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The stereoisomers of 7-phenyl-1-oxa-4-thiaspiro[4.5]decan-7-ol, C
14H
18O
2S, have the same stereochemistry at the C atom bearing an OH group,
i.e. axial OH and equatorial phenyl groups. However, the acetal S and O atoms are axial and equatorial, respectively, in one isomer and reversed in the second. Furthermore, the crystals of one isomer are composed of hydrogen-bonded molecules involving the hydroxyl H atom and the O atom of the five-membered heterocyclic ring, with an O
O distance of 2.962 (3) Å, forming a polymeric chain along the
b axis. The asymmetric unit of the other isomer is composed of two molecules, wherein hydroxyl H atoms and the O atoms of the five-membered heterocyclic rings display intramolecular O—H
O hydrogen bonds with O
O separations of 2.820 (2) and 2.834 (2) Å.
Supporting information
CCDC references: 164652; 164653
The two title stereoisomers, (IIa) and (IIb), were prepared according to the
literature protocol of Mertes (1961). Condensation of mercaptoethanol and
cyclohexane-1,3-dione in benzene at reflux furnished a mixture of the acetals
(Ia) and (Ib). This mixture was reacted further with PhMgBr in Et2O to
obtain a mixture of the desired compounds (IIa) and (IIb) in quantitative
yield.
The asymmetric unit of (IIb) is composed of two independent molecules, which are
related by pseudo centres of symmetry located at -0.375, -0.126, 0.000 and
-0.125, 0.624, 0.000. The cell constants and space group were verified on a
Nonius KappaCCD instrument. The corresponding atoms S1, C1 and C2 of the
heterocyclic rings in both the molecules of (IIb) were disordered, with
inequivalent site occupancy factors; the major fractions were 0.717 (18) and
0.794 (16) in the two molecules. Atoms O1 and C3 did not seem to be affected by
this disorder. For both compounds (IIa) and (IIb), most of the H atoms were
located from difference Fourier syntheses and all were included in the
refinements at geometrically idealized positions, with C—H 0.93 and 0.97,
and O—H 0.82 Å, utilizing a riding model. In order to avoid collisions
with the cryogenic system, reflections with k > 10 could not be collected for
both crystals.
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97.
(IIa) 7-phenyl-1-oxa-4-thiaspiro[4.5]decan-7-ol
top
Crystal data top
C14H18O2S | F(000) = 1072 |
Mr = 250.34 | Dx = 1.295 Mg m−3 |
Orthorhombic, Pbca | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 12.313 (2) Å | θ = 20–30° |
b = 10.674 (5) Å | µ = 2.13 mm−1 |
c = 19.535 (2) Å | T = 293 K |
V = 2568 (1) Å3 | Needle, colourless |
Z = 8 | 0.52 × 0.18 × 0.10 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1529 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.00 |
Graphite monochromator | θmax = 68°, θmin = 5° |
ω/2θ scans | h = 0→14 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | k = 0→10 |
Tmin = 0.40, Tmax = 0.82 | l = −23→0 |
2199 measured reflections | 3 standard reflections every 200 reflections |
2199 independent reflections | intensity decay: <0.1% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.082P)2 + 0.255P] where P = (Fo2 + 2Fc2)/3 |
2199 reflections | (Δ/σ)max < 0.01 |
155 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C14H18O2S | V = 2568 (1) Å3 |
Mr = 250.34 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 12.313 (2) Å | µ = 2.13 mm−1 |
b = 10.674 (5) Å | T = 293 K |
c = 19.535 (2) Å | 0.52 × 0.18 × 0.10 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1529 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.00 |
Tmin = 0.40, Tmax = 0.82 | 3 standard reflections every 200 reflections |
2199 measured reflections | intensity decay: <0.1% |
2199 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.32 e Å−3 |
2199 reflections | Δρmin = −0.25 e Å−3 |
155 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.39544 (7) | 0.72254 (8) | 0.69252 (4) | 0.0607 (3) | |
O1 | 0.28413 (17) | 0.90777 (19) | 0.74269 (11) | 0.0608 (6) | |
O2 | 0.39003 (15) | 0.54544 (19) | 0.81541 (10) | 0.0509 (5) | |
H2 | 0.3390 | 0.5089 | 0.7973 | 0.076* | |
C1 | 0.3596 (4) | 0.8486 (4) | 0.63612 (19) | 0.0845 (12) | |
H1A | 0.4220 | 0.8736 | 0.6091 | 0.101* | |
H1B | 0.3021 | 0.8226 | 0.6053 | 0.101* | |
C2 | 0.3228 (3) | 0.9529 (3) | 0.67882 (17) | 0.0760 (11) | |
H2A | 0.3825 | 1.0105 | 0.6864 | 0.091* | |
H2B | 0.2652 | 0.9979 | 0.6555 | 0.091* | |
C3 | 0.3547 (2) | 0.8137 (3) | 0.76904 (14) | 0.0475 (7) | |
C4 | 0.2867 (2) | 0.7381 (3) | 0.81889 (13) | 0.0452 (7) | |
H4A | 0.2299 | 0.6956 | 0.7935 | 0.054* | |
