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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.064
• wR factor = 0.154
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

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Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.98
           From the CIF: _reflns_number_total               2581
           Count of symmetry unique reflns         1514
           Completeness (_total/calc)            170.48%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1067
           Fraction of Friedel pairs measured     0.705
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C8     ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

(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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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

Crystal data

C11H14O5S	F(000) = 544
Mr = 258.28	Dx = 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) Å^3	Block, colorless
Z = 4	0.40 × 0.20 × 0.20 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.063	H-atom parameters constrained
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.06P)^2 + P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2581 reflections	Δρmax = 0.31 e Å^−3
154 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O3^i	0.93	2.52	3.297 (5)	141
C6—H6A···O1^ii	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.