Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013597/da1148sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013597/da1148IIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013597/da1148IIIasup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013597/da1148IVbsup4.hkl |
CCDC references: 158261; 158262; 158263
Cyclohexanone was hydroxymethylated following the Baylis-Hillman reaction (Rezgui & Gaied, 1998) to furnish 2-hydroxymethyl-2-cyclohexenone which, when condensed with mercaptoethanol in the presence of 2 mol% pyridinium p-toluenesulfonate in benzene under azeotropic removal of water, produced an acetal. Finally, Wittig olefination of the aldehyde that was formed from the oxidation of the acetal with pyridinium dichromate generated the desired diene, 6-vinyl-1-oxa-4-thia-spiro[4.5]dec-6-ene, (I).
For compounds (IIa) and (IIIa), the space groups P21 and P21/c, respectively, were determined from the systematic absences, packing considerations, statistical analyses of intensity distribution and the successful solution and refinement of the structures. The number of equivalent reflections measured for (IIa) was not sufficient to establish an absolute structure. However, based on the final Flack parameter (Flack, 1983) of 0.04 (3), compared with the value of 0.15 (3) obtained from the inverted structure, the absolute structure presented in this paper appears to be correct. For compound (IVb), the space group P1 was determined from the packing considerations, a statistical analysis of intensity distribution and the successful solution and refinement of the structure. In all three structures, most of the H atoms were located from difference maps and all H atoms were placed at geometrically idealized positions (C—H 0.93–1.00 Å) utilizing riding models, and torsional parameters were refined for each methyl group in (IIIa) and (IVb).
Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (IIa), (IVb); MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (IIIa). Cell refinement: CAD-4 Software for (IIa), (IVb); MSC/AFC Diffractometer Control Software for (IIIa). For all compounds, 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.
C20H21NO3S | F(000) = 376 |
Mr = 355.44 | Dx = 1.363 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 12.047 (2) Å | Cell parameters from 25 reflections |
b = 7.808 (2) Å | θ = 12.5–20.0° |
c = 9.718 (1) Å | µ = 1.82 mm−1 |
β = 108.71 (1)° | T = 293 K |
V = 865.8 (3) Å3 | Prismatic, colourless |
Z = 2 | 0.6 × 0.4 × 0.2 mm |
Enraf-Nonius CAD4 diffractometer | 1653 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
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→9 |
Tmin = 0.41, Tmax = 0.71 | l = −11→11 |
1788 measured reflections | 3 standard reflections every 200 reflections |
1705 independent reflections | intensity decay: <0.1% |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.092P)2 + 0.087P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max < 0.01 |
1705 reflections | Δρmax = 0.64 e Å−3 |
226 parameters | Δρmin = −0.29 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (3) |
C20H21NO3S | V = 865.8 (3) Å3 |
Mr = 355.44 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 12.047 (2) Å | µ = 1.82 mm−1 |
b = 7.808 (2) Å | T = 293 K |
c = 9.718 (1) Å | 0.6 × 0.4 × 0.2 mm |
β = 108.71 (1)° |
Enraf-Nonius CAD4 diffractometer | 1653 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.014 |
Tmin = 0.41, Tmax = 0.71 | 3 standard reflections every 200 reflections |
1788 measured reflections | intensity decay: <0.1% |
1705 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.125 | Δρmax = 0.64 e Å−3 |
S = 1.15 | Δρmin = −0.29 e Å−3 |
1705 reflections | Absolute structure: Flack (1983) |
226 parameters | Absolute structure parameter: 0.04 (3) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
S1 | 0.88594 (8) | 0.63046 (18) | 0.52902 (8) | 0.0682 (3) | |
O1 | 0.8664 (2) | 0.8123 (4) | 0.7480 (3) | 0.0604 (7) | |
O2 | 1.3804 (2) | 0.3284 (3) | 0.8778 (2) | 0.0550 (6) | |
O3 | 1.3394 (2) | 0.7431 (3) | 1.1878 (3) | 0.0586 (6) | |
N1 | 1.3778 (2) | 0.5111 (3) | 1.0629 (3) | 0.0400 (5) | |
C1 | 0.7687 (4) | 0.7831 (7) | 0.5018 (5) | 0.0769 (13) | |
H1A | 0.7506 | 0.8382 | 0.4077 | 0.092* | |
H1B | 0.6984 | 0.7285 | 0.5091 | 0.092* | |
C2 | 0.8161 (4) | 0.9078 (7) | 0.6210 (5) | 0.0778 (13) | |
H2A | 0.8747 | 0.9798 | 0.6010 | 0.093* | |
H2B | 0.7539 | 0.9802 | 0.6314 | 0.093* | |
C3 | 0.9339 (2) | 0.6699 (5) | 0.7283 (3) | 0.0446 (7) | |
C4 | 0.9050 (3) | 0.5202 (6) | 0.8093 (4) | 0.0553 (9) | |
H4A | 0.9146 | 0.5551 | 0.9082 | 0.066* | |
H4B | 0.8235 | 0.4888 | 0.7636 | 0.066* | |
C5 | 0.9810 (3) | 0.3659 (5) | 0.8124 (5) | 0.0643 (10) | |
H5A | 0.9639 | 0.3212 | 0.7147 | 0.077* | |
H5B | 0.9629 | 0.2773 | 0.8719 | 0.077* | |
C6 | 1.1110 (3) | 0.4108 (5) | 0.8733 (5) | 0.0568 (9) | |
H6A | 1.1578 | 0.3104 | 0.8709 | 0.068* | |
