A118.6O4—C10—C8125.9 (5)
C2—C3—H3A118.6O5—C10—C8107.6 (5)
C3—C4—C5118.0 (4)O5—C11—H11A109.5
C3—C4—H4A121.0O5—C11—H11B109.5
C5—C4—H4A121.0H11A—C11—H11B109.5
C6—C5—C4120.8 (4)O5—C11—H11C109.5
C6—C5—S121.1 (4)H11A—C11—H11C109.5
C4—C5—S118.1 (3)H11B—C11—H11C109.5
C5—C6—C7119.8 (5)
O1—S—O3—C844.2 (4)C4—C5—C6—C70.9 (8)
O2—S—O3—C8173.3 (3)S—C5—C6—C7−179.0 (4)
C5—S—O3—C8−73.6 (4)C3—C2—C7—C6−3.5 (9)
C7—C2—C3—C43.2 (8)C1—C2—C7—C6179.3 (5)
C1—C2—C3—C4−179.6 (5)C5—C6—C7—C21.6 (9)
C2—C3—C4—C5−0.8 (7)S—O3—C8—C9135.0 (4)
C3—C4—C5—C6−1.3 (6)S—O3—C8—C10−104.8 (4)
C3—C4—C5—S178.7 (3)C11—O5—C10—O4−2.2 (9)
O1—S—C5—C6−177.6 (4)C11—O5—C10—C8172.4 (5)
O2—S—C5—C648.2 (5)O3—C8—C10—O4−15.7 (7)
O3—S—C5—C6−60.9 (4)C9—C8—C10—O4100.0 (7)
O1—S—C5—C42.4 (4)O3—C8—C10—O5169.7 (4)
O2—S—C5—C4−131.7 (3)C9—C8—C10—O5−74.6 (6)
O3—S—C5—C4119.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O10.932.532.910 (6)104
C4—H4A···O3i0.932.523.297 (5)141
C6—H6A···O1ii0.932.553.478 (6)172
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O10.932.532.910 (6)104
C4—H4A···O3i0.932.523.297 (5)141
C6—H6A···O1ii0.932.553.478 (6)172
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Chan, J. H., Walker, F., Tseng, C. K., Baker, D. R. & Arneklev, D. R. (1975). J. Agric. Food Chem. 23, 1008–1010.

Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Talbert, R. E., Frans, R. E. & Ramthun, L. E. (1974). Arkansas Agric. 11, 226–244.