(1S*,2R*,2′R*)-2-Phenyl-1-phenyl­thio-1-(tetra­hydro­pyran-2-yl­thio)­propan-2-ol at 193 K

2-Phenyl-1-phenyl­thio-1-(tetra­hydro­pyran-2-yl­thio)­propan-2-ol, C₂₀H₂₄O₂S₂, was synthesized as a mixture of four di­as­tereoisomers. An isomer which crystallizes in the centrosymmetric monoclinic space group P2₁/c with the relative configuration (1S*,2R*,2′R*) is presented. Intermolecular hydrogen bonds between the hydroxyl group and the O atom of the tetra­hydro­pyran ring of a neighbouring mol­ecule [O...O 2.751 (2) Å] form zigzag chains in the c-axis direction. The tetra­hydro­pyran ring has a chair conformation with an axial S-side chain.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.046
• wR factor = 0.107
• Data-to-parameter ratio = 15.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

According to the crystallographic atomic labelling of 2-phenyl-1-phenylthio-1-(tetrahydropyran-2-ylthio)propan-2-ol (Fig. 1), the C atom bearing the S-side chain in the tetrahydropyran ring is C16 and thus the relative configuration of the title compound may also be named (1S*,2R*,16R*), (I). We have earlier reported the structure of another diastereoisomer (1S*,2S*,16R*), (II) (Kansikas et al., 1995). A very closely related compound 1-phenyl-2-phenylthio-2-(tetrahydropyran-2-ylthio)ethanol, (C₁₉H₂₂O₂S₂), where the methyl group is replaced by an H atom, also forms four diastereoisomers. Applying the above labelling scheme, atom C15 is now in the tetrahydropyran ring bonded to S. Three of the ethanol diastereoisomers crystallize in non-centrosymmetric space groups as conglomerates of enantiomeric crystals with the configurations (1S,2S,15R), (III) (Kansikas et al., 1996), (1R,2S,15S), (IV), and (1S,2S,15S), (V) (Kansikas and Sipilä, 2000). The fourth diastereoisomer crystallizes in a centrosymmetric space group with the relative configuration (1R*,2S*,15R*), (VI) (Sipilä et al., 2001). Some interatomic distances, angles and torsion angles for (I) are listed in Table 1. The S—C distances fall well within the values found in the compounds (II)–(VI), but the C1—S1—C4 angle of 99.21 (1)° is the smallest among them. Torsion angles around the S atoms in compounds (I)–(VI) vary considerably and that gives rise to very different appearances of these otherwise rather similar molecules. In the compound (I) the hydroxyl group forms an intermolecular hydrogen bond to the O atom of the tetrahydropyran ring of the neighbouring molecule at the equivalent position (x, 1/2 - y, z - 1/2) (Fig. 2 and Table 2). A comparable intermolecular hydrogen bond, but between the molecules with the symmetry code (x, y, z - 1), is found in the ethanol derivative (V). The O···O distances are 2.751 (2) Å for (I) and 2.764 (3) Å for (V). The title isomer (I) crystallizes in the space group P2₁/c (No. 14), whereas the ethanol derivative (IV) with the same relative configuration crystallizes in the non-centrosymmetric space group P2₁2₁2₁ (No. 19) and possesses an intramolecular hydrogen bond between the hydroxyl group and the O atom of the tetrahydropyran ring similar to (II) and (III).

S2. Experimental

2-Phenyl-1-phenylthio-1-(tetrahydropyran-2-ylthio)propan-2-ol was synthesized as a mixture of four diastereoisomers according to a procedure reported previously (Kansikas et al., 1995). The diastereoisomers (1S*,2R*,2'R*)-2-phenyl-1-phenylthio-1-(tetrahydropyran-2-ylthio)propan-2-ol, (I), and (1S*,2S*,2'R*)-2-phenyl-1-phenylthio-1-(tetrahydropyran-2-ylthio)propan-2-ol, (II) (Kansikas et al., 1995), were separated by high-pressure liquid chromatography (HPLC) from the crude product and recrystallized from absolute ethanol. The relative amounts of the diastereoisomers in elution order were: 31% (II) and 19% (I). The remaining two diastereoisomers (50% of the total amount) could not be separated by this procedure. HPLC separation was performed with an ISCO 2350 liquid chromatograph equipped with a Shimadzu SPD-6 A UV spectrophotometric detector and a Shimadzu C—R6A Chromatopac. Components were monitored measuring the absorption at 254 nm. The column used was Merck Lichrocart Si 60 (250 × 10 mm ID), 5 µm, the mobile phase 2% ethyl acetate in dichloromethane; flow rate 7 ml min^-1. The NMR spectra were recorded on a Varian Gemini 200 spectrometer using tetramethylsilane as an internal standard. The assignments are based on chemical-shift data and DEPT measurements. 1H NMR (200 MHz, CDCl₃): δ 1.4–1.9 (6H, m; CH₂), 1.80 (s, CH₃), 3.4–3.6 and 3.6–3.7 (2H, m; OCH₂), 4.7 (1H, s, SCHS), 4.9 (1H, s, OH), 5.5–5.3 (1H, m, OCHS), 7.2–7.6 (10H, m; arom·H). ¹³C NMR (50 MHz; CDCl₃): δ 21.7 and 25.1 and 30.7 (CH₂), 29.5 (CH₃), 65.1 (OCH₂), 68.5 (SCHS), 78.2 (CPh), 80.1 (OCS), 125.1–147.3 (aromatic C).