H6B | 1.1298 | 0.4473 | 0.9736 | 0.068* | |
C7 | 1.1403 (2) | 0.5549 (4) | 0.7830 (3) | 0.0390 (6) | |
H7 | 1.1170 | 0.5136 | 0.6825 | 0.047* | |
C8 | 1.0646 (2) | 0.7073 (4) | 0.7834 (3) | 0.0378 (6) | |
C9 | 1.1027 (3) | 0.8609 (4) | 0.8343 (4) | 0.0450 (7) | |
H9 | 1.0472 | 0.9448 | 0.8310 | 0.054* | |
C10 | 1.2294 (3) | 0.9087 (4) | 0.8969 (4) | 0.0527 (8) | |
H10A | 1.2410 | 0.9703 | 0.9871 | 0.063* | |
H10B | 1.2495 | 0.9853 | 0.8300 | 0.063* | |
C11 | 1.3107 (3) | 0.7573 (4) | 0.9261 (4) | 0.0433 (7) | |
H11 | 1.3845 | 0.7984 | 0.9156 | 0.052* | |
C12 | 1.2742 (2) | 0.6018 (4) | 0.8264 (3) | 0.0401 (6) | |
H12 | 1.2959 | 0.6195 | 0.7385 | 0.048* | |
C13 | 1.3494 (2) | 0.4627 (4) | 0.9178 (3) | 0.0405 (6) | |
C14 | 1.3413 (2) | 0.6802 (4) | 1.0756 (3) | 0.0415 (7) | |
C15 | 1.4371 (2) | 0.4058 (4) | 1.1842 (3) | 0.0391 (6) | |
C16 | 1.3981 (3) | 0.2408 (5) | 1.1927 (4) | 0.0522 (8) | |
H16 | 1.3333 | 0.1986 | 1.1198 | 0.063* | |
C17 | 1.4555 (3) | 0.1393 (6) | 1.3096 (4) | 0.0609 (9) | |
H17 | 1.4304 | 0.0275 | 1.3147 | 0.073* | |
C18 | 1.5498 (3) | 0.2027 (5) | 1.4189 (4) | 0.0562 (8) | |
H18 | 1.5870 | 0.1351 | 1.4993 | 0.067* | |
C19 | 1.5890 (3) | 0.3653 (6) | 1.4092 (4) | 0.0555 (8) | |
H19 | 1.6536 | 0.4070 | 1.4828 | 0.067* | |
C20 | 1.5342 (3) | 0.4677 (5) | 1.2921 (3) | 0.0480 (7) | |
H20 | 1.5620 | 0.5774 | 1.2854 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0563 (5) | 0.1032 (8) | 0.0379 (4) | −0.0106 (5) | 0.0050 (3) | −0.0046 (5) |
O1 | 0.0424 (11) | 0.0773 (17) | 0.0578 (13) | 0.0145 (12) | 0.0108 (10) | 0.0061 (13) |
O2 | 0.0534 (12) | 0.0608 (15) | 0.0478 (12) | 0.0161 (12) | 0.0122 (10) | −0.0144 (11) |
O3 | 0.0657 (14) | 0.0569 (15) | 0.0506 (13) | 0.0056 (12) | 0.0152 (11) | −0.0162 (12) |
N1 | 0.0374 (11) | 0.0413 (13) | 0.0400 (12) | −0.0002 (11) | 0.0105 (9) | −0.0071 (11) |
C1 | 0.061 (2) | 0.092 (3) | 0.060 (2) | −0.009 (2) | −0.0052 (17) | 0.028 (2) |
C2 | 0.062 (2) | 0.075 (3) | 0.083 (3) | 0.007 (2) | 0.005 (2) | 0.024 (3) |
C3 | 0.0350 (13) | 0.0599 (19) | 0.0358 (13) | 0.0026 (13) | 0.0069 (11) | 0.0028 (13) |
C4 | 0.0355 (14) | 0.074 (2) | 0.0553 (19) | −0.0083 (16) | 0.0126 (13) | 0.0092 (18) |
C5 | 0.0459 (17) | 0.052 (2) | 0.092 (3) | −0.0125 (16) | 0.0184 (17) | 0.013 (2) |
C6 | 0.0419 (17) | 0.0465 (19) | 0.079 (2) | −0.0030 (14) | 0.0152 (16) | 0.0129 (18) |
C7 | 0.0362 (13) | 0.0430 (16) | 0.0367 (13) | −0.0019 (12) | 0.0101 (11) | −0.0060 (11) |
C8 | 0.0342 (13) | 0.0472 (15) | 0.0310 (12) | 0.0010 (12) | 0.0089 (10) | 0.0039 (12) |
C9 | 0.0410 (15) | 0.0459 (16) | 0.0452 (15) | 0.0053 (13) | 0.0098 (12) | 0.0034 (13) |
C10 | 0.0453 (17) | 0.0394 (16) | 0.069 (2) | −0.0032 (13) | 0.0117 (15) | −0.0027 (15) |
C11 | 0.0346 (14) | 0.0426 (16) | 0.0527 (17) | −0.0048 (12) | 0.0140 (12) | −0.0033 (14) |
C12 | 0.0368 (13) | 0.0473 (16) | 0.0388 (13) | −0.0025 (12) | 0.0159 (11) | −0.0029 (13) |
C13 | 0.0321 (12) | 0.0491 (16) | 0.0410 (14) | −0.0003 (12) | 0.0129 (11) | −0.0056 (13) |
C14 | 0.0358 (13) | 0.0427 (15) | 0.0443 (15) | −0.0061 (12) | 0.0104 (11) | −0.0103 (13) |
C15 | 0.0344 (13) | 0.0458 (15) | 0.0376 (13) | −0.0024 (12) | 0.0123 (11) | −0.0078 (12) |
C16 | 0.0457 (17) | 0.054 (2) | 0.0528 (18) | −0.0124 (15) | 0.0095 (14) | −0.0027 (15) |
C17 | 0.0583 (19) | 0.056 (2) | 0.068 (2) | −0.0037 (18) | 0.0194 (16) | 0.0097 (19) |
C18 | 0.0530 (17) | 0.066 (2) | 0.0499 (17) | 0.0122 (17) | 0.0163 (14) | 0.0059 (16) |
C19 | 0.0458 (16) | 0.066 (2) | 0.0484 (17) | 0.0001 (17) | 0.0063 (13) | −0.0097 (17) |
C20 | 0.0423 (14) | 0.0501 (17) | 0.0469 (16) | −0.0036 (14) | 0.0075 (12) | −0.0112 (14) |
S1—C1 | 1.802 (6) | C7—C8 | 1.500 (4) |
S1—C3 | 1.860 (3) | C7—C12 | 1.574 (4) |
O1—C2 | 1.403 (5) | C7—H7 | 0.9800 |
O1—C3 | 1.427 (4) | C8—C9 | 1.322 (5) |
O2—C13 | 1.218 (4) | C9—C10 | 1.497 (4) |
O3—C14 | 1.203 (4) | C9—H9 | 0.9300 |
N1—C13 | 1.392 (4) | C10—C11 | 1.503 (5) |
N1—C14 | 1.409 (4) | C10—H10A | 0.9700 |
N1—C15 | 1.427 (4) | C10—H10B | 0.9700 |
C1—C2 | 1.480 (7) | C11—C14 | 1.506 (4) |
C1—H1A | 0.9700 | C11—C12 | 1.528 (4) |
C1—H1B | 0.9700 | C11—H11 | 0.9800 |
C2—H2A | 0.9700 | C12—C13 | 1.508 (4) |
C2—H2B | 0.9700 | C12—H12 | 0.9800 |
C3—C4 | 1.511 (5) | C15—C20 | 1.383 (4) |
C3—C8 | 1.519 (4) | C15—C16 | 1.383 (5) |
C4—C5 | 1.508 (6) | C16—C17 | 1.375 (5) |
C4—H4A | 0.9700 | C16—H16 | 0.9300 |
C4—H4B | 0.9700 | C17—C18 | 1.375 (6) |
C5—C6 | 1.527 (5) | C17—H17 | 0.9300 |
C5—H5A | 0.9700 | C18—C19 | 1.368 (6) |
C5—H5B | 0.9700 | C18—H18 | 0.9300 |
C6—C7 | 1.536 (4) | C19—C20 | 1.375 (5) |
C6—H6A | 0.9700 | C19—H19 | 0.9300 |
C6—H6B | 0.9700 | C20—H20 | 0.9300 |
C1—S1—C3 | 90.60 (18) | C9—C8—C3 | 120.2 (3) |
C2—O1—C3 | 113.5 (3) | C7—C8—C3 | 114.1 (3) |
C13—N1—C14 | 111.2 (3) | C8—C9—C10 | 124.4 (3) |
C13—N1—C15 | 125.2 (3) | C8—C9—H9 | 117.8 |
C14—N1—C15 | 123.7 (2) | C10—C9—H9 | 117.8 |
C2—C1—S1 | 103.4 (3) | C9—C10—C11 | 113.5 (3) |
C2—C1—H1A | 111.1 | C9—C10—H10A | 108.9 |
