Absolute configuration of a C₂-symmetric bis­(thio­phenol)

In order to determine the absolute configuration of the new chiral auxiliary trans-1,2-cyclo­pentane­diyl­bis(2-benzene­thiol), one of the diastereomeric bis-esters with (-)-menthol, used in the resolution of the auxiliary, was subjected to X-ray study. This (-)-diastereomer proved to be (1S,2S)-1,2-bis{2-[(-)-3-p-menthyl­oxy­carbonyl­thio]­phenyl}­cyclo­pentane, C₃₉H₅₄O₄S₂.

S1. Comment

In order to determine the absolute configuration of the new chiral auxiliary trans-1,2-cyclopentanediylbis(2-thiophenol), (II) (Kane et al., 1999),one of the diastereomeric bis-esters with (-)-menthol, used in the resolution of the auxiliary, was subjected to X-ray study. This (-)-diastereomer proved to be (1S,2S)-1,2-bis{2-[(-)-3-p-menthyloxycarbonylthio]phenyl}cyclopentane (I).

S2. Experimental

Compound (II) was prepared as described (Kane et al., 1999). Crystals (m.p. 409–411 K) were grown by slow evaporation of a methanol solution. Samples of the other diastereomer (m.p. 355–356 K) treated similarly were determined to be an amorphous glass.

S3. Refinement

Data collection was performed on two different, but similarly sized and shaped crystals due to the loss of crystal (I) before higher-angle data could be collected. The first provided a shell covering 0.0 < θ < 21.1° and the second a shell covering 4.5 < θ < 25.5°. The identically integrated and reduced data sets were scaled and joined, but not merged within XPREP (Bruker, 1997b) to provide the set used in refinement. H atoms were placed in idealized positions, forced to ride on the atom to which they are bonded (C—H 0.96–1.00 Å) and had displacement parameters equal to 1.2 or 1.5 times that of the atom to which they are bonded. Methyl H atoms were allowed to rotate about the C—C bond while retaining an idealized tetrahedral geometry.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.

(1S,2S)-1,2-bis(2'-thiophenyl)cyclopentane bis-(-)- menthylcarbonate

Crystal data

C39H54O4S2	Melting point: 136-138 C K
Mr = 650.94	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6122	Cell parameters from 5895 reflections
a = 9.3218 (7) Å	θ = 2.5–21.0°
c = 73.631 (8) Å	µ = 0.18 mm^−1
V = 5541.0 (8) Å^3	T = 170 K
Z = 6	Plate, colourless
F(000) = 2112	0.35 × 0.22 × 0.02 mm
Dx = 1.170 Mg m^−3

Data collection

Bruker CCD area-detector diffractometer	3445 independent reflections
Radiation source: fine-focus sealed tube	2275 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ϕ and ω scans	θmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −11→8
Tmin = 0.879, Tmax = 0.977	k = −10→11
46321 measured reflections	l = −87→88

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0604P)^2 + 1.0971P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.119	(Δ/σ)max = 0.002
S = 1.00	Δρmax = 0.19 e Å^−3
3445 reflections	Δρmin = −0.22 e Å^−3
209 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0040 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 975 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.03 (11)