H4B | 0.2518 | 0.7954 | 0.8505 | 0.054* | |
C5 | 0.3495 (2) | 0.6409 (2) | 0.86000 (13) | 0.0414 (6) | |
C6 | 0.4505 (2) | 0.7005 (3) | 0.89227 (15) | 0.0540 (8) | |
H6A | 0.4280 | 0.7577 | 0.9282 | 0.065* | |
H6B | 0.4944 | 0.6354 | 0.9131 | 0.065* | |
C7 | 0.5188 (2) | 0.7713 (3) | 0.84053 (17) | 0.0634 (9) | |
H7A | 0.5796 | 0.8105 | 0.8637 | 0.076* | |
H7B | 0.5476 | 0.7129 | 0.8071 | 0.076* | |
C8 | 0.4530 (3) | 0.8702 (3) | 0.80434 (16) | 0.0585 (8) | |
H8A | 0.4982 | 0.9120 | 0.7707 | 0.070* | |
H8B | 0.4291 | 0.9325 | 0.8373 | 0.070* | |
C9 | 0.2818 (2) | 0.5811 (3) | 0.91640 (13) | 0.0429 (6) | |
C10 | 0.3233 (3) | 0.4801 (3) | 0.95213 (15) | 0.0549 (8) | |
H10 | 0.3904 | 0.4474 | 0.9394 | 0.066* | |
C11 | 0.2681 (3) | 0.4265 (3) | 1.00598 (16) | 0.0645 (9) | |
H11 | 0.2984 | 0.3591 | 1.0293 | 0.077* | |
C12 | 0.1691 (3) | 0.4719 (3) | 1.02521 (16) | 0.0641 (9) | |
H12 | 0.1319 | 0.4358 | 1.0616 | 0.077* | |
C13 | 0.1251 (3) | 0.5709 (3) | 0.99051 (17) | 0.0636 (9) | |
H13 | 0.0577 | 0.6022 | 1.0035 | 0.076* | |
C14 | 0.1802 (2) | 0.6247 (3) | 0.93627 (15) | 0.0516 (7) | |
H14 | 0.1488 | 0.6912 | 0.9127 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0746 (6) | 0.0581 (6) | 0.0494 (4) | 0.0001 (4) | 0.0134 (4) | −0.0050 (4) |
O1 | 0.0663 (14) | 0.0577 (13) | 0.0586 (13) | 0.0126 (11) | 0.0117 (10) | 0.0109 (10) |
O2 | 0.0496 (11) | 0.0518 (12) | 0.0512 (12) | 0.0029 (9) | 0.0071 (9) | −0.0093 (9) |
C1 | 0.107 (3) | 0.089 (3) | 0.058 (2) | 0.016 (2) | 0.016 (2) | 0.015 (2) |
C2 | 0.097 (3) | 0.067 (2) | 0.064 (2) | 0.005 (2) | 0.014 (2) | 0.0172 (18) |
C3 | 0.0469 (15) | 0.0480 (17) | 0.0474 (15) | 0.0008 (13) | 0.0074 (12) | −0.0006 (13) |
C4 | 0.0383 (13) | 0.0516 (17) | 0.0458 (15) | −0.0019 (12) | 0.0046 (11) | −0.0023 (13) |
C5 | 0.0391 (13) | 0.0454 (16) | 0.0398 (14) | 0.0009 (12) | 0.0037 (11) | −0.0056 (12) |
C6 | 0.0469 (16) | 0.0629 (19) | 0.0524 (17) | −0.0080 (15) | −0.0063 (13) | −0.0032 (14) |
C7 | 0.0441 (16) | 0.077 (2) | 0.069 (2) | −0.0131 (16) | −0.0041 (15) | −0.0023 (18) |
C8 | 0.0599 (18) | 0.0538 (19) | 0.0617 (19) | −0.0159 (16) | 0.0078 (15) | −0.0038 (15) |
C9 | 0.0449 (15) | 0.0459 (16) | 0.0380 (14) | −0.0048 (12) | −0.0004 (11) | −0.0074 (12) |
C10 | 0.0562 (17) | 0.0562 (19) | 0.0525 (17) | 0.0075 (15) | −0.0001 (14) | 0.0027 (15) |
C11 | 0.076 (2) | 0.067 (2) | 0.0508 (18) | −0.0029 (19) | −0.0047 (16) | 0.0093 (16) |
C12 | 0.074 (2) | 0.072 (2) | 0.0469 (16) | −0.019 (2) | 0.0072 (16) | 0.0009 (16) |
C13 | 0.0569 (19) | 0.070 (2) | 0.064 (2) | −0.0079 (17) | 0.0168 (16) | −0.0019 (17) |
C14 | 0.0458 (15) | 0.0534 (18) | 0.0557 (18) | −0.0012 (15) | 0.0052 (13) | −0.0003 (14) |
Geometric parameters (Å, º) top
S1—C1 | 1.794 (4) | C6—H6A | 0.9700 |
S1—C3 | 1.853 (3) | C6—H6B | 0.9700 |
O1—C2 | 1.420 (4) | C7—C8 | 1.507 (4) |
O1—C3 | 1.424 (3) | C7—H7A | 0.9700 |
O2—C5 | 1.430 (3) | C7—H7B | 0.9700 |
O2—H2 | 0.8200 | C8—H8A | 0.9700 |
C1—C2 | 1.463 (5) | C8—H8B | 0.9700 |
C1—H1A | 0.9700 | C9—C10 | 1.383 (4) |
C1—H1B | 0.9700 | C9—C14 | 1.390 (4) |
C2—H2A | 0.9700 | C10—C11 | 1.377 (4) |
C2—H2B | 0.9700 | C10—H10 | 0.9300 |
C3—C4 | 1.517 (4) | C11—C12 | 1.365 (5) |
C3—C8 | 1.518 (4) | C11—H11 | 0.9300 |
C4—C5 | 1.523 (4) | C12—C13 | 1.367 (5) |
C4—H4A | 0.9700 | C12—H12 | 0.9300 |
C4—H4B | 0.9700 | C13—C14 | 1.383 (4) |
C5—C9 | 1.522 (4) | C13—H13 | 0.9300 |
C5—C6 | 1.533 (4) | C14—H14 | 0.9300 |
C6—C7 | 1.516 (4) | | |
| | | |
C1—S1—C3 | 92.00 (16) | C5—C6—H6A | 109.1 |
C2—O1—C3 | 110.6 (2) | C7—C6—H6B | 109.1 |
C5—O2—H2 | 109.5 | C5—C6—H6B | 109.1 |
C2—C1—S1 | 107.3 (3) | H6A—C6—H6B | 107.8 |
C2—C1—H1A | 110.3 | C8—C7—C6 | 111.3 (3) |
S1—C1—H1A | 110.3 | C8—C7—H7A | 109.4 |
C2—C1—H1B | 110.3 | C6—C7—H7A | 109.4 |
S1—C1—H1B | 110.3 | C8—C7—H7B | 109.4 |
H1A—C1—H1B | 108.5 | C6—C7—H7B | 109.4 |
O1—C2—C1 | 110.3 (3) | H7A—C7—H7B | 108.0 |
O1—C2—H2A | 109.6 | C7—C8—C3 | 111.3 (2) |
C1—C2—H2A | 109.6 | C7—C8—H8A | 109.4 |
O1—C2—H2B | 109.6 | C3—C8—H8A | 109.4 |
C1—C2—H2B | 109.6 | C7—C8—H8B | 109.4 |
H2A—C2—H2B | 108.1 | C3—C8—H8B | 109.4 |
O1—C3—C4 | 105.7 (2) | H8A—C8—H8B | 108.0 |
O1—C3—C8 | 111.7 (2) | C10—C9—C14 | 116.9 (3) |
C4—C3—C8 | 111.1 (2) | C10—C9—C5 | 119.3 (2) |
O1—C3—S1 | 104.12 (18) | C14—C9—C5 | 123.7 (2) |
C4—C3—S1 | 112.8 (2) | C11—C10—C9 | 121.8 (3) |
C8—C3—S1 | 111.1 (2) | C11—C10—H10 | 119.1 |
C3—C4—C5 | 114.9 (2) | C9—C10—H10 | 119.1 |
C3—C4—H4A | 108.5 | C12—C11—C10 | 120.2 (3) |
C5—C4—H4A | 108.5 | C12—C11—H11 | 119.9 |
C3—C4—H4B | 108.5 | C10—C11—H11 | 119.9 |