S1—C1—H1A | 111.1 | C11—C10—H10A | 108.9 |
C2—C1—H1B | 111.1 | C9—C10—H10B | 108.9 |
S1—C1—H1B | 111.1 | C11—C10—H10B | 108.9 |
H1A—C1—H1B | 109.0 | H10A—C10—H10B | 107.7 |
O1—C2—C1 | 106.8 (4) | C10—C11—C14 | 116.1 (3) |
O1—C2—H2A | 110.4 | C10—C11—C12 | 117.9 (3) |
C1—C2—H2A | 110.4 | C14—C11—C12 | 103.1 (2) |
O1—C2—H2B | 110.4 | C10—C11—H11 | 106.3 |
C1—C2—H2B | 110.4 | C14—C11—H11 | 106.3 |
H2A—C2—H2B | 108.6 | C12—C11—H11 | 106.3 |
O1—C3—C4 | 107.2 (3) | C13—C12—C11 | 101.7 (2) |
O1—C3—C8 | 111.9 (3) | C13—C12—C7 | 111.2 (2) |
C4—C3—C8 | 110.5 (2) | C11—C12—C7 | 114.7 (2) |
O1—C3—S1 | 105.6 (2) | C13—C12—H12 | 109.7 |
C4—C3—S1 | 111.6 (2) | C11—C12—H12 | 109.7 |
C8—C3—S1 | 109.88 (19) | C7—C12—H12 | 109.7 |
C5—C4—C3 | 112.9 (3) | O2—C13—N1 | 123.8 (3) |
C5—C4—H4A | 109.0 | O2—C13—C12 | 128.3 (3) |
C3—C4—H4A | 109.0 | N1—C13—C12 | 107.9 (2) |
C5—C4—H4B | 109.0 | O3—C14—N1 | 124.0 (3) |
C3—C4—H4B | 109.0 | O3—C14—C11 | 129.9 (3) |
H4A—C4—H4B | 107.8 | N1—C14—C11 | 106.0 (2) |
C4—C5—C6 | 111.4 (3) | C20—C15—C16 | 120.1 (3) |
C4—C5—H5A | 109.3 | C20—C15—N1 | 120.2 (3) |
C6—C5—H5A | 109.3 | C16—C15—N1 | 119.8 (3) |
C4—C5—H5B | 109.3 | C17—C16—C15 | 119.7 (3) |
C6—C5—H5B | 109.3 | C17—C16—H16 | 120.1 |
H5A—C5—H5B | 108.0 | C15—C16—H16 | 120.1 |
C5—C6—C7 | 110.0 (3) | C18—C17—C16 | 120.2 (4) |
C5—C6—H6A | 109.7 | C18—C17—H17 | 119.9 |
C7—C6—H6A | 109.7 | C16—C17—H17 | 119.9 |
C5—C6—H6B | 109.7 | C19—C18—C17 | 119.9 (4) |
C7—C6—H6B | 109.7 | C19—C18—H18 | 120.0 |
H6A—C6—H6B | 108.2 | C17—C18—H18 | 120.0 |
C8—C7—C6 | 109.2 (2) | C18—C19—C20 | 120.8 (3) |
C8—C7—C12 | 112.7 (2) | C18—C19—H19 | 119.6 |
C6—C7—C12 | 114.9 (3) | C20—C19—H19 | 119.6 |
C8—C7—H7 | 106.5 | C19—C20—C15 | 119.3 (3) |
C6—C7—H7 | 106.5 | C19—C20—H20 | 120.4 |
C12—C7—H7 | 106.5 | C15—C20—H20 | 120.4 |
C9—C8—C7 | 125.6 (2) | ||
C3—S1—C1—C2 | 30.4 (3) | C14—C11—C12—C7 | 88.9 (3) |
C3—O1—C2—C1 | 43.2 (4) | C8—C7—C12—C13 | 142.4 (2) |
S1—C1—C2—O1 | −46.2 (4) | C6—C7—C12—C13 | 16.5 (3) |
C2—O1—C3—C4 | −137.4 (3) | C8—C7—C12—C11 | 27.8 (3) |
C2—O1—C3—C8 | 101.2 (3) | C6—C7—C12—C11 | −98.1 (3) |
C2—O1—C3—S1 | −18.3 (3) | C14—N1—C13—O2 | 173.4 (3) |
C1—S1—C3—O1 | −8.4 (3) | C15—N1—C13—O2 | −5.9 (4) |
C1—S1—C3—C4 | 107.7 (3) | C14—N1—C13—C12 | −7.9 (3) |
C1—S1—C3—C8 | −129.3 (3) | C15—N1—C13—C12 | 172.8 (2) |
O1—C3—C4—C5 | −173.2 (3) | C11—C12—C13—O2 | −156.7 (3) |
C8—C3—C4—C5 | −51.0 (4) | C7—C12—C13—O2 | 80.8 (4) |
S1—C3—C4—C5 | 71.6 (3) | C11—C12—C13—N1 | 24.6 (3) |
C3—C4—C5—C6 | 54.6 (5) | C7—C12—C13—N1 | −97.8 (3) |
C4—C5—C6—C7 | −57.3 (4) | C13—N1—C14—O3 | 168.3 (3) |
C5—C6—C7—C8 | 57.4 (4) | C15—N1—C14—O3 | −12.3 (4) |
C5—C6—C7—C12 | −174.8 (3) | C13—N1—C14—C11 | −12.9 (3) |
C6—C7—C8—C9 | 119.3 (3) | C15—N1—C14—C11 | 166.4 (2) |
C12—C7—C8—C9 | −9.7 (4) | C10—C11—C14—O3 | −23.2 (5) |
C6—C7—C8—C3 | −56.6 (3) | C12—C11—C14—O3 | −153.6 (3) |
C12—C7—C8—C3 | 174.5 (2) | C10—C11—C14—N1 | 158.1 (2) |
O1—C3—C8—C9 | −3.6 (4) | C12—C11—C14—N1 | 27.8 (3) |
C4—C3—C8—C9 | −123.0 (3) | C13—N1—C15—C20 | 129.1 (3) |
S1—C3—C8—C9 | 113.4 (3) | C14—N1—C15—C20 | −50.1 (4) |
O1—C3—C8—C7 | 172.5 (2) | C13—N1—C15—C16 | −50.1 (4) |
C4—C3—C8—C7 | 53.1 (3) | C14—N1—C15—C16 | 130.7 (3) |
S1—C3—C8—C7 | −70.5 (3) | C20—C15—C16—C17 | 0.7 (5) |
C7—C8—C9—C10 | 1.7 (5) | N1—C15—C16—C17 | 179.9 (3) |
C3—C8—C9—C10 | 177.3 (3) | C15—C16—C17—C18 | 1.3 (6) |
C8—C9—C10—C11 | −12.1 (5) | C16—C17—C18—C19 | −2.0 (6) |
C9—C10—C11—C14 | −91.3 (3) | C17—C18—C19—C20 | 0.9 (5) |
C9—C10—C11—C12 | 31.5 (4) | C18—C19—C20—C15 | 1.0 (5) |
C10—C11—C12—C13 | −160.3 (3) | C16—C15—C20—C19 | −1.8 (5) |
C14—C11—C12—C13 | −31.1 (3) | N1—C15—C20—C19 | 179.0 (3) |
C10—C11—C12—C7 | −40.3 (4) |
C13H17N3O3S | F(000) = 624 |
Mr = 295.36 | Dx = 1.458 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 13.258 (2) Å | Cell parameters from 12 reflections |
b = 7.3897 (17) Å | θ = 10–15° |
c = 14.2874 (13) Å | µ = 0.25 mm−1 |
β = 105.944 (9)° | T = 170 K |
V = 1345.9 (4) Å3 | Block, colourless |
Z = 4 | 0.42 × 0.35 × 0.31 mm |
Rigaku AFC-6S diffractometer | 1337 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = 0→15 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | k = 0→8 |
Tmin = 0.90, Tmax = 0.93 | l = −17→16 |
2487 measured reflections | 3 standard reflections every 200 reflections |
2380 independent reflections | intensity decay: <0.1% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.264P] where P = (Fo2 + 2Fc2)/3 |
2380 reflections | (Δ/σ)max < 0.01 |
182 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C13H17N3O3S | V = 1345.9 (4) Å3 |
Mr = 295.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.258 (2) Å | µ = 0.25 mm−1 |
b = 7.3897 (17) Å | T = 170 K |
c = 14.2874 (13) Å | 0.42 × 0.35 × 0.31 mm |
β = 105.944 (9)° |
Rigaku AFC-6S diffractometer | 1337 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.047 |
Tmin = 0.90, Tmax = 0.93 | 3 standard reflections every 200 reflections |