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
S1	0.42837 (10)	0.94525 (8)	0.038077 (9)	0.0476 (2)
O1	0.4573 (2)	0.9375 (2)	0.07214 (2)	0.0458 (5)
O2	0.5655 (3)	1.1976 (2)	0.06127 (2)	0.0561 (6)
C6	0.4955 (4)	1.0499 (3)	0.05917 (3)	0.0429 (7)
C7	0.5041 (4)	1.0019 (3)	0.09096 (3)	0.0428 (7)
H7A	0.4861	1.0982	0.0927	0.051*
C8	0.3898 (4)	0.8613 (3)	0.10353 (3)	0.0433 (7)
H8A	0.4135	0.7690	0.1016	0.052*
C12	0.6843 (4)	1.0565 (4)	0.09414 (3)	0.0492 (7)
H12A	0.7535	1.1477	0.0857	0.059*
H12B	0.7029	0.9629	0.0915	0.059*
C2'	0.5189 (4)	1.1192 (3)	0.02316 (3)	0.0450 (7)
C9	0.4425 (4)	0.9234 (4)	0.12306 (3)	0.0545 (8)
H9A	0.4237	1.0174	0.1253	0.065*
H9B	0.3724	0.8336	0.1316	0.065*
C4	−0.0299 (5)	1.0000	0.0000	0.0675 (13)
H4A	−0.0631	1.0544	−0.0087	0.081*
C1'	0.4233 (3)	1.1554 (3)	0.01144 (3)	0.0428 (7)
C1	0.2398 (3)	1.0454 (3)	0.00927 (3)	0.0435 (7)
H1A	0.1996	0.9601	0.0191	0.052*
C11	0.7377 (4)	1.1148 (4)	0.11357 (4)	0.0508 (8)
H11A	0.7252	1.2139	0.1157	0.061*
C6'	0.5087 (4)	1.2957 (4)	0.00040 (4)	0.0548 (8)
H6'A	0.4472	1.3238	−0.0077	0.066*
C3'	0.6907 (4)	1.2161 (4)	0.02328 (4)	0.0616 (9)
H3'A	0.7540	1.1879	0.0311	0.074*
C5	0.1303 (4)	1.1253 (4)	0.00921 (4)	0.0626 (9)
H5A	0.1088	1.1476	0.0218	0.075*
H5B	0.1843	1.2309	0.0024	0.075*
C10	0.6225 (4)	0.9785 (4)	0.12664 (4)	0.0565 (8)
H10A	0.6396	0.8823	0.1254	0.068*
H10B	0.6507	1.0196	0.1393	0.068*
C16	0.9186 (4)	1.1656 (4)	0.11673 (4)	0.0711 (10)
H16A	0.9502	1.2069	0.1292	0.107*
H16B	0.9887	1.2530	0.1081	0.107*
H16C	0.9332	1.0695	0.1149	0.107*
C5'	0.6768 (5)	1.3933 (4)	0.00085 (4)	0.0698 (10)
H5'A	0.7299	1.4893	−0.0066	0.084*
C4'	0.7702 (4)	1.3535 (4)	0.01207 (4)	0.0756 (11)
H4'A	0.8876	1.4195	0.0121	0.091*
C15	0.0958 (4)	0.6417 (5)	0.11153 (5)	0.0793 (11)
H15A	0.1378	0.5641	0.1113	0.119*
H15B	−0.0180	0.5866	0.1069	0.119*
H15C	0.0974	0.6782	0.1240	0.119*
C13	0.2051 (4)	0.7916 (4)	0.09966 (4)	0.0537 (8)
H13A	0.1859	0.7519	0.0868	0.064*
C14	0.1493 (4)	0.9194 (5)	0.10114 (5)	0.0759 (11)
H14A	0.0306	0.8665	0.0985	0.114*
H14B	0.2112	1.0090	0.0924	0.114*
H14C	0.1701	0.9649	0.1135	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0635 (5)	0.0379 (4)	0.0334 (4)	0.0194 (4)	−0.0028 (3)	0.0000 (3)
O1	0.0742 (14)	0.0363 (10)	0.0280 (9)	0.0284 (10)	0.0002 (9)	0.0005 (8)
O2	0.0904 (16)	0.0383 (12)	0.0379 (11)	0.0309 (12)	0.0041 (10)	0.0004 (9)
C6	0.0586 (18)	0.0368 (17)	0.0368 (15)	0.0266 (15)	0.0047 (13)	0.0033 (13)
C7	0.0638 (19)	0.0379 (15)	0.0328 (14)	0.0299 (14)	0.0007 (13)	−0.0037 (11)
C8	0.064 (2)	0.0415 (16)	0.0315 (14)	0.0316 (15)	0.0052 (13)	0.0032 (12)
C12	0.065 (2)	0.0448 (17)	0.0410 (16)	0.0302 (16)	0.0019 (14)	0.0011 (14)
C2'	0.0522 (19)	0.0390 (16)	0.0308 (14)	0.0131 (15)	0.0025 (13)	−0.0049 (12)
C9	0.077 (2)	0.061 (2)	0.0295 (14)	0.0376 (18)	0.0066 (14)	0.0042 (13)
C4	0.069 (2)	0.083 (4)	0.055 (3)	0.0417 (18)	0.0049 (13)	0.010 (3)
C1'	0.0596 (19)	0.0316 (16)	0.0273 (14)	0.0153 (15)	0.0051 (13)	−0.0018 (12)
C1	0.0552 (19)	0.0404 (16)	0.0301 (13)	0.0202 (15)	0.0028 (13)	0.0007 (12)
C11	0.068 (2)	0.0495 (18)	0.0449 (17)	0.0365 (17)	−0.0095 (15)	−0.0067 (14)
C6'	0.077 (2)	0.0364 (17)	0.0350 (15)	0.0163 (18)	0.0026 (15)	0.0015 (13)
C3'	0.054 (2)	0.064 (2)	0.0467 (18)	0.0145 (18)	−0.0012 (15)	−0.0062 (16)
C5	0.077 (2)	0.069 (2)	0.0533 (19)	0.045 (2)	0.0014 (17)	−0.0056 (17)
C10	0.076 (2)	0.062 (2)	0.0402 (16)	0.0407 (18)	−0.0080 (16)	−0.0009 (15)
C16	0.068 (2)	0.071 (2)	0.079 (2)	0.038 (2)	−0.0138 (18)	−0.0059 (18)
C5'	0.086 (3)	0.0411 (19)	0.0391 (18)	0.000 (2)	0.0160 (18)	0.0011 (15)
C4'	0.061 (2)	0.066 (2)	0.052 (2)	−0.0046 (19)	0.0112 (18)	−0.0043 (18)
C15	0.069 (2)	0.072 (2)	0.084 (2)	0.026 (2)	0.013 (2)	0.017 (2)
C13	0.065 (2)	0.058 (2)	0.0397 (16)	0.0312 (18)	0.0020 (14)	0.0002 (14)
C14	0.077 (3)	0.089 (3)	0.080 (2)	0.055 (2)	−0.004 (2)	0.005 (2)

