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

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

doi:10.1107/S1600536808010064

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o864

doi:10.1107/S1600536808010064

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

Wei Chen,^a Shan Liu,^a Qing-Yan Chu,^a Wei Luo ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 31 March 2008; accepted 12 April 2008; online 18 April 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₁H₁₄O₅S
M_r = 258.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.4890 (15) Å
b = 10.150 (2) Å
c = 17.362 (4) Å
V = 1319.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 (2) K
0.40 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.906, T_max = 0.951
2933 measured reflections
2581 independent reflections
1703 reflections with I > 2σ(I)
R_int = 0.063
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.154
S = 1.01
2581 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 1073 Friedel pairs
Flack parameter: 0.20 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1	0.93	2.53	2.910 (6)	104
C4—H4A⋯O3ⁱ	0.93	2.52	3.297 (5)	141
C6—H6A⋯O1ⁱⁱ	0.93	2.55	3.478 (6)	172
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010064/is2285sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010064/is2285Isup2.hkl

checkCIF report

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.

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

	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.
	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

C₁₁H₁₄O₅S	F(000) = 544
M_r = 258.28	D_x = 1.300 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.4890 (15) Å	θ = 9–14°
b = 10.150 (2) Å	µ = 0.25 mm⁻¹
c = 17.362 (4) Å	T = 298 K
V = 1319.7 (5) Å³	Block, colorless
Z = 4	0.40 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1703 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.063
Graphite monochromator	θ_max = 26.0°, θ_min = 2.3°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.906, T_max = 0.951	l = 0→21
2933 measured reflections	3 standard reflections every 200 reflections
2581 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.06P)² + P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2581 reflections	Δρ_max = 0.31 e Å⁻³
154 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1073 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.20 (16)

Crystal data top

C₁₁H₁₄O₅S	V = 1319.7 (5) Å³
M_r = 258.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.4890 (15) Å	µ = 0.25 mm⁻¹
b = 10.150 (2) Å	T = 298 K
c = 17.362 (4) Å	0.40 × 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)	R_int = 0.063
T_min = 0.906, T_max = 0.951	3 standard reflections every 200 reflections
2933 measured reflections	intensity decay: none
2581 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.154	Δρ_max = 0.31 e Å⁻³
S = 1.01	Δρ_min = −0.29 e Å⁻³
2581 reflections	Absolute structure: Flack (1983), 1073 Friedel pairs
154 parameters	Absolute structure parameter: 0.20 (16)
0 restraints