C5—C4—H4B | 108.5 | C11—C12—C13 | 119.5 (3) |
H4A—C4—H4B | 107.5 | C11—C12—H12 | 120.3 |
O2—C5—C9 | 109.5 (2) | C13—C12—H12 | 120.3 |
O2—C5—C4 | 110.0 (2) | C12—C13—C14 | 120.4 (3) |
C9—C5—C4 | 112.9 (2) | C12—C13—H13 | 119.8 |
O2—C5—C6 | 105.2 (2) | C14—C13—H13 | 119.8 |
C9—C5—C6 | 108.7 (2) | C13—C14—C9 | 121.1 (3) |
C4—C5—C6 | 110.2 (2) | C13—C14—H14 | 119.5 |
C7—C6—C5 | 112.5 (2) | C9—C14—H14 | 119.5 |
C7—C6—H6A | 109.1 | | |
| | | |
C3—S1—C1—C2 | 2.0 (3) | C6—C7—C8—C3 | −57.3 (3) |
C3—O1—C2—C1 | 43.0 (4) | O1—C3—C8—C7 | 172.0 (2) |
S1—C1—C2—O1 | −24.6 (4) | C4—C3—C8—C7 | 54.2 (3) |
C2—O1—C3—C4 | −157.9 (3) | S1—C3—C8—C7 | −72.2 (3) |
C2—O1—C3—C8 | 81.2 (3) | O2—C5—C9—C10 | 48.9 (3) |
C2—O1—C3—S1 | −38.8 (3) | C4—C5—C9—C10 | 171.7 (2) |
C1—S1—C3—O1 | 20.2 (2) | C6—C5—C9—C10 | −65.6 (3) |
C1—S1—C3—C4 | 134.3 (2) | O2—C5—C9—C14 | −133.3 (3) |
C1—S1—C3—C8 | −100.1 (2) | C4—C5—C9—C14 | −10.4 (4) |
O1—C3—C4—C5 | −173.0 (2) | C6—C5—C9—C14 | 112.2 (3) |
C8—C3—C4—C5 | −51.7 (3) | C14—C9—C10—C11 | −1.4 (4) |
S1—C3—C4—C5 | 73.8 (3) | C5—C9—C10—C11 | 176.6 (3) |
C3—C4—C5—O2 | −65.9 (3) | C9—C10—C11—C12 | 0.6 (5) |
C3—C4—C5—C9 | 171.5 (2) | C10—C11—C12—C13 | 0.1 (5) |
C3—C4—C5—C6 | 49.7 (3) | C11—C12—C13—C14 | 0.0 (5) |
O2—C5—C6—C7 | 67.2 (3) | C12—C13—C14—C9 | −0.9 (5) |
C9—C5—C6—C7 | −175.6 (2) | C10—C9—C14—C13 | 1.6 (4) |
C4—C5—C6—C7 | −51.3 (3) | C5—C9—C14—C13 | −176.3 (3) |
C5—C6—C7—C8 | 56.3 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 2.14 | 2.962 (3) | 175 |
Symmetry code: (i) −x+1/2, y−1/2, z. |
(IIb) 7-phenyl-1-oxa-4-thiaspiro[4.5]decan-7-ol
top
Crystal data top
C14H18O2S | F(000) = 2144 |
Mr = 250.34 | Dx = 1.303 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
a = 22.136 (8) Å | Cell parameters from 25 reflections |
b = 10.144 (2) Å | θ = 20–30° |
c = 24.923 (6) Å | µ = 2.15 mm−1 |
β = 114.17 (2)° | T = 293 K |
V = 5106 (2) Å3 | Block, colourless |
Z = 16 | 0.41 × 0.33 × 0.31 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2869 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 68°, θmin = 5° |
ω/2θ scans | h = −25→0 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | k = −10→0 |
Tmin = 0.43, Tmax = 0.51 | l = −27→29 |
4577 measured reflections | 3 standard reflections every 200 reflections |
4459 independent reflections | intensity decay: 1.1% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.057P)2 + 2.16P] where P = (Fo2 + 2Fc2)/3 |
4459 reflections | (Δ/σ)max < 0.01 |
365 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C14H18O2S | V = 5106 (2) Å3 |
Mr = 250.34 | Z = 16 |
Monoclinic, C2/c | Cu Kα radiation |
a = 22.136 (8) Å | µ = 2.15 mm−1 |
b = 10.144 (2) Å | T = 293 K |
c = 24.923 (6) Å | 0.41 × 0.33 × 0.31 mm |
β = 114.17 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2869 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.022 |
Tmin = 0.43, Tmax = 0.51 | 3 standard reflections every 200 reflections |
4577 measured reflections | intensity decay: 1.1% |
4459 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.16 e Å−3 |
4459 reflections | Δρmin = −0.18 e Å−3 |
365 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.07869 (12) | −0.3682 (3) | 0.49358 (11) | 0.0620 (10) | 0.717 (18) |
C1 | 0.1483 (8) | −0.3168 (15) | 0.4822 (5) | 0.063 (3) | 0.717 (18) |
H1A | 0.1445 | −0.3413 | 0.4433 | 0.076* | 0.717 (18) |
H1B | 0.1544 | −0.2222 | 0.4870 | 0.076* | 0.717 (18) |
C2 | 0.2042 (3) | −0.3897 (10) | 0.5293 (2) | 0.0565 (16) | 0.717 (18) |
H2A | 0.2045 | −0.4809 | 0.5176 | 0.068* | 0.717 (18) |
H2B | 0.2462 | −0.3500 | 0.5347 | 0.068* | 0.717 (18) |
S1' | 0.0780 (4) | −0.3668 (9) | 0.4945 (4) | 0.092 (4) | 0.283 (18) |
C1' | 0.1536 (19) | −0.345 (4) | 0.4797 (15) | 0.080 (11) | 0.283 (18) |
H1'1 | 0.1636 | −0.4244 | 0.4633 | 0.096* | 0.283 (18) |
H1'2 | 0.1481 | −0.2723 | 0.4527 | 0.096* | 0.283 (18) |
C2' | 0.2058 (8) | −0.316 (3) | 0.5379 (7) | 0.066 (5) | 0.283 (18) |
H2'1 | 0.2484 | −0.3396 | 0.5384 | 0.079* | 0.283 (18) |
H2'2 | 0.2062 | −0.2220 | 0.5455 | 0.079* | 0.283 (18) |
O1 | 0.19592 (8) | −0.38421 (17) | 0.58134 (7) | 0.0541 (5) | |
O2 | 0.22455 (7) | −0.58800 (18) | 0.66598 (8) | 0.0574 (5) | |
H2 | 0.2342 | −0.5281 | 0.6488 | 0.086* | |
C3 | 0.12878 (11) | −0.4062 (2) | 0.57218 (9) | 0.0439 (5) | |
C4 | 0.11861 (11) | −0.5492 (2) | 0.58480 (9) | 0.0427 (5) | |
H4A | 0.1342 | −0.6057 | 0.5617 | 0.051* | |
H4B | 0.0716 | −0.5652 | 0.5721 | 0.051* | |
C5 | 0.15445 (10) | −0.5873 (2) | 0.64997 (9) | 0.0406 (5) | |
C6 | 0.13858 (13) | −0.4885 (2) | 0.68876 (10) | 0.0512 (6) | |
H6A | 0.0923 | −0.4970 | 0.6818 | 0.061* | |