Geometric parameters (Å, º)

S1—C6	1.773 (3)	C11—C16	1.524 (4)
S1—C2'	1.783 (3)	C11—C10	1.526 (4)
O1—C6	1.328 (3)	C11—H11A	1.0000
O1—C7	1.487 (3)	C6'—C5'	1.364 (4)
O2—C6	1.203 (3)	C6'—H6'A	0.9500
C7—C12	1.510 (4)	C3'—C4'	1.387 (4)
C7—C8	1.521 (4)	C3'—H3'A	0.9500
C7—H7A	1.0000	C5—H5A	0.9900
C8—C13	1.532 (4)	C5—H5B	0.9900
C8—C9	1.536 (4)	C10—H10A	0.9900
C8—H8A	1.0000	C10—H10B	0.9900
C12—C11	1.523 (4)	C16—H16A	0.9800
C12—H12A	0.9900	C16—H16B	0.9800
C12—H12B	0.9900	C16—H16C	0.9800
C2'—C3'	1.391 (4)	C5'—C4'	1.378 (5)
C2'—C1'	1.398 (4)	C5'—H5'A	0.9500
C9—C10	1.512 (4)	C4'—H4'A	0.9500
C9—H9A	0.9900	C15—C13	1.527 (4)
C9—H9B	0.9900	C15—H15A	0.9800
C4—C5	1.520 (4)	C15—H15B	0.9800
C4—C5^i	1.520 (4)	C15—H15C	0.9800
C4—H4A	0.9602	C13—C14	1.524 (4)
C1'—C6'	1.402 (4)	C13—H13A	1.0000
C1'—C1	1.499 (4)	C14—H14A	0.9800
C1—C5	1.535 (4)	C14—H14B	0.9800
C1—C1^i	1.550 (5)	C14—H14C	0.9800
C1—H1A	1.0000
C6—S1—C2'	99.38 (12)	C10—C11—H11A	108.1
C6—O1—C7	116.28 (19)	C5'—C6'—C1'	122.4 (3)
O2—C6—O1	126.1 (2)	C5'—C6'—H6'A	118.8
O2—C6—S1	125.6 (2)	C1'—C6'—H6'A	118.8
O1—C6—S1	108.31 (19)	C4'—C3'—C2'	120.4 (3)
O1—C7—C12	109.4 (2)	C4'—C3'—H3'A	119.8
O1—C7—C8	106.3 (2)	C2'—C3'—H3'A	119.8
C12—C7—C8	112.2 (2)	C4—C5—C1	105.3 (3)
O1—C7—H7A	109.6	C4—C5—H5A	110.7
C12—C7—H7A	109.6	C1—C5—H5A	110.7
C8—C7—H7A	109.6	C4—C5—H5B	110.7
C7—C8—C13	114.0 (2)	C1—C5—H5B	110.7
C7—C8—C9	106.9 (2)	H5A—C5—H5B	108.8
C13—C8—C9	114.4 (2)	C9—C10—C11	111.9 (2)
C7—C8—H8A	107.0	C9—C10—H10A	109.2
C13—C8—H8A	107.0	C11—C10—H10A	109.2
C9—C8—H8A	107.0	C9—C10—H10B	109.2
C7—C12—C11	112.1 (2)	C11—C10—H10B	109.2
C7—C12—H12A	109.2	H10A—C10—H10B	107.9
C11—C12—H12A	109.2	C11—C16—H16A	109.5
C7—C12—H12B	109.2	C11—C16—H16B	109.5
C11—C12—H12B	109.2	H16A—C16—H16B	109.5
H12A—C12—H12B	107.9	C11—C16—H16C	109.5
C3'—C2'—C1'	120.9 (3)	H16A—C16—H16C	109.5
C3'—C2'—S1	117.0 (2)	H16B—C16—H16C	109.5
C1'—C2'—S1	122.1 (2)	C6'—C5'—C4'	120.3 (3)
C10—C9—C8	112.5 (2)	C6'—C5'—H5'A	119.8
