(1R,2S,5R)-(-)-Menthyl (S)-2-(methoxy-carbonyl)-benzene-sulfinate.

In the title chiral sulfinic acid ester, C18H26O4S, the cyclo-hexane ring of the menthyl fragment adopts a chair conformation. The mol-ecular shape is defined by the dihedral angle of 47.87 (8)° between the mean planes of the cyclo-hexane and benzene rings. In the crystal, mol-ecules related by the screw axis are connected into chains along [010] by weak Car-H⋯O=S contacts.

Related literature

For the synthesis of the title compound, see: Klunder & Sharpless (1987 ▶) and of chiral sulfoxides, see: Drabowicz et al. (1982 ▶); Solladié et al. (1987 ▶). For applications of menthol in synthetic chemistry, see Oertling et al. (2007 ▶). For structural studies of analogous chiral sulfinic acid esters, see: Mariz et al. (2010 ▶); Heinemann et al. (2007 ▶); Cherkaoui & Nicoud (1995 ▶).

Experimental

Crystal data

C18H26O4S

M = 338.45

Monoclinic,

a = 9.7918 (2) Å

b = 9.3938 (2) Å

c = 10.6998 (2) Å

β = 112.176 (2)°

V = 911.39 (3) Å3

Z = 2

Cu Kα radiation

μ = 1.72 mm−1

T = 150 K

0.26 × 0.22 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur PX diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.660, T max = 0.872

4681 measured reflections

2354 independent reflections

2115 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.078

S = 1.07

2354 reflections

209 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 767 Friedel pairs

Flack parameter: 0.038 (18)

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PARST (Nardelli, 1995 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009112/yk2089sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009112/yk2089Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813009112/yk2089Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H26O4S	F(000) = 364
Mr = 338.45	Dx = 1.233 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.5418 Å
a = 9.7918 (2) Å	Cell parameters from 3618 reflections
b = 9.3938 (2) Å	θ = 4.5–64.6°
c = 10.6998 (2) Å	µ = 1.72 mm−1
β = 112.176 (2)°	T = 150 K
V = 911.39 (3) Å3	Platelet, colourless
Z = 2	0.26 × 0.22 × 0.08 mm

Oxford Diffraction Xcalibur PX diffractometer	2354 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2115 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 8.1241 pixels mm-1	θmax = 64.8°, θmin = 4.5°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −10→8
Tmin = 0.660, Tmax = 0.872	l = −11→12
4681 measured reflections

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)] = 0.031	H-atom parameters constrained
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0533P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2354 reflections	Δρmax = 0.15 e Å−3
209 parameters	Δρmin = −0.22 e Å−3
1 restraint	Absolute structure: Flack (1983), 767 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.038 (18)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
S1	0.13357 (6)	0.36878 (7)	0.29567 (5)	0.02816 (16)
O1	−0.12928 (17)	0.2413 (2)	0.29271 (17)	0.0370 (5)
O2	−0.14622 (19)	0.0826 (2)	0.44178 (18)	0.0456 (5)
O3	0.10664 (16)	0.26365 (17)	0.16750 (14)	0.0276 (4)
O4	0.27015 (18)	0.4479 (2)	0.31899 (17)	0.0393 (5)
C1	0.1889 (2)	0.2232 (3)	0.4157 (2)	0.0276 (6)
C2	0.0910 (3)	0.1423 (3)	0.4543 (2)	0.0278 (5)
C3	0.1479 (3)	0.0401 (3)	0.5550 (2)	0.0351 (6)
H3	0.0830	−0.0130	0.5844	0.042*
C4	0.2987 (3)	0.0150 (3)	0.6128 (2)	0.0401 (7)
H4	0.3364	−0.0556	0.6808	0.048*
C5	0.3939 (3)	0.0927 (3)	0.5715 (2)	0.0417 (7)
H5	0.4969	0.0741	0.6096	0.050*
C6	0.3395 (3)	0.1976 (3)	0.4747 (2)	0.0350 (6)
H6	0.4056	0.2526	0.4484	0.042*
C7	−0.0714 (2)	0.1625 (3)	0.3865 (2)	0.0288 (5)
C8	−0.3054 (3)	0.0939 (4)	0.3802 (3)	0.0586 (9)
H8A	−0.3501	0.0279	0.4248	0.088*
H8B	−0.3386	0.0700	0.2842	0.088*
H8C	−0.3353	0.1915	0.3901	0.088*
C9	0.0431 (2)	0.3366 (2)	0.03670 (19)	0.0252 (5)
H9	0.0707	0.4396	0.0496	0.030*
C10	0.1105 (3)	0.2704 (3)	−0.0566 (2)	0.0322 (6)
H10	0.0819	0.1676	−0.0660	0.039*
C11	0.0369 (3)	0.3372 (3)	−0.1967 (2)	0.0404 (7)
H11A	0.0642	0.4391	−0.1920	0.048*
H11B	0.0742	0.2898	−0.2602	0.048*
C12	−0.1312 (3)	0.3239 (3)	−0.2505 (2)	0.0439 (7)
H12A	−0.1740	0.3709	−0.3397	0.053*
H12B	−0.1588	0.2220	−0.2628	0.053*
C13	−0.1943 (3)	0.3903 (3)	−0.1564 (2)	0.0377 (7)
H13	−0.1691	0.4939	−0.1486	0.045*
C14	−0.1233 (2)	0.3239 (3)	−0.0165 (2)	0.0333 (6)
H14A	−0.1609	0.3721	0.0464	0.040*
H14B	−0.1511	0.2222	−0.0210	0.040*
C15	−0.3628 (3)	0.3767 (5)	−0.2088 (3)	0.0574 (8)
H15A	−0.3992	0.4212	−0.1445	0.086*
H15B	−0.3903	0.2757	−0.2188	0.086*
H15C	−0.4067	0.4242	−0.2964	0.086*
C16	0.2812 (3)	0.2752 (3)	0.0022 (3)	0.0397 (7)
H16	0.3151	0.2284	0.0928	0.048*
C17	0.3439 (3)	0.4256 (3)	0.0237 (3)	0.0487 (8)
H17A	0.3020	0.4796	0.0791	0.073*
H17B	0.3188	0.4728	−0.0639	0.073*
H17C	0.4514	0.4214	0.0697	0.073*
C18	0.3433 (4)	0.1894 (4)	−0.0842 (3)	0.0599 (9)
H18A	0.3017	0.0932	−0.0970	0.090*
H18B	0.4509	0.1839	−0.0393	0.090*
H18C	0.3176	0.2358	−0.1722	0.090*