H6B | 0.1650 | −0.5092 | 0.7298 | 0.061* | |
C7 | 0.15215 (15) | −0.3471 (3) | 0.67682 (11) | 0.0600 (7) | |
H7A | 0.1991 | −0.3360 | 0.6870 | 0.072* | |
H7B | 0.1398 | −0.2877 | 0.7011 | 0.072* | |
C8 | 0.11287 (13) | −0.3130 (3) | 0.61213 (11) | 0.0571 (7) | |
H8A | 0.0659 | −0.3175 | 0.6029 | 0.068* | |
H8B | 0.1231 | −0.2234 | 0.6050 | 0.068* | |
C9 | 0.13527 (11) | −0.7260 (2) | 0.65987 (9) | 0.0421 (5) | |
C10 | 0.18134 (13) | −0.8246 (3) | 0.68430 (10) | 0.0524 (6) | |
H10 | 0.2260 | −0.8069 | 0.6951 | 0.063* | |
C11 | 0.16190 (16) | −0.9493 (3) | 0.69293 (12) | 0.0647 (8) | |
H11 | 0.1937 | −1.0144 | 0.7096 | 0.078* | |
C12 | 0.09714 (16) | −0.9783 (3) | 0.67748 (12) | 0.0647 (8) | |
H12 | 0.0845 | −1.0627 | 0.6833 | 0.078* | |
C13 | 0.05050 (15) | −0.8817 (3) | 0.65319 (13) | 0.0651 (8) | |
H13 | 0.0059 | −0.9007 | 0.6422 | 0.078* | |
C14 | 0.06945 (12) | −0.7565 (3) | 0.64496 (11) | 0.0536 (6) | |
H14 | 0.0374 | −0.6914 | 0.6291 | 0.064* | |
S1A | −0.17349 (11) | −0.1055 (2) | 0.49505 (8) | 0.0550 (7) | 0.794 (16) |
C1A | −0.1058 (5) | −0.0630 (10) | 0.4801 (3) | 0.063 (2) | 0.794 (16) |
H1A1 | −0.1129 | −0.0885 | 0.4404 | 0.076* | 0.794 (16) |
H1A2 | −0.0975 | 0.0311 | 0.4846 | 0.076* | 0.794 (16) |
C2A | −0.0486 (2) | −0.1401 (9) | 0.5255 (2) | 0.0557 (15) | 0.794 (16) |
H2A2 | −0.0502 | −0.2313 | 0.5133 | 0.067* | 0.794 (16) |
H2A3 | −0.0066 | −0.1027 | 0.5295 | 0.067* | 0.794 (16) |
S1A' | −0.1738 (8) | −0.1171 (18) | 0.4944 (6) | 0.140 (7) | 0.206 (16) |
C1A' | −0.094 (2) | −0.080 (4) | 0.4814 (16) | 0.086 (14) | 0.206 (16) |
H1A3 | −0.0837 | −0.1543 | 0.4620 | 0.103* | 0.206 (16) |
H1A4 | −0.1004 | −0.0025 | 0.4571 | 0.103* | 0.206 (16) |
C2A' | −0.0444 (9) | −0.061 (4) | 0.5362 (10) | 0.067 (7) | 0.206 (16) |
H2A4 | −0.0421 | 0.0324 | 0.5460 | 0.080* | 0.206 (16) |
H2A5 | −0.0024 | −0.0858 | 0.5357 | 0.080* | 0.206 (16) |
O1A | −0.05462 (8) | −0.13291 (17) | 0.57908 (7) | 0.0540 (5) | |
O2A | −0.02599 (7) | −0.34124 (19) | 0.66071 (8) | 0.0579 (5) | |
H2A1 | −0.0163 | −0.2785 | 0.6450 | 0.087* | |
C3A | −0.12113 (11) | −0.1512 (2) | 0.57221 (9) | 0.0445 (6) | |
C4A | −0.13313 (11) | −0.2940 (2) | 0.58343 (9) | 0.0431 (6) | |
H4A1 | −0.1202 | −0.3502 | 0.5584 | 0.052* | |
H4A2 | −0.1801 | −0.3067 | 0.5724 | 0.052* | |
C5A | −0.09502 (10) | −0.3369 (2) | 0.64782 (9) | 0.0412 (5) | |
C6A | −0.10607 (13) | −0.2395 (2) | 0.68970 (10) | 0.0521 (6) | |
H6A1 | −0.1516 | −0.2457 | 0.6852 | 0.062* | |
H6A2 | −0.0777 | −0.2632 | 0.7299 | 0.062* | |
C7A | −0.09154 (16) | −0.0978 (3) | 0.67847 (11) | 0.0634 (8) | |
H7A1 | −0.1014 | −0.0391 | 0.7045 | 0.076* | |
H7A2 | −0.0449 | −0.0890 | 0.6868 | 0.076* | |
C8A | −0.13300 (14) | −0.0592 (3) | 0.61484 (11) | 0.0588 (7) | |
H8A1 | −0.1795 | −0.0613 | 0.6075 | 0.071* | |
H8A2 | −0.1221 | 0.0302 | 0.6083 | 0.071* | |
C9A | −0.11606 (11) | −0.4747 (2) | 0.65716 (9) | 0.0433 (6) | |
C10A | −0.07107 (13) | −0.5755 (3) | 0.68012 (11) | 0.0548 (6) | |
H10A | −0.0265 | −0.5599 | 0.6895 | 0.066* | |
C11A | −0.09089 (16) | −0.6992 (3) | 0.68953 (12) | 0.0672 (8) | |
H11A | −0.0596 | −0.7656 | 0.7054 | 0.081* | |
C12A | −0.15592 (16) | −0.7246 (3) | 0.67570 (12) | 0.0658 (8) | |
H12A | −0.1691 | −0.8081 | 0.6819 | 0.079* | |
C13A | −0.20161 (14) | −0.6270 (3) | 0.65277 (12) | 0.0614 (7) | |
H13A | −0.2461 | −0.6442 | 0.6432 | 0.074* | |
C14A | −0.18207 (12) | −0.5018 (3) | 0.64368 (10) | 0.0523 (6) | |
H14A | −0.2136 | −0.4356 | 0.6284 | 0.063* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0608 (14) | 0.0836 (18) | 0.0325 (14) | 0.0086 (14) | 0.0099 (10) | 0.0194 (11) |
C1 | 0.092 (6) | 0.066 (4) | 0.043 (4) | 0.001 (3) | 0.039 (4) | 0.014 (4) |
C2 | 0.064 (3) | 0.062 (4) | 0.057 (3) | −0.008 (3) | 0.038 (2) | −0.004 (3) |
S1' | 0.085 (5) | 0.128 (7) | 0.056 (6) | −0.067 (5) | 0.021 (4) | 0.013 (4) |
C1' | 0.077 (16) | 0.11 (3) | 0.060 (13) | −0.039 (16) | 0.036 (12) | −0.026 (13) |
C2' | 0.082 (8) | 0.071 (12) | 0.048 (7) | −0.020 (9) | 0.031 (6) | 0.011 (8) |
O1 | 0.0505 (10) | 0.0693 (12) | 0.0443 (9) | −0.0127 (8) | 0.0211 (8) | 0.0067 (8) |
O2 | 0.0439 (9) | 0.0629 (13) | 0.0595 (11) | −0.0031 (8) | 0.0153 (8) | 0.0087 (9) |
C3 | 0.0494 (13) | 0.0492 (14) | 0.0345 (11) | −0.0055 (11) | 0.0187 (10) | 0.0030 (10) |
C4 | 0.0481 (13) | 0.0483 (14) | 0.0335 (11) | −0.0088 (11) | 0.0184 (10) | −0.0021 (10) |
C5 | 0.0413 (12) | 0.0442 (14) | 0.0356 (11) | −0.0019 (10) | 0.0150 (9) | 0.0010 (10) |
C6 | 0.0749 (17) | 0.0486 (15) | 0.0355 (12) | −0.0002 (13) | 0.0283 (12) | 0.0009 (11) |