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

	x	y	z	U_iso*/U_eq
S	0.06641 (15)	0.89958 (12)	0.71844 (7)	0.0628 (3)
O1	0.1083 (4)	0.7829 (3)	0.67754 (18)	0.0765 (10)
O2	0.1557 (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)
C1	0.1382 (8)	0.7979 (7)	1.0589 (3)	0.102 (2)
H1B	0.1073	0.8750	1.0881	0.152*
H1C	0.2598	0.7741	1.0695	0.152*
H1D	0.0608	0.7266	1.0732	0.152*
C2	0.1173 (7)	0.8265 (7)	0.9740 (3)	0.0853 (17)
C3	0.1522 (6)	0.7282 (5)	0.9202 (3)	0.0723 (13)
H3A	0.1874	0.6457	0.9377	0.087*
C4	0.1371 (6)	0.7478 (4)	0.8434 (3)	0.0589 (11)
H4A	0.1627	0.6807	0.8086	0.071*
C5	0.0814 (5)	0.8730 (4)	0.8176 (3)	0.0561 (11)
C6	0.0417 (8)	0.9679 (5)	0.8676 (3)	0.0805 (14)
H6A	0.0034	1.0498	0.8500	0.097*
C7	0.0576 (9)	0.9444 (6)	0.9464 (3)	0.0910 (17)
H7A	0.0267	1.0106	0.9810	0.109*
C8	−0.2695 (6)	0.8272 (5)	0.7102 (3)	0.0715 (13)
H8A	−0.2174	0.7494	0.7350	0.086*
C9	−0.4204 (7)	0.8807 (6)	0.7576 (3)	0.0969 (17)
H9A	−0.3782	0.9008	0.8084	0.145*
H9B	−0.5139	0.8162	0.7607	0.145*
H9C	−0.4659	0.9593	0.7339	0.145*
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	−0.5745	0.5736	0.5671	0.186*
H11B	−0.4134	0.6334	0.5213	0.186*
H11C	−0.5782	0.7219	0.5420	0.186*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0524 (6)	0.0593 (6)	0.0768 (7)	−0.0042 (6)	0.0029 (6)	0.0051 (6)
O1	0.077 (2)	0.080 (2)	0.072 (2)	0.0056 (18)	−0.0007 (17)	−0.0045 (17)
O2	0.078 (2)	0.078 (2)	0.093 (3)	−0.0125 (18)	0.0042 (18)	0.0086 (19)
O3	0.0576 (17)	0.0589 (18)	0.090 (2)	0.0055 (14)	−0.0090 (16)	0.0238 (16)
O4	0.142 (4)	0.119 (4)	0.076 (3)	−0.042 (3)	−0.004 (2)	0.026 (3)
O5	0.098 (3)	0.081 (2)	0.116 (3)	−0.011 (2)	−0.025 (2)	0.012 (2)
C1	0.092 (4)	0.137 (6)	0.075 (4)	−0.009 (4)	−0.007 (3)	−0.003 (4)
C2	0.057 (3)	0.118 (5)	0.081 (4)	−0.014 (3)	−0.012 (3)	−0.005 (4)
C3	0.058 (3)	0.070 (3)	0.089 (4)	−0.009 (2)	−0.017 (2)	0.008 (3)
C4	0.061 (3)	0.043 (2)	0.072 (3)	−0.0061 (19)	−0.006 (2)	−0.001 (2)
C5	0.036 (2)	0.052 (3)	0.080 (3)	−0.0096 (19)	−0.002 (2)	0.001 (2)
C6	0.090 (4)	0.061 (3)	0.090 (4)	0.011 (3)	0.004 (3)	−0.005 (3)
C7	0.087 (4)	0.096 (4)	0.090 (4)	−0.012 (4)	0.007 (3)	−0.032 (3)
C8	0.053 (2)	0.076 (3)	0.085 (4)	−0.010 (2)	−0.008 (2)	0.023 (3)
C9	0.078 (3)	0.114 (4)	0.099 (4)	−0.010 (4)	0.017 (3)	0.005 (3)
C10	0.053 (3)	0.085 (4)	0.089 (4)	−0.005 (3)	−0.004 (3)	0.021 (3)
C11	0.140 (7)	0.111 (5)	0.121 (6)	−0.019 (5)	−0.036 (4)	−0.009 (4)

Geometric parameters (Å, º) top

S—O1	1.416 (3)	C4—C5	1.411 (6)
S—O2	1.444 (3)	C4—H4A	0.9300
S—O3	1.581 (3)	C5—C6	1.331 (6)
S—C5	1.746 (5)	C6—C7	1.395 (8)
O3—C8	1.470 (5)	C6—H6A	0.9300
O4—C10	1.174 (6)	C7—H7A	0.9300
O5—C10	1.299 (6)	C8—C9	1.500 (7)
O5—C11	1.444 (7)	C8—C10	1.507 (7)
C1—C2	1.511 (7)	C8—H8A	0.9800
C1—H1B	0.9600	C9—H9A	0.9600
C1—H1C	0.9600	C9—H9B	0.9600
C1—H1D	0.9600	C9—H9C	0.9600
C2—C7	1.364 (8)	C11—H11A	0.9600
C2—C3	1.392 (8)	C11—H11B	0.9600
C3—C4	1.353 (6)	C11—H11C	0.9600
C3—H3A	0.9300