	U11	U22	U33	U12	U13	U23
S1	0.0300 (3)	0.0257 (3)	0.0306 (3)	−0.0036 (3)	0.0135 (2)	−0.0045 (3)
O1	0.0298 (9)	0.0443 (12)	0.0374 (9)	0.0010 (8)	0.0133 (8)	0.0100 (9)
O2	0.0312 (9)	0.0591 (14)	0.0451 (10)	−0.0078 (9)	0.0127 (9)	0.0180 (10)
O3	0.0333 (8)	0.0240 (9)	0.0245 (8)	0.0019 (7)	0.0099 (7)	−0.0007 (7)
O4	0.0361 (9)	0.0407 (11)	0.0410 (9)	−0.0146 (9)	0.0144 (8)	−0.0045 (9)
C1	0.0289 (12)	0.0302 (15)	0.0209 (11)	−0.0024 (11)	0.0065 (10)	−0.0045 (10)
C2	0.0302 (12)	0.0306 (15)	0.0225 (11)	0.0002 (11)	0.0097 (9)	−0.0035 (10)
C3	0.0395 (14)	0.0363 (16)	0.0276 (12)	−0.0029 (12)	0.0104 (12)	−0.0004 (12)
C4	0.0456 (16)	0.0387 (18)	0.0291 (13)	0.0101 (13)	0.0062 (13)	0.0005 (12)
C5	0.0318 (14)	0.0530 (19)	0.0331 (13)	0.0105 (13)	0.0040 (12)	−0.0082 (14)
C6	0.0303 (13)	0.0414 (17)	0.0332 (13)	0.0015 (12)	0.0119 (11)	−0.0065 (12)
C7	0.0310 (13)	0.0292 (15)	0.0279 (12)	−0.0023 (11)	0.0131 (11)	−0.0033 (12)
C8	0.0299 (14)	0.083 (3)	0.0579 (18)	−0.0111 (16)	0.0109 (14)	0.0230 (18)
C9	0.0300 (11)	0.0190 (15)	0.0264 (11)	−0.0018 (10)	0.0102 (9)	0.0021 (10)
C10	0.0383 (13)	0.0275 (15)	0.0333 (12)	−0.0012 (12)	0.0163 (11)	0.0009 (11)
C11	0.0554 (16)	0.038 (2)	0.0332 (12)	−0.0040 (13)	0.0226 (12)	0.0031 (12)
C12	0.0538 (16)	0.0390 (18)	0.0301 (12)	−0.0056 (13)	0.0058 (11)	0.0043 (12)
C13	0.0370 (13)	0.0301 (18)	0.0368 (12)	−0.0022 (12)	0.0034 (11)	0.0035 (13)
C14	0.0284 (12)	0.0338 (17)	0.0352 (12)	−0.0003 (11)	0.0092 (10)	0.0000 (11)
C15	0.0369 (13)	0.068 (2)	0.0492 (15)	−0.0022 (17)	−0.0037 (12)	0.0096 (18)
C16	0.0421 (15)	0.0395 (18)	0.0469 (15)	0.0020 (13)	0.0275 (12)	0.0043 (14)
C17	0.0396 (15)	0.053 (2)	0.0575 (18)	−0.0113 (14)	0.0229 (14)	−0.0056 (15)
C18	0.065 (2)	0.056 (2)	0.076 (2)	0.0083 (18)	0.0462 (17)	−0.0065 (19)