C7 | 0.101 (2) | 0.0422 (16) | 0.0464 (14) | −0.0017 (15) | 0.0401 (15) | −0.0036 (12) |
C8 | 0.0792 (18) | 0.0451 (16) | 0.0577 (15) | 0.0058 (13) | 0.0390 (14) | 0.0091 (12) |
C9 | 0.0508 (13) | 0.0439 (14) | 0.0339 (11) | −0.0015 (11) | 0.0195 (10) | 0.0009 (10) |
C10 | 0.0599 (15) | 0.0483 (16) | 0.0456 (13) | 0.0080 (12) | 0.0182 (12) | 0.0036 (12) |
C11 | 0.092 (2) | 0.0457 (17) | 0.0557 (16) | 0.0161 (15) | 0.0292 (16) | 0.0087 (13) |
C12 | 0.097 (2) | 0.0436 (17) | 0.0600 (17) | −0.0082 (16) | 0.0389 (16) | 0.0012 (13) |
C13 | 0.0710 (18) | 0.0586 (19) | 0.0705 (18) | −0.0131 (15) | 0.0339 (15) | 0.0049 (15) |
C14 | 0.0547 (15) | 0.0462 (15) | 0.0608 (15) | −0.0030 (12) | 0.0245 (12) | 0.0087 (12) |
S1A | 0.0536 (11) | 0.0727 (13) | 0.0326 (10) | −0.0056 (8) | 0.0115 (8) | 0.0162 (7) |
C1A | 0.085 (5) | 0.072 (4) | 0.044 (3) | 0.006 (3) | 0.038 (3) | 0.021 (3) |
C2A | 0.063 (3) | 0.061 (4) | 0.054 (2) | −0.002 (2) | 0.036 (2) | 0.001 (2) |
S1A' | 0.118 (10) | 0.193 (15) | 0.080 (9) | −0.021 (8) | 0.010 (7) | 0.041 (8) |
C1A' | 0.070 (17) | 0.11 (3) | 0.11 (2) | −0.057 (19) | 0.061 (16) | −0.044 (19) |
C2A' | 0.079 (11) | 0.060 (15) | 0.065 (11) | −0.008 (10) | 0.032 (9) | 0.018 (10) |
O1A | 0.0523 (10) | 0.0679 (12) | 0.0435 (9) | −0.0127 (8) | 0.0214 (8) | 0.0060 (8) |
O2A | 0.0458 (9) | 0.0654 (13) | 0.0596 (11) | −0.0051 (8) | 0.0184 (8) | 0.0104 (9) |
C3A | 0.0496 (13) | 0.0518 (15) | 0.0332 (11) | −0.0037 (11) | 0.0179 (10) | 0.0050 (10) |
C4A | 0.0473 (13) | 0.0517 (15) | 0.0313 (11) | −0.0082 (11) | 0.0172 (10) | −0.0007 (10) |
C5A | 0.0424 (12) | 0.0477 (14) | 0.0337 (11) | −0.0044 (10) | 0.0157 (9) | 0.0017 (10) |
C6A | 0.0725 (17) | 0.0514 (16) | 0.0354 (12) | −0.0060 (13) | 0.0253 (12) | −0.0007 (11) |
C7A | 0.103 (2) | 0.0499 (17) | 0.0433 (14) | −0.0094 (15) | 0.0364 (15) | −0.0080 (12) |
C8A | 0.0814 (18) | 0.0489 (16) | 0.0534 (15) | 0.0044 (14) | 0.0349 (14) | 0.0056 (12) |
C9A | 0.0527 (14) | 0.0454 (15) | 0.0317 (11) | −0.0024 (11) | 0.0171 (10) | −0.0001 (10) |
C10A | 0.0618 (16) | 0.0513 (17) | 0.0493 (14) | 0.0021 (13) | 0.0207 (12) | 0.0036 (12) |
C11A | 0.087 (2) | 0.0522 (19) | 0.0597 (17) | 0.0094 (16) | 0.0272 (15) | 0.0100 (14) |
C12A | 0.100 (2) | 0.0465 (18) | 0.0576 (16) | −0.0112 (16) | 0.0388 (16) | 0.0002 (13) |
C13A | 0.0693 (18) | 0.0591 (19) | 0.0607 (16) | −0.0186 (15) | 0.0315 (14) | −0.0042 (14) |
C14A | 0.0575 (15) | 0.0521 (16) | 0.0483 (14) | −0.0069 (12) | 0.0228 (12) | 0.0030 (12) |
Geometric parameters (Å, º) top
S1—C1 | 1.757 (15) | S1A—C1A | 1.741 (10) |
S1—C3 | 1.854 (3) | S1A—C3A | 1.852 (3) |
C1—C2 | 1.506 (16) | C1A—C2A | 1.525 (11) |
C1—H1A | 0.9700 | C1A—H1A1 | 0.9700 |
C1—H1B | 0.9700 | C1A—H1A2 | 0.9700 |
C2—O1 | 1.383 (5) | C2A—O1A | 1.397 (4) |
C2—H2A | 0.9700 | C2A—H2A2 | 0.9700 |
C2—H2B | 0.9700 | C2A—H2A3 | 0.9700 |
S1'—C3 | 1.841 (8) | S1A'—C3A | 1.842 (13) |
S1'—C1' | 1.87 (4) | S1A'—C1A' | 1.95 (4) |
C1'—C2' | 1.47 (4) | C1A'—C2A' | 1.38 (4) |
C1'—H1'1 | 0.9700 | C1A'—H1A3 | 0.9700 |
C1'—H1'2 | 0.9700 | C1A'—H1A4 | 0.9700 |
C2'—O1 | 1.377 (12) | C2A'—O1A | 1.389 (15) |
C2'—H2'1 | 0.9700 | C2A'—H2A4 | 0.9700 |
C2'—H2'2 | 0.9700 | C2A'—H2A5 | 0.9700 |
O1—C3 | 1.426 (3) | O1A—C3A | 1.423 (3) |
O2—C5 | 1.435 (3) | O2A—C5A | 1.428 (3) |
O2—H2 | 0.8200 | O2A—H2A1 | 0.8200 |
C3—C8 | 1.515 (3) | C3A—C8A | 1.516 (3) |
C3—C4 | 1.520 (3) | C3A—C4A | 1.519 (3) |
C4—C5 | 1.537 (3) | C4A—C5A | 1.539 (3) |
C4—H4A | 0.9700 | C4A—H4A1 | 0.9700 |
C4—H4B | 0.9700 | C4A—H4A2 | 0.9700 |
C5—C9 | 1.519 (3) | C5A—C9A | 1.521 (3) |
C5—C6 | 1.530 (3) | C5A—C6A | 1.528 (3) |
C6—C7 | 1.519 (3) | C6A—C7A | 1.523 (3) |
C6—H6A | 0.9700 | C6A—H6A1 | 0.9700 |
C6—H6B | 0.9700 | C6A—H6A2 | 0.9700 |
C7—C8 | 1.526 (3) | C7A—C8A | 1.523 (3) |
C7—H7A | 0.9700 | C7A—H7A1 | 0.9700 |
C7—H7B | 0.9700 | C7A—H7A2 | 0.9700 |
C8—H8A | 0.9700 | C8A—H8A1 | 0.9700 |
C8—H8B | 0.9700 | C8A—H8A2 | 0.9700 |
C9—C10 | 1.379 (3) | C9A—C10A | 1.378 (3) |
C9—C14 | 1.383 (3) | C9A—C14A | 1.386 (3) |
C10—C11 | 1.381 (4) | C10A—C11A | 1.381 (4) |
C10—H10 | 0.9300 | C10A—H10A | 0.9300 |
C11—C12 | 1.356 (4) | C11A—C12A | 1.360 (4) |
C11—H11 | 0.9300 | C11A—H11A | 0.9300 |
C12—C13 | 1.372 (4) | C12A—C13A | 1.363 (4) |
C12—H12 | 0.9300 | C12A—H12A | 0.9300 |
C13—C14 | 1.379 (3) | C13A—C14A | 1.389 (3) |
C13—H13 | 0.9300 | C13A—H13A | 0.9300 |
C14—H14 | 0.9300 | C14A—H14A | 0.9300 |
| | | |
C1—S1—C3 | 92.7 (4) | C1A—S1A—C3A | 93.3 (3) |
C2—C1—S1 | 102.9 (7) | C2A—C1A—S1A | 103.9 (4) |
C2—C1—H1A | 111.2 | C2A—C1A—H1A1 | 111.0 |
S1—C1—H1A | 111.2 | S1A—C1A—H1A1 | 111.0 |