2487 measured reflections | intensity decay: <0.1% |
2380 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.24 e Å−3 |
2380 reflections | Δρmin = −0.27 e Å−3 |
182 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.51331 (7) | 0.27399 (13) | 0.57718 (7) | 0.0331 (3) | |
O1 | 0.65908 (18) | 0.0560 (3) | 0.68045 (17) | 0.0357 (6) | |
O2 | 1.00119 (18) | 0.2512 (4) | 0.39467 (19) | 0.0434 (7) | |
O3 | 0.75030 (18) | 0.6868 (3) | 0.37666 (17) | 0.0344 (6) | |
N1 | 0.8668 (2) | 0.2852 (4) | 0.4679 (2) | 0.0273 (6) | |
N2 | 0.7777 (2) | 0.4016 (4) | 0.4459 (2) | 0.0266 (7) | |
N3 | 0.8899 (2) | 0.5003 (4) | 0.3698 (2) | 0.0304 (7) | |
C1 | 0.4744 (3) | 0.0719 (5) | 0.6291 (3) | 0.0409 (9) | |
H1A | 0.4122 | 0.0953 | 0.6530 | 0.049* | |
H1B | 0.4577 | −0.0269 | 0.5805 | 0.049* | |
C2 | 0.5683 (3) | 0.0240 (5) | 0.7120 (3) | 0.0412 (10) | |
H2A | 0.5698 | 0.0996 | 0.7696 | 0.049* | |
H2B | 0.5650 | −0.1047 | 0.7301 | 0.049* | |
C3 | 0.6551 (2) | 0.2299 (5) | 0.6385 (2) | 0.0275 (8) | |
C4 | 0.6972 (3) | 0.3752 (5) | 0.7150 (2) | 0.0344 (9) | |
H4A | 0.6536 | 0.3784 | 0.7612 | 0.041* | |
H4B | 0.7697 | 0.3437 | 0.7521 | 0.041* | |
C5 | 0.6970 (3) | 0.5610 (5) | 0.6699 (3) | 0.0347 (9) | |
H5A | 0.7268 | 0.6504 | 0.7216 | 0.042* | |
H5B | 0.6239 | 0.5973 | 0.6372 | 0.042* | |
C6 | 0.7610 (3) | 0.5610 (5) | 0.5960 (3) | 0.0343 (9) | |
H6A | 0.8357 | 0.5378 | 0.6296 | 0.041* | |
H6B | 0.7558 | 0.6810 | 0.5642 | 0.041* | |
C7 | 0.7199 (2) | 0.4148 (4) | 0.5191 (2) | 0.0245 (8) | |
H7 | 0.6458 | 0.4467 | 0.4844 | 0.029* | |
C8 | 0.7180 (2) | 0.2321 (4) | 0.5654 (2) | 0.0227 (7) | |
C9 | 0.7730 (2) | 0.0919 (4) | 0.5494 (3) | 0.0272 (8) | |
H9 | 0.7663 | −0.0191 | 0.5806 | 0.033* | |
C10 | 0.8447 (3) | 0.0973 (4) | 0.4854 (3) | 0.0280 (8) | |
H10A | 0.9108 | 0.0332 | 0.5171 | 0.034* | |
H10B | 0.8114 | 0.0363 | 0.4228 | 0.034* | |
C11 | 0.9287 (3) | 0.3358 (5) | 0.4090 (2) | 0.0291 (8) | |
C12 | 0.7997 (3) | 0.5467 (5) | 0.3956 (2) | 0.0273 (8) | |
C13 | 0.9333 (3) | 0.6084 (6) | 0.3050 (3) | 0.0440 (10) | |
H13A | 0.9888 | 0.6869 | 0.3437 | 0.066* | |
H13B | 0.8777 | 0.6829 | 0.2632 | 0.066* | |
H13C | 0.9626 | 0.5282 | 0.2645 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0256 (4) | 0.0355 (5) | 0.0385 (5) | 0.0031 (4) | 0.0093 (4) | 0.0053 (4) |
O1 | 0.0337 (13) | 0.0351 (15) | 0.0430 (15) | 0.0110 (11) | 0.0186 (12) | 0.0174 (12) |
O2 | 0.0310 (13) | 0.0533 (18) | 0.0529 (17) | 0.0117 (13) | 0.0233 (12) | 0.0096 (14) |
O3 | 0.0368 (14) | 0.0299 (14) | 0.0380 (15) | 0.0067 (12) | 0.0130 (12) | 0.0087 (11) |
N1 | 0.0261 (14) | 0.0264 (15) | 0.0317 (15) | 0.0055 (13) | 0.0119 (12) | 0.0033 (13) |
N2 | 0.0273 (15) | 0.0248 (16) | 0.0306 (16) | 0.0062 (12) | 0.0131 (13) | 0.0043 (12) |
N3 | 0.0266 (15) | 0.0349 (18) | 0.0310 (16) | 0.0011 (13) | 0.0098 (13) | 0.0092 (14) |
C1 | 0.040 (2) | 0.037 (2) | 0.050 (2) | −0.0026 (18) | 0.0207 (19) | 0.0030 (19) |
C2 | 0.043 (2) | 0.041 (2) | 0.047 (2) | 0.0020 (18) | 0.0246 (19) | 0.0129 (19) |
C3 | 0.0265 (17) | 0.0273 (19) | 0.0288 (18) | 0.0059 (15) | 0.0079 (14) | 0.0053 (15) |
C4 | 0.0337 (19) | 0.047 (2) | 0.0238 (19) | 0.0022 (18) | 0.0103 (16) | −0.0031 (17) |
C5 | 0.038 (2) | 0.033 (2) | 0.037 (2) | −0.0049 (17) | 0.0168 (17) | −0.0175 (18) |
C6 | 0.039 (2) | 0.0253 (19) | 0.040 (2) | −0.0040 (16) | 0.0133 (17) | −0.0049 (17) |
C7 | 0.0216 (17) | 0.0222 (18) | 0.0307 (19) | 0.0050 (14) | 0.0090 (15) | 0.0006 (15) |
C8 | 0.0187 (15) | 0.0267 (18) | 0.0209 (16) | −0.0020 (14) | 0.0021 (12) | −0.0005 (14) |
C9 | 0.0270 (17) | 0.0213 (18) | 0.0352 (19) | 0.0002 (15) | 0.0117 (15) | −0.0001 (15) |
C10 | 0.0306 (18) | 0.0214 (18) | 0.0329 (19) | 0.0059 (15) | 0.0103 (15) | 0.0016 (15) |
C11 | 0.0220 (17) | 0.035 (2) | 0.0308 (19) | −0.0011 (15) | 0.0078 (15) | −0.0005 (16) |
C12 | 0.0300 (19) | 0.0264 (19) | 0.0257 (18) | 0.0006 (16) | 0.0080 (15) | 0.0004 (15) |
C13 | 0.031 (2) | 0.056 (3) | 0.048 (2) | 0.0047 (19) | 0.0155 (18) | 0.019 (2) |
S1—C1 | 1.805 (4) | C3—C4 | 1.524 (5) |
S1—C3 | 1.872 (3) | C4—C5 | 1.516 (5) |
O1—C3 | 1.413 (4) | C4—H4A | 0.9900 |
O1—C2 | 1.417 (4) | C4—H4B | 0.9900 |
O2—C11 | 1.210 (4) | C5—C6 | 1.525 (5) |
O3—C12 | 1.215 (4) | C5—H5A | 0.9900 |
N1—C11 | 1.379 (4) | C5—H5B | 0.9900 |
N1—N2 | 1.425 (4) | C6—C7 | 1.530 (5) |
N1—C10 | 1.455 (4) | C6—H6A | 0.9900 |
N2—C12 | 1.366 (4) | C6—H6B | 0.9900 |
N2—C7 | 1.460 (4) | C7—C8 | 1.506 (4) |
N3—C11 | 1.378 (4) | C7—H7 | 1.0000 |
N3—C12 | 1.388 (4) | C8—C9 | 1.322 (4) |
N3—C13 | 1.454 (4) | C9—C10 | 1.490 (5) |
C1—C2 | 1.506 (5) | C9—H9 | 0.9500 |
C1—H1A | 0.9900 | C10—H10A | 0.9900 |
C1—H1B | 0.9900 | C10—H10B | 0.9900 |
C2—H2A | 0.9900 | C13—H13A | 0.9800 |
C2—H2B | 0.9900 | C13—H13B | 0.9800 |
C3—C8 | 1.506 (4) | C13—H13C | 0.9800 |
C1—S1—C3 | 91.56 (17) | C6—C5—H5B | 109.4 |
C3—O1—C2 | 110.5 (3) | H5A—C5—H5B | 108.0 |
C11—N1—N2 | 107.3 (3) | C5—C6—C7 | 109.9 (3) |