Computing details

Data collection: AFC-7S software; cell refinement: AFC-7S software; data reduction: TEXSAN (Molecular Structure Corporation, 1993); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. View of (I) showing the crystallographic atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Fraction of the molecular packing showing the hydrogen-bond scheme of (I) in the c axis direction.

(I)

Crystal data

C20H24O2S2	F(000) = 768
Mr = 360.51	Dx = 1.263 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.2440 (18) Å	Cell parameters from 25 reflections
b = 19.239 (4) Å	θ = 4–10°
c = 10.682 (2) Å	µ = 0.29 mm^−1
β = 93.37 (3)°	T = 193 K
V = 1896.5 (6) Å^3	Prismatic, colourless
Z = 4	0.36 × 0.30 × 0.25 mm

Data collection

Rigaku AFC-7S diffractometer	Rint = 0.029
Radiation source: fine-focus sealed tube	θmax = 25.3°, θmin = 2.9°
Graphite monochromator	h = 0→11
ω/2θ scans	k = 0→23
3637 measured reflections	l = −12→12
3418 independent reflections	3 standard reflections every 100 reflections
2438 reflections with I > 2σ(I)	intensity decay: <0.1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0501P)^2 + 0.1099P] where P = (Fo^2 + 2Fc^2)/3
3418 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