C2—C1—H1B | 111.2 | C2A—C1A—H1A2 | 111.0 |
S1—C1—H1B | 111.2 | S1A—C1A—H1A2 | 111.0 |
H1A—C1—H1B | 109.1 | H1A1—C1A—H1A2 | 109.0 |
O1—C2—C1 | 109.3 (7) | O1A—C2A—C1A | 107.9 (5) |
O1—C2—H2A | 109.8 | O1A—C2A—H2A2 | 110.1 |
C1—C2—H2A | 109.8 | C1A—C2A—H2A2 | 110.1 |
O1—C2—H2B | 109.8 | O1A—C2A—H2A3 | 110.1 |
C1—C2—H2B | 109.8 | C1A—C2A—H2A3 | 110.1 |
H2A—C2—H2B | 108.3 | H2A2—C2A—H2A3 | 108.4 |
C3—S1'—C1' | 91.4 (11) | C3A—S1A'—C1A' | 89.1 (13) |
C2'—C1'—S1' | 104 (2) | C2A'—C1A'—S1A' | 106 (2) |
C2'—C1'—H1'1 | 111.0 | C2A'—C1A'—H1A3 | 110.6 |
S1'—C1'—H1'1 | 111.0 | S1A'—C1A'—H1A3 | 110.6 |
C2'—C1'—H1'2 | 111.0 | C2A'—C1A'—H1A4 | 110.6 |
S1'—C1'—H1'2 | 111.0 | S1A'—C1A'—H1A4 | 110.6 |
H1'1—C1'—H1'2 | 109.0 | H1A3—C1A'—H1A4 | 108.7 |
O1—C2'—C1' | 111.3 (19) | C1A'—C2A'—O1A | 112 (2) |
O1—C2'—H2'1 | 109.4 | C1A'—C2A'—H2A4 | 109.3 |
C1'—C2'—H2'1 | 109.4 | O1A—C2A'—H2A4 | 109.3 |
O1—C2'—H2'2 | 109.4 | C1A'—C2A'—H2A5 | 109.3 |
C1'—C2'—H2'2 | 109.4 | O1A—C2A'—H2A5 | 109.3 |
H2'1—C2'—H2'2 | 108.0 | H2A4—C2A'—H2A5 | 107.9 |
C2'—O1—C2 | 32.7 (9) | C2A'—O1A—C2A | 35.2 (13) |
C2'—O1—C3 | 116.3 (7) | C2A'—O1A—C3A | 117.6 (8) |
C2—O1—C3 | 111.9 (3) | C2A—O1A—C3A | 112.2 (3) |
C5—O2—H2 | 109.5 | C5A—O2A—H2A1 | 109.5 |
O1—C3—C8 | 107.74 (19) | O1A—C3A—C8A | 107.6 (2) |
O1—C3—C4 | 110.42 (19) | O1A—C3A—C4A | 110.65 (19) |
C8—C3—C4 | 111.44 (18) | C8A—C3A—C4A | 111.37 (19) |
O1—C3—S1' | 106.4 (3) | O1A—C3A—S1A' | 106.3 (5) |
C8—C3—S1' | 110.5 (4) | C8A—C3A—S1A' | 113.9 (6) |
C4—C3—S1' | 110.2 (3) | C4A—C3A—S1A' | 106.9 (6) |
O1—C3—S1 | 105.66 (16) | O1A—C3A—S1A | 105.61 (15) |
C8—C3—S1 | 111.43 (19) | C8A—C3A—S1A | 111.05 (18) |
C4—C3—S1 | 109.98 (18) | C4A—C3A—S1A | 110.33 (17) |
S1'—C3—S1 | 1.0 (4) | S1A'—C3A—S1A | 3.7 (6) |
C3—C4—C5 | 113.73 (18) | C3A—C4A—C5A | 113.53 (18) |
C3—C4—H4A | 108.8 | C3A—C4A—H4A1 | 108.9 |
C5—C4—H4A | 108.8 | C5A—C4A—H4A1 | 108.9 |
C3—C4—H4B | 108.8 | C3A—C4A—H4A2 | 108.9 |
C5—C4—H4B | 108.8 | C5A—C4A—H4A2 | 108.9 |
H4A—C4—H4B | 107.7 | H4A1—C4A—H4A2 | 107.7 |
O2—C5—C9 | 107.00 (18) | O2A—C5A—C9A | 107.69 (19) |
O2—C5—C6 | 109.25 (19) | O2A—C5A—C6A | 108.80 (19) |
C9—C5—C6 | 110.63 (18) | C9A—C5A—C6A | 110.18 (18) |
O2—C5—C4 | 109.06 (18) | O2A—C5A—C4A | 108.82 (17) |
C9—C5—C4 | 110.30 (18) | C9A—C5A—C4A | 110.37 (18) |
C6—C5—C4 | 110.52 (19) | C6A—C5A—C4A | 110.90 (19) |
C7—C6—C5 | 112.29 (19) | C7A—C6A—C5A | 112.30 (19) |
C7—C6—H6A | 109.1 | C7A—C6A—H6A1 | 109.1 |
C5—C6—H6A | 109.1 | C5A—C6A—H6A1 | 109.1 |
C7—C6—H6B | 109.1 | C7A—C6A—H6A2 | 109.1 |
C5—C6—H6B | 109.1 | C5A—C6A—H6A2 | 109.1 |
H6A—C6—H6B | 107.9 | H6A1—C6A—H6A2 | 107.9 |
C6—C7—C8 | 110.4 (2) | C8A—C7A—C6A | 110.6 (2) |
C6—C7—H7A | 109.6 | C8A—C7A—H7A1 | 109.5 |
C8—C7—H7A | 109.6 | C6A—C7A—H7A1 | 109.5 |
C6—C7—H7B | 109.6 | C8A—C7A—H7A2 | 109.5 |
C8—C7—H7B | 109.6 | C6A—C7A—H7A2 | 109.5 |
H7A—C7—H7B | 108.1 | H7A1—C7A—H7A2 | 108.1 |
C3—C8—C7 | 111.6 (2) | C3A—C8A—C7A | 111.6 (2) |
C3—C8—H8A | 109.3 | C3A—C8A—H8A1 | 109.3 |
C7—C8—H8A | 109.3 | C7A—C8A—H8A1 | 109.3 |
C3—C8—H8B | 109.3 | C3A—C8A—H8A2 | 109.3 |
C7—C8—H8B | 109.3 | C7A—C8A—H8A2 | 109.3 |
H8A—C8—H8B | 108.0 | H8A1—C8A—H8A2 | 108.0 |
C10—C9—C14 | 117.6 (2) | C10A—C9A—C14A | 117.6 (2) |
C10—C9—C5 | 122.5 (2) | C10A—C9A—C5A | 122.1 (2) |
C14—C9—C5 | 119.8 (2) | C14A—C9A—C5A | 120.3 (2) |
C9—C10—C11 | 120.8 (2) | C9A—C10A—C11A | 121.3 (3) |
C9—C10—H10 | 119.6 | C9A—C10A—H10A | 119.4 |
C11—C10—H10 | 119.6 | C11A—C10A—H10A | 119.4 |
C12—C11—C10 | 121.0 (3) | C12A—C11A—C10A | 120.4 (3) |
C12—C11—H11 | 119.5 | C12A—C11A—H11A | 119.8 |
C10—C11—H11 | 119.5 | C10A—C11A—H11A | 119.8 |
C11—C12—C13 | 119.2 (3) | C11A—C12A—C13A | 119.7 (3) |
C11—C12—H12 | 120.4 | C11A—C12A—H12A | 120.1 |
C13—C12—H12 | 120.4 | C13A—C12A—H12A | 120.1 |
C12—C13—C14 | 120.3 (3) | C12A—C13A—C14A | 120.3 (3) |
C12—C13—H13 | 119.9 | C12A—C13A—H13A | 119.8 |
C14—C13—H13 | 119.9 | C14A—C13A—H13A | 119.8 |
C13—C14—C9 | 121.1 (3) | C9A—C14A—C13A | 120.7 (3) |
C13—C14—H14 | 119.4 | C9A—C14A—H14A | 119.7 |
C9—C14—H14 | 119.4 | C13A—C14A—H14A | 119.7 |
| | | |
C3—S1—C1—C2 | 25.1 (9) | C3A—S1A—C1A—C2A | 23.4 (6) |
S1—C1—C2—O1 | −42.8 (12) | S1A—C1A—C2A—O1A | −41.4 (8) |
C3—S1'—C1'—C2' | −23 (3) | C3A—S1A'—C1A'—C2A' | −17 (3) |
S1'—C1'—C2'—O1 | 35 (3) | S1A'—C1A'—C2A'—O1A | 30 (4) |
C1'—C2'—O1—C2 | 57 (3) | C1A'—C2A'—O1A—C2A | 55 (3) |
C1'—C2'—O1—C3 | −33 (3) | C1A'—C2A'—O1A—C3A | −34 (4) |
C1—C2—O1—C2' | −62.0 (15) | C1A—C2A—O1A—C2A' | −63.6 (14) |
C1—C2—O1—C3 | 43.0 (10) | C1A—C2A—O1A—C3A | 43.2 (8) |
C2'—O1—C3—C8 | −105.1 (15) | C2A'—O1A—C3A—C8A | −103.9 (19) |