C11—N1—C10 | 123.0 (3) | C5—C6—H6A | 109.7 |
N2—N1—C10 | 114.8 (2) | C7—C6—H6A | 109.7 |
C12—N2—N1 | 107.8 (2) | C5—C6—H6B | 109.7 |
C12—N2—C7 | 123.7 (3) | C7—C6—H6B | 109.7 |
N1—N2—C7 | 116.7 (2) | H6A—C6—H6B | 108.2 |
C11—N3—C12 | 111.3 (3) | N2—C7—C8 | 109.2 (3) |
C11—N3—C13 | 125.0 (3) | N2—C7—C6 | 114.1 (3) |
C12—N3—C13 | 123.6 (3) | C8—C7—C6 | 111.4 (3) |
C2—C1—S1 | 104.5 (3) | N2—C7—H7 | 107.3 |
C2—C1—H1A | 110.9 | C8—C7—H7 | 107.3 |
S1—C1—H1A | 110.9 | C6—C7—H7 | 107.3 |
C2—C1—H1B | 110.9 | C9—C8—C3 | 123.3 (3) |
S1—C1—H1B | 110.9 | C9—C8—C7 | 123.4 (3) |
H1A—C1—H1B | 108.9 | C3—C8—C7 | 113.1 (3) |
O1—C2—C1 | 107.5 (3) | C8—C9—C10 | 124.1 (3) |
O1—C2—H2A | 110.2 | C8—C9—H9 | 118.0 |
C1—C2—H2A | 110.2 | C10—C9—H9 | 118.0 |
O1—C2—H2B | 110.2 | N1—C10—C9 | 108.9 (3) |
C1—C2—H2B | 110.2 | N1—C10—H10A | 109.9 |
H2A—C2—H2B | 108.5 | C9—C10—H10A | 109.9 |
O1—C3—C8 | 109.9 (3) | N1—C10—H10B | 109.9 |
O1—C3—C4 | 111.9 (3) | C9—C10—H10B | 109.9 |
C8—C3—C4 | 109.1 (3) | H10A—C10—H10B | 108.3 |
O1—C3—S1 | 105.8 (2) | O2—C11—N3 | 127.8 (3) |
C8—C3—S1 | 110.5 (2) | O2—C11—N1 | 126.6 (3) |
C4—C3—S1 | 109.6 (2) | N3—C11—N1 | 105.6 (3) |
C5—C4—C3 | 112.1 (3) | O3—C12—N2 | 127.3 (3) |
C5—C4—H4A | 109.2 | O3—C12—N3 | 127.0 (3) |
C3—C4—H4A | 109.2 | N2—C12—N3 | 105.7 (3) |
C5—C4—H4B | 109.2 | N3—C13—H13A | 109.5 |
C3—C4—H4B | 109.2 | N3—C13—H13B | 109.5 |
H4A—C4—H4B | 107.9 | H13A—C13—H13B | 109.5 |
C4—C5—C6 | 111.0 (3) | N3—C13—H13C | 109.5 |
C4—C5—H5A | 109.4 | H13A—C13—H13C | 109.5 |
C6—C5—H5A | 109.4 | H13B—C13—H13C | 109.5 |
C4—C5—H5B | 109.4 | ||
C11—N1—N2—C12 | −15.9 (3) | C4—C3—C8—C7 | −55.5 (3) |
C10—N1—N2—C12 | −156.6 (3) | S1—C3—C8—C7 | 65.1 (3) |
C11—N1—N2—C7 | −160.3 (3) | N2—C7—C8—C9 | 8.3 (4) |
C10—N1—N2—C7 | 59.0 (4) | C6—C7—C8—C9 | −118.6 (3) |
C3—S1—C1—C2 | 17.6 (3) | N2—C7—C8—C3 | −177.0 (3) |
C3—O1—C2—C1 | 49.5 (4) | C6—C7—C8—C3 | 56.1 (3) |
S1—C1—C2—O1 | −39.9 (4) | C3—C8—C9—C10 | −173.1 (3) |
C2—O1—C3—C8 | −153.0 (3) | C7—C8—C9—C10 | 1.1 (5) |
C2—O1—C3—C4 | 85.7 (3) | C11—N1—C10—C9 | −178.1 (3) |
C2—O1—C3—S1 | −33.7 (3) | N2—N1—C10—C9 | −44.3 (4) |
C1—S1—C3—O1 | 7.8 (2) | C8—C9—C10—N1 | 16.2 (5) |
C1—S1—C3—C8 | 126.7 (3) | C12—N3—C11—O2 | 174.0 (4) |
C1—S1—C3—C4 | −113.1 (3) | C13—N3—C11—O2 | −2.7 (6) |
O1—C3—C4—C5 | 177.8 (3) | C12—N3—C11—N1 | −5.3 (4) |
C8—C3—C4—C5 | 55.9 (4) | C13—N3—C11—N1 | 178.0 (3) |
S1—C3—C4—C5 | −65.1 (3) | N2—N1—C11—O2 | −166.7 (3) |
C3—C4—C5—C6 | −57.4 (4) | C10—N1—C11—O2 | −30.0 (5) |
C4—C5—C6—C7 | 55.5 (4) | N2—N1—C11—N3 | 12.7 (3) |
C12—N2—C7—C8 | −175.3 (3) | C10—N1—C11—N3 | 149.4 (3) |
N1—N2—C7—C8 | −37.1 (4) | N1—N2—C12—O3 | −168.2 (3) |
C12—N2—C7—C6 | −50.0 (4) | C7—N2—C12—O3 | −26.9 (5) |
N1—N2—C7—C6 | 88.2 (3) | N1—N2—C12—N3 | 12.2 (3) |
C5—C6—C7—N2 | −178.8 (3) | C7—N2—C12—N3 | 153.5 (3) |
C5—C6—C7—C8 | −54.6 (4) | C11—N3—C12—O3 | 176.0 (3) |
O1—C3—C8—C9 | −3.8 (4) | C13—N3—C12—O3 | −7.3 (5) |
C4—C3—C8—C9 | 119.2 (3) | C11—N3—C12—N2 | −4.5 (4) |
S1—C3—C8—C9 | −120.2 (3) | C13—N3—C12—N2 | 172.3 (3) |
O1—C3—C8—C7 | −178.5 (2) |
C16H20O5S | Z = 2 |
Mr = 324.38 | F(000) = 344 |
Triclinic, P1 | Dx = 1.375 Mg m−3 |
a = 6.812 (3) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 10.494 (7) Å | Cell parameters from 25 reflections |
c = 11.023 (5) Å | θ = 20–25° |
α = 96.014 (7)° | µ = 2.03 mm−1 |
β = 90.97 (1)° | T = 293 K |
γ = 90.21 (2)° | Prismatic, colourless |
V = 783.5 (7) Å3 | 0.38 × 0.25 × 0.09 mm |
Enraf-Nonius CAD4 diffractometer | 2323 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 68°, θmin = 5° |
ω/2θ scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | k = −12→12 |
Tmin = 0.51, Tmax = 0.84 | l = −13→13 |
3104 measured reflections | 3 standard reflections every 200 reflections |
2843 independent reflections | intensity decay: <0.1% |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.170 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.112P)2 + 0.183P] where P = (Fo2 + 2Fc2)/3 |
2843 reflections | (Δ/σ)max < 0.01 |
201 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C16H20O5S | γ = 90.21 (2)° |
Mr = 324.38 | V = 783.5 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.812 (3) Å | Cu Kα radiation |
b = 10.494 (7) Å | µ = 2.03 mm−1 |
c = 11.023 (5) Å | T = 293 K |
α = 96.014 (7)° | 0.38 × 0.25 × 0.09 mm |
β = 90.97 (1)° |
Enraf-Nonius CAD4 diffractometer | 2323 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.012 |
Tmin = 0.51, Tmax = 0.84 | 3 standard reflections every 200 reflections |
3104 measured reflections | intensity decay: <0.1% |
2843 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.170 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.42 e Å−3 |
2843 reflections | Δρmin = −0.30 e Å−3 |
201 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.58348 (12) | 0.36498 (7) | 0.79550 (6) | 0.0543 (3) | |
O1 | 0.5846 (3) | 0.13171 (17) | 0.85698 (15) | 0.0438 (4) | |
O2 | 0.9950 (4) | 0.2531 (2) | 1.4438 (2) | 0.0755 (7) | |