O1—S—O2	120.5 (2)	C5—C6—H6A	120.1
O1—S—O3	109.0 (2)	C7—C6—H6A	120.1
O2—S—O3	103.07 (19)	C2—C7—C6	121.5 (5)
O1—S—C5	110.5 (2)	C2—C7—H7A	119.3
O2—S—C5	108.5 (2)	C6—C7—H7A	119.3
O3—S—C5	103.75 (18)	O3—C8—C9	105.8 (4)
C8—O3—S	118.7 (3)	O3—C8—C10	106.9 (4)
C10—O5—C11	115.4 (5)	C9—C8—C10	112.5 (4)
C2—C1—H1B	109.5	O3—C8—H8A	110.5
C2—C1—H1C	109.5	C9—C8—H8A	110.5
H1B—C1—H1C	109.5	C10—C8—H8A	110.5
C2—C1—H1D	109.5	C8—C9—H9A	109.5
H1B—C1—H1D	109.5	C8—C9—H9B	109.5
H1C—C1—H1D	109.5	H9A—C9—H9B	109.5
C7—C2—C3	117.0 (5)	C8—C9—H9C	109.5
C7—C2—C1	123.0 (6)	H9A—C9—H9C	109.5
C3—C2—C1	119.9 (6)	H9B—C9—H9C	109.5
C4—C3—C2	122.8 (5)	O4—C10—O5	126.3 (6)
C4—C3—H3A	118.6	O4—C10—C8	125.9 (5)
C2—C3—H3A	118.6	O5—C10—C8	107.6 (5)
C3—C4—C5	118.0 (4)	O5—C11—H11A	109.5
C3—C4—H4A	121.0	O5—C11—H11B	109.5
C5—C4—H4A	121.0	H11A—C11—H11B	109.5
C6—C5—C4	120.8 (4)	O5—C11—H11C	109.5
C6—C5—S	121.1 (4)	H11A—C11—H11C	109.5
C4—C5—S	118.1 (3)	H11B—C11—H11C	109.5
C5—C6—C7	119.8 (5)

O1—S—O3—C8	44.2 (4)	C4—C5—C6—C7	0.9 (8)
O2—S—O3—C8	173.3 (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—C4	3.2 (8)	C1—C2—C7—C6	179.3 (5)
C1—C2—C3—C4	−179.6 (5)	C5—C6—C7—C2	1.6 (9)
C2—C3—C4—C5	−0.8 (7)	S—O3—C8—C9	135.0 (4)
C3—C4—C5—C6	−1.3 (6)	S—O3—C8—C10	−104.8 (4)
C3—C4—C5—S	178.7 (3)	C11—O5—C10—O4	−2.2 (9)
O1—S—C5—C6	−177.6 (4)	C11—O5—C10—C8	172.4 (5)
O2—S—C5—C6	48.2 (5)	O3—C8—C10—O4	−15.7 (7)
O3—S—C5—C6	−60.9 (4)	C9—C8—C10—O4	100.0 (7)
O1—S—C5—C4	2.4 (4)	O3—C8—C10—O5	169.7 (4)
O2—S—C5—C4	−131.7 (3)	C9—C8—C10—O5	−74.6 (6)
O3—S—C5—C4	119.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1	0.93	2.53	2.910 (6)	104
C4—H4A···O3ⁱ	0.93	2.52	3.297 (5)	141
C6—H6A···O1ⁱⁱ	0.93	2.55	3.478 (6)	172

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄O₅S
M_r	258.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.4890 (15), 10.150 (2), 17.362 (4)
V (Å³)	1319.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.906, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	2933, 2581, 1703
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.154, 1.01
No. of reflections	2581
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.29
Absolute structure	Flack (1983), 1073 Friedel pairs
Absolute structure parameter	0.20 (16)

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1	0.93	2.53	2.910 (6)	104
C4—H4A···O3ⁱ	0.93	2.52	3.297 (5)	141
C6—H6A···O1ⁱⁱ	0.93	2.55	3.478 (6)	172

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2.

Acknowledgements

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

References

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