C2—O1—C3—C8 | −140.6 (5) | C2A—O1A—C3A—C8A | −142.4 (4) |
C2'—O1—C3—C4 | 133.0 (14) | C2A'—O1A—C3A—C4A | 134.2 (19) |
C2—O1—C3—C4 | 97.5 (5) | C2A—O1A—C3A—C4A | 95.7 (4) |
C2'—O1—C3—S1' | 13.4 (15) | C2A'—O1A—C3A—S1A' | 19 (2) |
C2—O1—C3—S1' | −22.2 (6) | C2A—O1A—C3A—S1A' | −20.0 (9) |
C2'—O1—C3—S1 | 14.1 (15) | C2A'—O1A—C3A—S1A | 14.8 (19) |
C2—O1—C3—S1 | −21.4 (5) | C2A—O1A—C3A—S1A | −23.7 (5) |
C1'—S1'—C3—O1 | 6.7 (13) | C1A'—S1A'—C3A—O1A | −0.1 (14) |
C1'—S1'—C3—C8 | 123.3 (13) | C1A'—S1A'—C3A—C8A | 118.2 (13) |
C1'—S1'—C3—C4 | −113.1 (13) | C1A'—S1A'—C3A—C4A | −118.3 (13) |
C1'—S1'—C3—S1 | −38 (18) | C1A'—S1A'—C3A—S1A | 80 (8) |
C1—S1—C3—O1 | −4.0 (6) | C1A—S1A—C3A—O1A | −1.7 (4) |
C1—S1—C3—C8 | 112.7 (6) | C1A—S1A—C3A—C8A | 114.7 (4) |
C1—S1—C3—C4 | −123.2 (6) | C1A—S1A—C3A—C4A | −121.4 (4) |
C1—S1—C3—S1' | 132 (19) | C1A—S1A—C3A—S1A' | −103 (8) |
O1—C3—C4—C5 | 67.8 (2) | O1A—C3A—C4A—C5A | 67.5 (2) |
C8—C3—C4—C5 | −51.9 (3) | C8A—C3A—C4A—C5A | −52.1 (3) |
S1'—C3—C4—C5 | −174.9 (3) | S1A'—C3A—C4A—C5A | −177.2 (5) |
S1—C3—C4—C5 | −175.93 (17) | S1A—C3A—C4A—C5A | −175.95 (16) |
C3—C4—C5—O2 | −69.5 (2) | C3A—C4A—C5A—O2A | −69.1 (2) |
C3—C4—C5—C9 | 173.32 (18) | C3A—C4A—C5A—C9A | 172.94 (18) |
C3—C4—C5—C6 | 50.7 (3) | C3A—C4A—C5A—C6A | 50.5 (3) |
O2—C5—C6—C7 | 66.8 (3) | O2A—C5A—C6A—C7A | 67.2 (3) |
C9—C5—C6—C7 | −175.6 (2) | C9A—C5A—C6A—C7A | −174.9 (2) |
C4—C5—C6—C7 | −53.2 (3) | C4A—C5A—C6A—C7A | −52.4 (3) |
C5—C6—C7—C8 | 57.0 (3) | C5A—C6A—C7A—C8A | 56.2 (3) |
O1—C3—C8—C7 | −66.6 (3) | O1A—C3A—C8A—C7A | −66.3 (3) |
C4—C3—C8—C7 | 54.6 (3) | C4A—C3A—C8A—C7A | 55.1 (3) |
S1'—C3—C8—C7 | 177.6 (3) | S1A'—C3A—C8A—C7A | 176.1 (6) |
S1—C3—C8—C7 | 177.9 (2) | S1A—C3A—C8A—C7A | 178.54 (19) |
C6—C7—C8—C3 | −57.3 (3) | C6A—C7A—C8A—C3A | −57.3 (3) |
O2—C5—C9—C10 | 4.5 (3) | O2A—C5A—C9A—C10A | 6.1 (3) |
C6—C5—C9—C10 | −114.4 (2) | C6A—C5A—C9A—C10A | −112.5 (2) |
C4—C5—C9—C10 | 123.0 (2) | C4A—C5A—C9A—C10A | 124.7 (2) |
O2—C5—C9—C14 | −176.5 (2) | O2A—C5A—C9A—C14A | −175.29 (19) |
C6—C5—C9—C14 | 64.6 (3) | C6A—C5A—C9A—C14A | 66.2 (3) |
C4—C5—C9—C14 | −58.0 (3) | C4A—C5A—C9A—C14A | −56.6 (3) |
C14—C9—C10—C11 | 0.6 (4) | C14A—C9A—C10A—C11A | −0.1 (4) |
C5—C9—C10—C11 | 179.6 (2) | C5A—C9A—C10A—C11A | 178.5 (2) |
C9—C10—C11—C12 | 0.2 (4) | C9A—C10A—C11A—C12A | 0.6 (4) |
C10—C11—C12—C13 | −0.3 (4) | C10A—C11A—C12A—C13A | −0.4 (4) |
C11—C12—C13—C14 | −0.4 (4) | C11A—C12A—C13A—C14A | −0.2 (4) |
C12—C13—C14—C9 | 1.2 (4) | C10A—C9A—C14A—C13A | −0.5 (3) |
C10—C9—C14—C13 | −1.2 (4) | C5A—C9A—C14A—C13A | −179.2 (2) |
C5—C9—C14—C13 | 179.7 (2) | C12A—C13A—C14A—C9A | 0.7 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 2.12 | 2.834 (2) | 145 |
O2A—H2A1···O1A | 0.82 | 2.11 | 2.820 (2) | 145 |
Experimental details
| (IIa) | (IIb) |
Crystal data |
Chemical formula | C14H18O2S | C14H18O2S |
Mr | 250.34 | 250.34 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, C2/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.313 (2), 10.674 (5), 19.535 (2) | 22.136 (8), 10.144 (2), 24.923 (6) |
α, β, γ (°) | 90, 90, 90 | 90, 114.17 (2), 90 |
V (Å3) | 2568 (1) | 5106 (2) |
Z | 8 | 16 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 2.13 | 2.15 |
Crystal size (mm) | 0.52 × 0.18 × 0.10 | 0.41 × 0.33 × 0.31 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | Empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) |
Tmin, Tmax | 0.40, 0.82 | 0.43, 0.51 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2199, 2199, 1529 | 4577, 4459, 2869 |
Rint | 0.00 | 0.022 |
(sin θ/λ)max (Å−1) | 0.601 | 0.601 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.150, 1.03 | 0.044, 0.124, 1.03 |
No. of reflections | 2199 | 4459 |
No. of parameters | 155 | 365 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.25 | 0.16, −0.18 |
Selected geometric parameters (Å, º) for (IIa) topS1—C1 | 1.794 (4) | O1—C3 | 1.424 (3) |
S1—C3 | 1.853 (3) | O2—C5 | 1.430 (3) |
O1—C2 | 1.420 (4) | | |
| | | |
C1—S1—C3 | 92.00 (16) | C2—O1—C3 | 110.6 (2) |
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 2.14 | 2.962 (3) | 175 |
Symmetry code: (i) −x+1/2, y−1/2, z. |
Selected geometric parameters (Å, º) for (IIb) topS1—C1 | 1.757 (15) | S1A—C1A | 1.741 (10) |
S1—C3 | 1.854 (3) | S1A—C3A | 1.852 (3) |
C2—O1 | 1.383 (5) | C2A—O1A | 1.397 (4) |
O1—C3 | 1.426 (3) | O1A—C3A | 1.423 (3) |
O2—C5 | 1.435 (3) | O2A—C5A | 1.428 (3) |
| | | |
C1—S1—C3 | 92.7 (4) | C1A—S1A—C3A | 93.3 (3) |
C2—O1—C3 | 111.9 (3) | C2A—O1A—C3A | 112.2 (3) |
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 2.12 | 2.834 (2) | 145 |