O3 | 1.1218 (3) | 0.42361 (19) | 1.37020 (18) | 0.0507 (5) | |
O4 | 0.5814 (4) | 0.1546 (2) | 1.4135 (2) | 0.0679 (7) | |
O5 | 0.7944 (3) | 0.02521 (17) | 1.31110 (16) | 0.0454 (5) | |
C1 | 0.7488 (6) | 0.2533 (4) | 0.7173 (3) | 0.0723 (10) | |
H1A | 0.6988 | 0.2252 | 0.6360 | 0.087* | |
H1B | 0.8769 | 0.2925 | 0.7105 | 0.087* | |
C2 | 0.7632 (5) | 0.1410 (3) | 0.7933 (3) | 0.0574 (8) | |
H2A | 0.7852 | 0.0625 | 0.7408 | 0.069* | |
H2B | 0.8725 | 0.1539 | 0.8508 | 0.069* | |
C3 | 0.5345 (4) | 0.2558 (2) | 0.9127 (2) | 0.0381 (5) | |
C4 | 0.3158 (4) | 0.2557 (3) | 0.9388 (2) | 0.0461 (6) | |
H4A | 0.2443 | 0.2237 | 0.8649 | 0.055* | |
H4B | 0.2740 | 0.3431 | 0.9616 | 0.055* | |
C5 | 0.2638 (4) | 0.1740 (3) | 1.0403 (2) | 0.0439 (6) | |
H5A | 0.1255 | 0.1838 | 1.0583 | 0.053* | |
H5B | 0.2870 | 0.0845 | 1.0129 | 0.053* | |
C6 | 0.3844 (4) | 0.2121 (2) | 1.1549 (2) | 0.0392 (5) | |
H6A | 0.3514 | 0.1570 | 1.2170 | 0.047* | |
H6B | 0.3549 | 0.2997 | 1.1859 | 0.047* | |
C7 | 0.6036 (3) | 0.2002 (2) | 1.1267 (2) | 0.0322 (5) | |
H7 | 0.6262 | 0.1118 | 1.0916 | 0.039* | |
C8 | 0.6537 (3) | 0.2871 (2) | 1.0300 (2) | 0.0330 (5) | |
C9 | 0.7826 (4) | 0.3808 (2) | 1.0498 (2) | 0.0371 (5) | |
H9 | 0.8044 | 0.4311 | 0.9867 | 0.045* | |
C10 | 0.8971 (4) | 0.4126 (2) | 1.1659 (2) | 0.0396 (6) | |
H10A | 0.8584 | 0.4967 | 1.2024 | 0.047* | |
H10B | 1.0355 | 0.4166 | 1.1474 | 0.047* | |
C11 | 0.8676 (3) | 0.3169 (2) | 1.2569 (2) | 0.0353 (5) | |
C12 | 0.7337 (3) | 0.2242 (2) | 1.2391 (2) | 0.0336 (5) | |
C13 | 0.9976 (4) | 0.3249 (3) | 1.3666 (2) | 0.0430 (6) | |
C14 | 1.2666 (5) | 0.4324 (4) | 1.4673 (3) | 0.0673 (9) | |
H14A | 1.2029 | 0.4274 | 1.5437 | 0.101* | |
H14B | 1.3356 | 0.5126 | 1.4695 | 0.101* | |
H14C | 1.3579 | 0.3631 | 1.4535 | 0.101* | |
C15 | 0.6962 (4) | 0.1334 (2) | 1.3337 (2) | 0.0385 (6) | |
C16 | 0.7653 (6) | −0.0685 (3) | 1.3968 (3) | 0.0635 (9) | |
H16A | 0.7895 | −0.0292 | 1.4783 | 0.095* | |
H16B | 0.8543 | −0.1384 | 1.3793 | 0.095* | |
H16C | 0.6326 | −0.1000 | 1.3895 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0683 (5) | 0.0610 (5) | 0.0367 (4) | −0.0008 (3) | −0.0040 (3) | 0.0205 (3) |
O1 | 0.0503 (10) | 0.0443 (10) | 0.0361 (9) | −0.0014 (8) | 0.0063 (8) | −0.0005 (7) |
O2 | 0.1008 (19) | 0.0750 (15) | 0.0545 (13) | −0.0214 (13) | −0.0312 (13) | 0.0311 (12) |
O3 | 0.0441 (10) | 0.0581 (12) | 0.0499 (11) | −0.0072 (9) | −0.0091 (8) | 0.0071 (9) |
O4 | 0.0743 (14) | 0.0831 (16) | 0.0530 (12) | 0.0224 (12) | 0.0307 (11) | 0.0336 (11) |
O5 | 0.0574 (11) | 0.0410 (10) | 0.0407 (10) | 0.0040 (8) | 0.0054 (8) | 0.0175 (8) |
C1 | 0.087 (2) | 0.083 (2) | 0.0489 (17) | −0.0094 (19) | 0.0238 (17) | 0.0109 (16) |
C2 | 0.0552 (17) | 0.0675 (19) | 0.0491 (16) | 0.0039 (14) | 0.0159 (13) | 0.0014 (14) |
C3 | 0.0453 (13) | 0.0379 (12) | 0.0315 (12) | 0.0011 (10) | 0.0002 (10) | 0.0060 (10) |
C4 | 0.0402 (13) | 0.0535 (15) | 0.0451 (14) | 0.0080 (11) | −0.0025 (11) | 0.0069 (12) |
C5 | 0.0364 (13) | 0.0443 (14) | 0.0507 (15) | 0.0005 (11) | 0.0038 (11) | 0.0027 (11) |
C6 | 0.0387 (12) | 0.0421 (13) | 0.0373 (13) | −0.0004 (10) | 0.0057 (10) | 0.0067 (10) |
C7 | 0.0370 (11) | 0.0287 (11) | 0.0316 (11) | 0.0022 (9) | 0.0055 (9) | 0.0060 (9) |
C8 | 0.0378 (12) | 0.0365 (12) | 0.0255 (11) | 0.0047 (9) | 0.0043 (9) | 0.0072 (9) |
C9 | 0.0451 (13) | 0.0339 (12) | 0.0345 (12) | −0.0007 (10) | 0.0036 (10) | 0.0129 (9) |
C10 | 0.0447 (13) | 0.0377 (13) | 0.0378 (13) | −0.0025 (10) | −0.0001 (10) | 0.0114 (10) |
C11 | 0.0410 (12) | 0.0363 (12) | 0.0298 (11) | 0.0021 (10) | 0.0019 (9) | 0.0084 (9) |
C12 | 0.0375 (12) | 0.0344 (12) | 0.0305 (11) | 0.0055 (9) | 0.0061 (9) | 0.0102 (9) |
C13 | 0.0469 (14) | 0.0452 (14) | 0.0372 (13) | 0.0044 (11) | 0.0008 (11) | 0.0058 (11) |
C14 | 0.0517 (17) | 0.080 (2) | 0.066 (2) | 0.0020 (16) | −0.0219 (15) | −0.0051 (17) |
C15 | 0.0403 (12) | 0.0452 (14) | 0.0322 (12) | 0.0008 (10) | 0.0035 (10) | 0.0146 (10) |
C16 | 0.090 (2) | 0.0492 (17) | 0.0558 (18) | 0.0012 (16) | 0.0003 (16) | 0.0298 (14) |
S1—C1 | 1.793 (4) | C5—H5B | 0.9700 |
S1—C3 | 1.848 (3) | C6—C7 | 1.533 (3) |
O1—C2 | 1.423 (3) | C6—H6A | 0.9700 |
O1—C3 | 1.425 (3) | C6—H6B | 0.9700 |
O2—C13 | 1.195 (3) | C7—C12 | 1.510 (3) |
O3—C13 | 1.332 (3) | C7—C8 | 1.516 (3) |
O3—C14 | 1.439 (3) | C7—H7 | 0.9800 |
O4—C15 | 1.191 (3) | C8—C9 | 1.314 (4) |
O5—C15 | 1.323 (3) | C9—C10 | 1.494 (3) |
O5—C16 | 1.448 (3) | C9—H9 | 0.9300 |
C1—C2 | 1.518 (5) | C10—C11 | 1.507 (3) |
C1—H1A | 0.9700 | C10—H10A | 0.9700 |
C1—H1B | 0.9700 | C10—H10B | 0.9700 |
C2—H2A | 0.9700 | C11—C12 | 1.329 (4) |
C2—H2B | 0.9700 | C11—C13 | 1.482 (3) |
C3—C8 | 1.521 (3) | C12—C15 | 1.509 (3) |
C3—C4 | 1.522 (4) | C14—H14A | 0.9600 |
C4—C5 | 1.524 (4) | C14—H14B | 0.9600 |
C4—H4A | 0.9700 | C14—H14C | 0.9600 |
C4—H4B | 0.9700 | C16—H16A | 0.9600 |
C5—C6 | 1.512 (4) | C16—H16B | 0.9600 |
C5—H5A | 0.9700 | C16—H16C | 0.9600 |
C1—S1—C3 | 92.04 (14) | C12—C7—C6 | 112.97 (19) |