S1—O4	1.4669 (17)	C10—C16	1.548 (3)
S1—O3	1.6287 (16)	C10—H10	1.0000
S1—C1	1.813 (2)	C11—C12	1.530 (3)
O1—C7	1.203 (3)	C11—H11A	0.9900
O2—C7	1.333 (3)	C11—H11B	0.9900
O2—C8	1.449 (3)	C12—C13	1.501 (4)
O3—C9	1.469 (2)	C12—H12A	0.9900
C1—C6	1.388 (3)	C12—H12B	0.9900
C1—C2	1.403 (3)	C13—C14	1.525 (3)
C2—C3	1.392 (4)	C13—C15	1.535 (3)
C2—C7	1.490 (3)	C13—H13	1.0000
C3—C4	1.389 (4)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.382 (4)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—C6	1.382 (4)	C15—H15C	0.9800
C5—H5	0.9500	C16—C18	1.517 (4)
C6—H6	0.9500	C16—C17	1.524 (4)
C8—H8A	0.9800	C16—H16	1.0000
C8—H8B	0.9800	C17—H17A	0.9800
C8—H8C	0.9800	C17—H17B	0.9800
C9—C14	1.514 (3)	C17—H17C	0.9800
C9—C10	1.522 (3)	C18—H18A	0.9800
C9—H9	1.0000	C18—H18B	0.9800
C10—C11	1.532 (3)	C18—H18C	0.9800
O4—S1—O3	107.34 (9)	C10—C11—H11A	109.2
O4—S1—C1	104.61 (10)	C12—C11—H11B	109.2
O3—S1—C1	92.81 (9)	C10—C11—H11B	109.2
C7—O2—C8	115.7 (2)	H11A—C11—H11B	107.9
C9—O3—S1	113.26 (13)	C13—C12—C11	111.8 (2)
C6—C1—C2	119.9 (2)	C13—C12—H12A	109.3
C6—C1—S1	115.80 (19)	C11—C12—H12A	109.3
C2—C1—S1	124.25 (17)	C13—C12—H12B	109.3
C3—C2—C1	118.9 (2)	C11—C12—H12B	109.3
C3—C2—C7	120.4 (2)	H12A—C12—H12B	107.9
C1—C2—C7	120.7 (2)	C12—C13—C14	109.7 (2)
C4—C3—C2	120.6 (2)	C12—C13—C15	112.2 (2)
C4—C3—H3	119.7	C14—C13—C15	110.7 (2)
C2—C3—H3	119.7	C12—C13—H13	108.0
C5—C4—C3	120.0 (3)	C14—C13—H13	108.0
C5—C4—H4	120.0	C15—C13—H13	108.0
C3—C4—H4	120.0	C9—C14—C13	111.34 (19)
C4—C5—C6	120.0 (2)	C9—C14—H14A	109.4
C4—C5—H5	120.0	C13—C14—H14A	109.4
C6—C5—H5	120.0	C9—C14—H14B	109.4
C5—C6—C1	120.5 (2)	C13—C14—H14B	109.4
C5—C6—H6	119.8	H14A—C14—H14B	108.0
C1—C6—H6	119.8	C13—C15—H15A	109.5
O1—C7—O2	123.5 (2)	C13—C15—H15B	109.5
O1—C7—C2	124.4 (2)	H15A—C15—H15B	109.5
O2—C7—C2	112.1 (2)	C13—C15—H15C	109.5
O2—C8—H8A	109.5	H15A—C15—H15C	109.5
O2—C8—H8B	109.5	H15B—C15—H15C	109.5
H8A—C8—H8B	109.5	C18—C16—C17	110.6 (2)
O2—C8—H8C	109.5	C18—C16—C10	110.9 (2)
H8A—C8—H8C	109.5	C17—C16—C10	113.6 (2)
H8B—C8—H8C	109.5	C18—C16—H16	107.1
O3—C9—C14	109.29 (17)	C17—C16—H16	107.1
O3—C9—C10	107.54 (18)	C10—C16—H16	107.1
C14—C9—C10	113.12 (18)	C16—C17—H17A	109.5
O3—C9—H9	108.9	C16—C17—H17B	109.5
C14—C9—H9	108.9	H17A—C17—H17B	109.5
C10—C9—H9	108.9	C16—C17—H17C	109.5
C9—C10—C11	108.34 (19)	H17A—C17—H17C	109.5
C9—C10—C16	112.98 (19)	H17B—C17—H17C	109.5
C11—C10—C16	115.0 (2)	C16—C18—H18A	109.5
C9—C10—H10	106.7	C16—C18—H18B	109.5
C11—C10—H10	106.7	H18A—C18—H18B	109.5
C16—C10—H10	106.7	C16—C18—H18C	109.5
C12—C11—C10	112.09 (19)	H18A—C18—H18C	109.5
C12—C11—H11A	109.2	H18B—C18—H18C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4i	0.95	2.42	3.337 (3)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O4i	0.95	2.42	3.337 (3)	161

Symmetry code: (i) .