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	0.61079 (7)	0.30678 (4)	0.07364 (6)	0.0355 (2)
O1	0.39674 (19)	0.21467 (9)	−0.04576 (15)	0.0329 (4)
H1A	0.3562	0.1792	−0.0773	0.049*
C1	0.4319 (3)	0.28763 (12)	0.1302 (2)	0.0252 (5)
H1B	0.4395	0.2883	0.2239	0.030*
S2	0.31071 (7)	0.35720 (3)	0.07562 (6)	0.02717 (17)
O2	0.2771 (2)	0.39432 (9)	0.31726 (15)	0.0333 (4)
C2	0.3857 (3)	0.21387 (13)	0.0866 (2)	0.0272 (6)
C3	0.4888 (3)	0.15934 (14)	0.1449 (3)	0.0379 (7)
H3A	0.4579	0.1130	0.1160	0.057*
H3B	0.4875	0.1616	0.2365	0.057*
H3C	0.5873	0.1684	0.1197	0.057*
C4	0.6601 (3)	0.37767 (14)	0.1741 (2)	0.0320 (6)
C5	0.6929 (3)	0.36759 (14)	0.3006 (3)	0.0360 (6)
H5A	0.6862	0.3224	0.3358	0.043*
C6	0.7355 (3)	0.42303 (15)	0.3758 (3)	0.0425 (7)
H6A	0.7576	0.4160	0.4629	0.051*
C7	0.7461 (3)	0.48869 (15)	0.3253 (3)	0.0427 (7)
H7A	0.7761	0.5268	0.3772	0.051*
C8	0.7132 (3)	0.49868 (15)	0.1999 (3)	0.0432 (7)
H8A	0.7210	0.5438	0.1650	0.052*
C9	0.6686 (3)	0.44362 (14)	0.1235 (3)	0.0368 (7)
H9A	0.6440	0.4511	0.0370	0.044*
C10	0.2298 (3)	0.20079 (12)	0.1215 (2)	0.0249 (5)
C11	0.1150 (3)	0.21167 (14)	0.0344 (2)	0.0326 (6)
H11A	0.1334	0.2230	−0.0497	0.039*
C12	−0.0263 (3)	0.20616 (15)	0.0692 (3)	0.0419 (7)
H12A	−0.1040	0.2148	0.0091	0.050*
C13	−0.0558 (3)	0.18841 (15)	0.1891 (3)	0.0429 (7)
H13A	−0.1532	0.1852	0.2123	0.051*
C14	0.0581 (3)	0.17519 (14)	0.2764 (3)	0.0365 (7)
H14A	0.0390	0.1612	0.3591	0.044*
C15	0.1994 (3)	0.18243 (13)	0.2426 (2)	0.0296 (6)
H15A	0.2770	0.1747	0.3034	0.036*
C16	0.1978 (3)	0.36796 (13)	0.2092 (2)	0.0280 (6)
H16A	0.1601	0.3210	0.2310	0.034*
C17	0.0689 (3)	0.41334 (14)	0.1720 (3)	0.0354 (6)
H17A	−0.0033	0.4099	0.2366	0.043*
H17B	0.0228	0.3965	0.0917	0.043*
C18	0.1132 (3)	0.48914 (14)	0.1576 (3)	0.0381 (7)
H18A	0.1735	0.4941	0.0845	0.046*
H18B	0.0257	0.5184	0.1429	0.046*
C19	0.1978 (3)	0.51272 (14)	0.2754 (3)	0.0436 (7)
H19A	0.1335	0.5131	0.3463	0.052*
H19B	0.2336	0.5606	0.2636	0.052*
C20	0.3249 (3)	0.46461 (14)	0.3054 (3)	0.0388 (7)
H20A	0.3936	0.4676	0.2379	0.047*
H20B	0.3765	0.4795	0.3848	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0289 (4)	0.0361 (4)	0.0426 (4)	−0.0044 (3)	0.0115 (3)	−0.0118 (3)
O1	0.0407 (11)	0.0316 (10)	0.0269 (9)	−0.0069 (8)	0.0051 (8)	−0.0079 (7)
C1	0.0232 (13)	0.0273 (13)	0.0252 (12)	0.0006 (11)	0.0036 (10)	−0.0018 (10)
S2	0.0316 (4)	0.0249 (3)	0.0253 (3)	0.0022 (3)	0.0036 (3)	0.0002 (3)
O2	0.0419 (11)	0.0317 (10)	0.0263 (9)	0.0086 (9)	0.0011 (8)	0.0008 (8)
C2	0.0286 (14)	0.0266 (14)	0.0266 (13)	0.0003 (11)	0.0026 (11)	−0.0027 (10)
C3	0.0352 (16)	0.0291 (15)	0.0494 (17)	0.0053 (12)	0.0028 (13)	−0.0003 (13)
C4	0.0226 (13)	0.0331 (15)	0.0408 (15)	−0.0034 (11)	0.0056 (12)	−0.0052 (12)
C5	0.0343 (15)	0.0297 (15)	0.0438 (16)	−0.0028 (12)	0.0002 (12)	0.0025 (12)
C6	0.0430 (17)	0.0411 (17)	0.0429 (17)	−0.0051 (14)	−0.0012 (14)	−0.0047 (14)
C7	0.0336 (16)	0.0357 (17)	0.059 (2)	−0.0050 (13)	0.0040 (14)	−0.0177 (14)
C8	0.0376 (17)	0.0299 (15)	0.063 (2)	−0.0031 (13)	0.0084 (15)	0.0021 (14)
C9	0.0334 (15)	0.0349 (16)	0.0429 (16)	−0.0053 (13)	0.0080 (12)	0.0029 (13)
C10	0.0279 (13)	0.0164 (12)	0.0300 (13)	−0.0019 (10)	−0.0011 (11)	−0.0042 (10)
C11	0.0341 (15)	0.0342 (15)	0.0290 (13)	−0.0005 (12)	−0.0027 (11)	−0.0025 (11)
C12	0.0286 (15)	0.0449 (18)	0.0509 (18)	−0.0024 (13)	−0.0087 (13)	−0.0026 (14)
C13	0.0291 (15)	0.0401 (17)	0.0602 (19)	−0.0096 (13)	0.0091 (14)	−0.0063 (15)
C14	0.0443 (17)	0.0285 (15)	0.0378 (15)	−0.0107 (13)	0.0109 (13)	0.0004 (12)
C15	0.0329 (14)	0.0239 (13)	0.0316 (14)	−0.0033 (11)	−0.0011 (11)	0.0007 (10)
C16	0.0310 (14)	0.0239 (13)	0.0299 (13)	−0.0015 (11)	0.0074 (11)	0.0009 (10)
C17	0.0261 (14)	0.0385 (16)	0.0418 (16)	0.0026 (13)	0.0029 (12)	−0.0037 (13)
C18	0.0357 (16)	0.0329 (16)	0.0456 (16)	0.0115 (13)	0.0012 (13)	0.0066 (13)
C19	0.0459 (18)	0.0239 (15)	0.061 (2)	0.0025 (13)	0.0037 (15)	−0.0067 (14)
C20	0.0420 (17)	0.0331 (16)	0.0402 (16)	0.0013 (14)	−0.0059 (13)	−0.0103 (12)

Geometric parameters (Å, º)