C2—O1—C3 | 108.8 (2) | C8—C7—C6 | 109.26 (18) |
C13—O3—C14 | 115.9 (2) | C12—C7—H7 | 107.3 |
C15—O5—C16 | 115.5 (2) | C8—C7—H7 | 107.3 |
C2—C1—S1 | 106.1 (2) | C6—C7—H7 | 107.3 |
C2—C1—H1A | 110.5 | C9—C8—C7 | 122.2 (2) |
S1—C1—H1A | 110.5 | C9—C8—C3 | 125.2 (2) |
C2—C1—H1B | 110.5 | C7—C8—C3 | 112.5 (2) |
S1—C1—H1B | 110.5 | C8—C9—C10 | 125.1 (2) |
H1A—C1—H1B | 108.7 | C8—C9—H9 | 117.5 |
O1—C2—C1 | 108.7 (3) | C10—C9—H9 | 117.5 |
O1—C2—H2A | 110.0 | C9—C10—C11 | 113.1 (2) |
C1—C2—H2A | 110.0 | C9—C10—H10A | 109.0 |
O1—C2—H2B | 110.0 | C11—C10—H10A | 109.0 |
C1—C2—H2B | 110.0 | C9—C10—H10B | 109.0 |
H2A—C2—H2B | 108.3 | C11—C10—H10B | 109.0 |
O1—C3—C8 | 110.03 (19) | H10A—C10—H10B | 107.8 |
O1—C3—C4 | 108.0 (2) | C12—C11—C13 | 119.8 (2) |
C8—C3—C4 | 110.6 (2) | C12—C11—C10 | 121.8 (2) |
O1—C3—S1 | 104.88 (16) | C13—C11—C10 | 118.4 (2) |
C8—C3—S1 | 113.62 (17) | C11—C12—C15 | 121.7 (2) |
C4—C3—S1 | 109.38 (17) | C11—C12—C7 | 124.6 (2) |
C3—C4—C5 | 112.9 (2) | C15—C12—C7 | 113.7 (2) |
C3—C4—H4A | 109.0 | O2—C13—O3 | 122.8 (3) |
C5—C4—H4A | 109.0 | O2—C13—C11 | 125.5 (3) |
C3—C4—H4B | 109.0 | O3—C13—C11 | 111.8 (2) |
C5—C4—H4B | 109.0 | O3—C14—H14A | 109.5 |
H4A—C4—H4B | 107.8 | O3—C14—H14B | 109.5 |
C6—C5—C4 | 111.4 (2) | H14A—C14—H14B | 109.5 |
C6—C5—H5A | 109.3 | O3—C14—H14C | 109.5 |
C4—C5—H5A | 109.3 | H14A—C14—H14C | 109.5 |
C6—C5—H5B | 109.3 | H14B—C14—H14C | 109.5 |
C4—C5—H5B | 109.3 | O4—C15—O5 | 124.9 (2) |
H5A—C5—H5B | 108.0 | O4—C15—C12 | 123.2 (2) |
C5—C6—C7 | 109.8 (2) | O5—C15—C12 | 111.7 (2) |
C5—C6—H6A | 109.7 | O5—C16—H16A | 109.5 |
C7—C6—H6A | 109.7 | O5—C16—H16B | 109.5 |
C5—C6—H6B | 109.7 | H16A—C16—H16B | 109.5 |
C7—C6—H6B | 109.7 | O5—C16—H16C | 109.5 |
H6A—C6—H6B | 108.2 | H16A—C16—H16C | 109.5 |
C12—C7—C8 | 112.41 (19) | H16B—C16—H16C | 109.5 |
C3—S1—C1—C2 | −3.3 (3) | C7—C8—C9—C10 | 1.0 (4) |
C3—O1—C2—C1 | −47.4 (3) | C3—C8—C9—C10 | 178.9 (2) |
S1—C1—C2—O1 | 28.2 (3) | C8—C9—C10—C11 | 6.3 (4) |
C2—O1—C3—C8 | −79.8 (2) | C9—C10—C11—C12 | −8.0 (3) |
C2—O1—C3—C4 | 159.4 (2) | C9—C10—C11—C13 | 169.8 (2) |
C2—O1—C3—S1 | 42.8 (2) | C13—C11—C12—C15 | 6.0 (3) |
C1—S1—C3—O1 | −21.7 (2) | C10—C11—C12—C15 | −176.2 (2) |
C1—S1—C3—C8 | 98.5 (2) | C13—C11—C12—C7 | −175.2 (2) |
C1—S1—C3—C4 | −137.3 (2) | C10—C11—C12—C7 | 2.5 (4) |
O1—C3—C4—C5 | 69.8 (3) | C8—C7—C12—C11 | 4.8 (3) |
C8—C3—C4—C5 | −50.6 (3) | C6—C7—C12—C11 | −119.4 (3) |
S1—C3—C4—C5 | −176.55 (18) | C8—C7—C12—C15 | −176.29 (18) |
C3—C4—C5—C6 | 53.7 (3) | C6—C7—C12—C15 | 59.5 (3) |
C4—C5—C6—C7 | −57.6 (3) | C14—O3—C13—O2 | 5.6 (4) |
C5—C6—C7—C12 | −174.42 (19) | C14—O3—C13—C11 | −174.3 (2) |
C5—C6—C7—C8 | 59.7 (3) | C12—C11—C13—O2 | 0.4 (4) |
C12—C7—C8—C9 | −6.6 (3) | C10—C11—C13—O2 | −177.5 (3) |
C6—C7—C8—C9 | 119.6 (3) | C12—C11—C13—O3 | −179.7 (2) |
C12—C7—C8—C3 | 175.22 (18) | C10—C11—C13—O3 | 2.5 (3) |
C6—C7—C8—C3 | −58.5 (2) | C16—O5—C15—O4 | −4.2 (4) |
O1—C3—C8—C9 | 116.4 (3) | C16—O5—C15—C12 | −179.3 (2) |
C4—C3—C8—C9 | −124.3 (3) | C11—C12—C15—O4 | 88.6 (3) |
S1—C3—C8—C9 | −0.9 (3) | C7—C12—C15—O4 | −90.3 (3) |
O1—C3—C8—C7 | −65.5 (2) | C11—C12—C15—O5 | −96.2 (3) |
C4—C3—C8—C7 | 53.8 (3) | C7—C12—C15—O5 | 84.9 (3) |
S1—C3—C8—C7 | 177.25 (15) |
Experimental details
(IIa) | (IIIa) | (IVb) | |
Crystal data | |||
Chemical formula | C20H21NO3S | C13H17N3O3S | C16H20O5S |
Mr | 355.44 | 295.36 | 324.38 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 293 | 170 | 293 |
a, b, c (Å) | 12.047 (2), 7.808 (2), 9.718 (1) | 13.258 (2), 7.3897 (17), 14.2874 (13) | 6.812 (3), 10.494 (7), 11.023 (5) |
α, β, γ (°) | 90, 108.71 (1), 90 | 90, 105.944 (9), 90 | 96.014 (7), 90.97 (1), 90.21 (2) |
V (Å3) | 865.8 (3) | 1345.9 (4) | 783.5 (7) |
Z | 2 | 4 | 2 |
Radiation type | Cu Kα | Mo Kα | Cu Kα |
µ (mm−1) | 1.82 | 0.25 | 2.03 |
Crystal size (mm) | 0.6 × 0.4 × 0.2 | 0.42 × 0.35 × 0.31 | 0.38 × 0.25 × 0.09 |
Data collection | |||
Diffractometer | Enraf-Nonius CAD4 diffractometer | Rigaku AFC-6S diffractometer | Enraf-Nonius CAD4 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) | Empirical (using intensity measurements) via ψ-scan (3 reflections) (North et al., 1968) |
Tmin, Tmax | 0.41, 0.71 | 0.90, 0.93 | 0.51, 0.84 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1788, 1705, 1653 | 2487, 2380, 1337 | 3104, 2843, 2323 |
Rint | 0.014 | 0.047 | 0.012 |
(sin θ/λ)max (Å−1) | 0.601 | 0.595 | 0.601 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.125, 1.15 | 0.042, 0.130, 1.00 | 0.054, 0.170, 1.06 |
No. of reflections | 1705 | 2380 | 2843 |
No. of parameters | 226 | 182 | 201 |
No. of restraints | 1 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.29 | 0.24, −0.27 | 0.42, −0.30 |
Absolute structure | Flack (1983) | ? | ? |
Absolute structure parameter | 0.04 (3) | ? | ? |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), CAD-4 Software, MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN, SHELXL97.