O2A—H2A1···O1A | 0.82 | 2.11 | 2.820 (2) | 145 |
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The most recent theory of products distribution relies upon the ground state relative abundance of the conformational isomers and argues against the transition state structure (Gung & Francis, 1993; Tomoda, 1999). 1-Oxa-4-thiaspiro[4.5]decan-7-one, (I), would be expected to exist as an equilibrium mixture of (Ia) and (Ib). The isomer (Ib) is 0.92 kcal/mol (1 kcal = 4.1868 J) more stable than the isomer (Ia), as determined from energy calculations using the program GAUSSIAN94 (Frisch et al., 1995). This small energy difference would correlate to (IIa):(IIb) = 1:1 on reaction with a nucleophile. Due to very similar geometry and to the high steric resistance arising from the acetal function to axial attack, the conformers (Ia) and (Ib) would be expected to undergo predominantly equatorial attack at equal rates. In order to investigate the validity of this prediction, we reacted (I) with phenylmagnesium bromide, PhMgBr, to obtain the two title products, (IIa) and (IIb). The stereochemical characterization of these products from spectrometric data was difficult. We therefore resorted to single-crystal X-ray determination for the structural characterization of these compounds. In this paper, we describe the crystal structures of (IIa) and (IIb). \sch
The structure of (IIa) (Fig. 1) is composed of molecules having intermolecular interactions between the hydroxyl H atom and the O atom of the five-membered heterocyclic ring, with O2···O1 2.962 (3) Å, forming a polymeric chain along the b axis (Fig. 2). The acetal S and O atoms are axial and equatorial, respectively, and the heterocyclic ring adopts an O-envelope conformation with O1 0.509 (4) Å out of the plane formed by the rest of the atoms of the ring; the maximum deviation of any atom from this plane is 0.014 (2) Å. The six-membered ring C3—C8 adopts a classical chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.542 (3) Å, and θ = 5.1 (3) and ϕ = 259 (4)°, while the phenyl ring (C9—C14) is essentially planar [maximum deviation 0.006 (2) Å].
The asymmetric unit of (IIb) (Fig. 3), on the other hand, is composed of two independent molecules separated by normal van der Waals distances. The hydroxyl H atoms and the O atoms of the five-membered heterocyclic rings in the two molecules display intramolecular interactions with O···O 2.834 (2) and 2.820 (2) Å, unlike the intermolecular hydrogen-bonding pattern observed in (IIa). The acetal S and O atoms in (IIb) have been reversed from (IIa) and are equatorial and axial, respectively. Atoms S1, C1 and C2 of the heterocyclic rings are disordered, resulting in S1/C1/C2/O1/C3 and S1'/C1'/C2'/O1/C3 rings in one molecule, and S1A/C1A/C2A/O1A/C3A and S1A'/C1A'/C2A'/O1/C3 rings in the second. These rings adopt C2, C2', C2A and C2A'-envelope conformations, with these atoms 0.557 (17), 0.44 (5), 0.559 (13) and 0.39 (5) Å, respectively, out of the planes formed by the rest of the atoms of the rings. This is also in contrast with the heterocyclic ring conformation in (IIa), which adopts an O-envelope conformation. The separation between the disordered fractions of atoms ranges between 0.035 and 0.843 Å for S1, S1' and C2A, C2A', respectively. The six-membered rings C3—C8 and C3A—C8A in (IIb) adopt a classical chair conformation, with puckering parameters Q = 0.552 (3) and 0.550 (3) Å, and θ = 5.2 (3) and 4.1 (3), and ϕ = 248 (4) and 259 (4)°, respectively. The phenyl rings (C9—C14 and C9A—C14A) are essentially planar.
The bond distances and angles in the two structures are normal and agree well with the corresponding values reported for similar compounds in the Cambridge Structural Database (Allen & Kennard, 1993). The S—Csp3 bond distances of 1.853 (3) and 1.794 (4) Å in (IIa), although significantly different from each other, are in excellent agreement with the corresponding bond distances in the two molecules of (IIb). Similar inequivalent S—C bond distances have been reported in the crystal structures of cyclohexanespiro-2'-(1',3'-oxathiolan-5-one 3'-oxide) (Frechina et al., 1992), (+)-(3S,4R)-6-phenyl-1-oxa-4-thiaspiro[4.5]decan-8-one (Sonoda et al., 1992), two derivatives of an oxathiaspirodecene (Parvez et al., 1997), 2-(7-ethylidene-6-methyl-1-oxa-4-thiaspiro[4.5]dec-7-yl)ethanol (Parvez et al., 1998), two derivatives of 1-oxa-4-thiaspirodecane (Parvez et al., 2000a) and some Diels-Alder adducts of an 1-oxa-4-thia-6-vinylspirodec-6-ene (Parvez et al., 2000b).