S1—C4	1.778 (3)	C6—C7	1.380 (4)
S1—C1	1.831 (2)	C7—C8	1.369 (4)
O1—C2	1.423 (3)	C8—C9	1.385 (4)
C1—C2	1.546 (3)	C10—C11	1.385 (3)
C1—S2	1.819 (2)	C10—C15	1.386 (3)
S2—C16	1.828 (2)	C11—C12	1.383 (4)
O2—C16	1.424 (3)	C12—C13	1.367 (4)
O2—C20	1.431 (3)	C13—C14	1.388 (4)
C2—C3	1.525 (4)	C14—C15	1.383 (4)
C2—C10	1.531 (3)	C16—C17	1.512 (3)
C4—C5	1.381 (4)	C17—C18	1.525 (4)
C4—C9	1.383 (4)	C18—C19	1.512 (4)
C5—C6	1.379 (4)	C19—C20	1.515 (4)
C4—S1—C1	99.20 (11)	C7—C8—C9	120.7 (3)
C2—C1—S2	115.16 (17)	C4—C9—C8	119.5 (3)
C2—C1—S1	108.91 (16)	C11—C10—C15	118.4 (2)
S2—C1—S1	107.30 (12)	C11—C10—C2	120.5 (2)
C1—S2—C16	101.66 (11)	C15—C10—C2	121.0 (2)
C16—O2—C20	114.32 (19)	C12—C11—C10	120.4 (3)
O1—C2—C3	109.5 (2)	C13—C12—C11	120.9 (3)
O1—C2—C10	111.5 (2)	C12—C13—C14	119.3 (3)
C3—C2—C10	111.2 (2)	C15—C14—C13	119.8 (3)
O1—C2—C1	104.76 (19)	C14—C15—C10	121.0 (2)
C3—C2—C1	110.7 (2)	O2—C16—C17	111.6 (2)
C10—C2—C1	108.95 (19)	O2—C16—S2	112.52 (16)
C5—C4—C9	119.8 (2)	C17—C16—S2	109.73 (17)
C5—C4—S1	121.1 (2)	C16—C17—C18	111.5 (2)
C9—C4—S1	119.1 (2)	C19—C18—C17	109.4 (2)
C6—C5—C4	120.0 (3)	C18—C19—C20	110.5 (2)
C5—C6—C7	120.3 (3)	O2—C20—C19	110.9 (2)
C8—C7—C6	119.6 (3)
C4—S1—C1—C2	−162.48 (17)	C1—C2—C10—C11	96.1 (3)
C4—S1—C1—S2	72.25 (15)	O1—C2—C10—C15	165.3 (2)
C2—C1—S2—C16	96.02 (18)	C3—C2—C10—C15	42.7 (3)
S1—C1—S2—C16	−142.57 (12)	C1—C2—C10—C15	−79.6 (3)
S2—C1—C2—O1	66.0 (2)	C15—C10—C11—C12	1.8 (4)
S1—C1—C2—O1	−54.5 (2)	C2—C10—C11—C12	−173.9 (2)
S2—C1—C2—C3	−176.06 (17)	C10—C11—C12—C13	−1.5 (4)
S1—C1—C2—C3	63.4 (2)	C11—C12—C13—C14	−0.6 (4)
S2—C1—C2—C10	−53.4 (2)	C12—C13—C14—C15	2.2 (4)
S1—C1—C2—C10	−173.97 (16)	C13—C14—C15—C10	−1.9 (4)
C1—S1—C4—C5	70.4 (2)	C11—C10—C15—C14	−0.1 (4)
C1—S1—C4—C9	−111.0 (2)	C2—C10—C15—C14	175.6 (2)
C9—C4—C5—C6	−0.7 (4)	C20—O2—C16—C17	−55.7 (3)
S1—C4—C5—C6	177.9 (2)	C20—O2—C16—S2	68.2 (2)
C4—C5—C6—C7	−0.3 (4)	C1—S2—C16—O2	67.04 (18)
C5—C6—C7—C8	0.4 (5)	C1—S2—C16—C17	−168.11 (18)
C6—C7—C8—C9	0.3 (4)	O2—C16—C17—C18	52.9 (3)
C5—C4—C9—C8	1.5 (4)	S2—C16—C17—C18	−72.5 (2)
S1—C4—C9—C8	−177.1 (2)	C16—C17—C18—C19	−53.0 (3)
C7—C8—C9—C4	−1.3 (4)	C17—C18—C19—C20	54.6 (3)
O1—C2—C10—C11	−19.1 (3)	C16—O2—C20—C19	57.6 (3)
C3—C2—C10—C11	−141.6 (2)	C18—C19—C20—O2	−56.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2^i	0.84	1.92	2.751 (2)	168

Symmetry code: (i) x, −y+1/2, z−1/2.