S1—C1 | 1.802 (6) | O3—C14 | 1.203 (4) |
S1—C3 | 1.860 (3) | N1—C13 | 1.392 (4) |
O1—C2 | 1.403 (5) | N1—C14 | 1.409 (4) |
O1—C3 | 1.427 (4) | N1—C15 | 1.427 (4) |
O2—C13 | 1.218 (4) | ||
C1—S1—C3 | 90.60 (18) | C13—N1—C15 | 125.2 (3) |
C2—O1—C3 | 113.5 (3) | C14—N1—C15 | 123.7 (2) |
C13—N1—C14 | 111.2 (3) |
S1—C1 | 1.805 (4) | N1—N2 | 1.425 (4) |
S1—C3 | 1.872 (3) | N1—C10 | 1.455 (4) |
O1—C3 | 1.413 (4) | N2—C12 | 1.366 (4) |
O1—C2 | 1.417 (4) | N2—C7 | 1.460 (4) |
O2—C11 | 1.210 (4) | N3—C11 | 1.378 (4) |
O3—C12 | 1.215 (4) | N3—C12 | 1.388 (4) |
N1—C11 | 1.379 (4) | N3—C13 | 1.454 (4) |
C1—S1—C3 | 91.56 (17) | C12—N2—C7 | 123.7 (3) |
C3—O1—C2 | 110.5 (3) | N1—N2—C7 | 116.7 (2) |
C11—N1—N2 | 107.3 (3) | C11—N3—C12 | 111.3 (3) |
C11—N1—C10 | 123.0 (3) | C11—N3—C13 | 125.0 (3) |
N2—N1—C10 | 114.8 (2) | C12—N3—C13 | 123.6 (3) |
C12—N2—N1 | 107.8 (2) |
S1—C1 | 1.793 (4) | O3—C13 | 1.332 (3) |
S1—C3 | 1.848 (3) | O3—C14 | 1.439 (3) |
O1—C2 | 1.423 (3) | O4—C15 | 1.191 (3) |
O1—C3 | 1.425 (3) | O5—C15 | 1.323 (3) |
O2—C13 | 1.195 (3) | O5—C16 | 1.448 (3) |
C1—S1—C3 | 92.04 (14) | C13—O3—C14 | 115.9 (2) |
C2—O1—C3 | 108.8 (2) | C15—O5—C16 | 115.5 (2) |
We have reacted 6-vinyl-1-oxa-4-thiaspiro[4.5]dec-6-ene, (I), with dienophiles such as N-phenylmaleimide (NPM), N-methyltriazoline-2,5-dione (MTAD) and dimethylacetylene dicarboxylate (DMAD), to study 1,3-diastereofacial selection caused by the acetyl function. In each case, a mixture of two adducts was obtained (see Scheme); the additions have been examined under a variety of conditions, including the use of selected Lewis acids, to achieve different product distributions and the results of this study will be reported elsewhere (Yadav et al., 2000). \sch
The products (IIa)-(IVa) were formed from addition syn to the acetyl sulfur. The compounds (IIa) and (IIb) were separated by radial chromatography and (IIa) was recrystallized from toluene to furnish a single diastereoisomer (m.p. 397 K). The products (IIIa) and (IIIb) were inseparable by routine chromatographic means; the major product (IIIa), however, recrystallized from methanol-dichloromethane as a diastereoisomeric mixture (m.p. 431 K). The products (IVa) and (IVb) were separated and the less polar, (IVb), recrystallized from ethyl acetate-petroleum ether (m.p. 357 K). The ratios of the adducts formed were determined from the relative integrals of the vinylic H atoms. The diastereodetermination was achieved from single-crystal X-ray crystallography of one of the two adducts formed. In this paper, we describe the crystal structures of (IIa), (IIIa) and (IVb)
The structure of (IIa) (Fig. 1) is composed of independent molecules which are separated by normal van der Waals distances. The heterocyclic ring S1/C1/C2/O1/C3 adopts a C2-envelope conformation, with C2 0.598 (6) 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 0.061 (2) Å. The heterocyclic ring N1/C13/C12/C11/C14 also adopts an envelope conformation, with C11 0.483 (4) Å out the plane of the rest of the ring atoms. The six-membered ring C3—C8 adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.561 (4) Å, and θ = 5.3 (4) and ϕ = 195 (4)°. The six-membered ring C7—C12 adopts a sofa conformation, with C11 0.402 (4) Å from the remaining atoms of the ring [maximum deviation 0.071 (2) Å] and the phenyl ring C15—C20 is essentially planar [maximum deviation 0.011 (3) Å].
The structure of (IIIa) (Fig. 2) is similarly composed of independent molecules which are separated by normal van der Waals distances. The heterocyclic ring S1/C1/C2/O1/C3 also adopts a C2-envelope conformation, with C2 0.566 (5) 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 0.061 (2) Å. The heterocyclic ring N1/N2/C12/N3/C11 is planar to within 0.082 (2) Å. The six-membered ring C3—C8 adopts a chair conformation, with puckering parameters Q = 0.569 (4) Å, and θ = 179.5 (4) and ϕ = 271 (17)°. The six-membered ring N1/N2/C7/C8/C9/C10 adopts a sofa conformation, with N1 0.540 (4) Å from the remaining atoms of the ring [maximum deviation 0.071 (2) Å].
Unlike the heterocyclic rings S1/C1/C2/O1/C3 in (IIa) and (IIIa), the corresponding ring in the structure of (IVb) (Fig. 3) adopts an O1-envelope conformation, with O1 0.564 (3) 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 0.024 (2) Å. The six-membered ring C3—C8 adopts a chair conformation, with puckering parameters Q = 0.571 (3) Å, and θ = 6.4 (3) and ϕ = 212 (2)°. The six-membered ring C7—C12 is essentially planar [maximum deviation 0.055 (2) Å], with the carboxylate groups O2/C13/O3/C14 and O4/C15/O5/C16 inclined to this ring at angles of 10.7 (2) and 84.53 (11)°, respectively. The structure is composed of independent molecules which are separated by normal van der Waals distances.
The S-Csp3 bond distances, although significantly different in all three structures [1.860 (3) and 1.802 (6) in (IIa), 1.872 (3) and 1.805 (4) in (IIIa), and 1.848 (3) and 1.793 (4) Å in (IVb)], are in excellent agreement with the corresponding bond distances 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 oxa-thia-spiro-decene (Parvez et al., 1997) and 2-(7-ethylidene-6-methyl-1-oxa-4-thiaspiro[4.5]dec-7-yl)ethanol (Parvez et al., 1998). The remaining bond distances and angles in the three structures are normal and agree well with the corresponding values reported for similar compounds contained in the Cambridge Structural Database (Allen & Kennard, 1993).