C10—C9—H9A	109.1	C4'—C5'—H5'A	119.8
C8—C9—H9A	109.1	C5'—C4'—C3'	119.2 (3)
C10—C9—H9B	109.1	C5'—C4'—H4'A	120.4
C8—C9—H9B	109.1	C3'—C4'—H4'A	120.4
H9A—C9—H9B	107.8	C13—C15—H15A	109.5
C5—C4—C5^i	106.5 (4)	C13—C15—H15B	109.5
C5—C4—H4A	110.2	H15A—C15—H15B	109.5
C5^i—C4—H4A	110.9	C13—C15—H15C	109.5
C2'—C1'—C6'	116.8 (3)	H15A—C15—H15C	109.5
C2'—C1'—C1	123.2 (2)	H15B—C15—H15C	109.5
C6'—C1'—C1	119.9 (3)	C14—C13—C15	110.0 (3)
C1'—C1—C5	118.4 (2)	C14—C13—C8	113.9 (3)
C1'—C1—C1^i	111.96 (18)	C15—C13—C8	112.1 (2)
C5—C1—C1^i	101.31 (17)	C14—C13—H13A	106.8
C1'—C1—H1A	108.2	C15—C13—H13A	106.8
C5—C1—H1A	108.2	C8—C13—H13A	106.8
C1^i—C1—H1A	108.2	C13—C14—H14A	109.5
C12—C11—C16	111.6 (2)	C13—C14—H14B	109.5
C12—C11—C10	109.1 (2)	H14A—C14—H14B	109.5
C16—C11—C10	111.8 (2)	C13—C14—H14C	109.5
C12—C11—H11A	108.1	H14A—C14—H14C	109.5
C16—C11—H11A	108.1	H14B—C14—H14C	109.5
C7—O1—C6—O2	0.9 (4)	C2'—C1'—C1—C1^i	−108.0 (3)
C7—O1—C6—S1	−179.98 (18)	C6'—C1'—C1—C1^i	67.0 (3)
C2'—S1—C6—O2	7.1 (3)	C7—C12—C11—C16	178.6 (2)
C2'—S1—C6—O1	−172.02 (19)	C7—C12—C11—C10	54.7 (3)
C6—O1—C7—C12	−82.1 (3)	C2'—C1'—C6'—C5'	0.2 (4)
C6—O1—C7—C8	156.5 (2)	C1—C1'—C6'—C5'	−175.2 (3)
O1—C7—C8—C13	−55.2 (3)	C1'—C2'—C3'—C4'	1.8 (4)
C12—C7—C8—C13	−174.9 (2)	S1—C2'—C3'—C4'	−179.9 (2)
O1—C7—C8—C9	177.3 (2)	C5^i—C4—C5—C1	−14.19 (13)
C12—C7—C8—C9	57.7 (3)	C1'—C1—C5—C4	159.4 (2)
O1—C7—C12—C11	−176.7 (2)	C1^i—C1—C5—C4	36.5 (3)
C8—C7—C12—C11	−58.9 (3)	C8—C9—C10—C11	57.6 (3)
C6—S1—C2'—C3'	62.1 (2)	C12—C11—C10—C9	−54.0 (3)
C6—S1—C2'—C1'	−119.7 (2)	C16—C11—C10—C9	−177.9 (2)
C7—C8—C9—C10	−57.3 (3)	C1'—C6'—C5'—C4'	1.8 (5)
C13—C8—C9—C10	175.5 (2)	C6'—C5'—C4'—C3'	−2.0 (5)
C3'—C2'—C1'—C6'	−1.9 (4)	C2'—C3'—C4'—C5'	0.2 (5)
S1—C2'—C1'—C6'	179.9 (2)	C7—C8—C13—C14	−59.1 (3)
C3'—C2'—C1'—C1	173.2 (2)	C9—C8—C13—C14	64.4 (3)
S1—C2'—C1'—C1	−5.0 (4)	C7—C8—C13—C15	175.2 (2)
C2'—C1'—C1—C5	134.6 (3)	C9—C8—C13—C15	−61.3 (3)
C6'—C1'—C1—C5	−50.4 (3)

Symmetry code: (i) x−y+1, −y+2, −z.