Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109045284/ga3134sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109045284/ga3134VIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109045284/ga3134VIIsup3.hkl |
CCDC references: 763612; 763613
For related literature, see: Lough et al. (2004); Shibata et al. (2006); Spek (2009); Villeneuve & Tam (2004).
Preparation of compound (VI) was achieved by addition of norbornene (72.0 mg, 765 mmol), (I), and chiral alkyne (III) (52.2 mg, 0.149 mmol) to Cp*Ru(cod)Cl (please define; 7.6 mg, 0.020 mmol) in THF (0.6 ml). The mixture was stirred for 18 h at 298 K, and subsequent column chromatography of the crude reaction mixture provided a 98% yield of the two diastereomeric cycloadducts in a 20:1 ratio. Evaporative recrystallization of the column-purified product in THF provided the major diastereomer (VI), giving colourless crystals suitable for X-ray analysis.
Similarly, compound (VII) was prepared by addition of norbornene (83.0 mg, 0.881 mmol), (I), and chiral alkyne (IV) (63.2 mg, 0.177 mmol) to Cp*Ru(cod)Cl (7.1 mg, 0.018 mmol) in THF (0.5 ml). The mixture was stirred for 17 h at 298 K, and subsequent column chromatography of the crude reaction mixture provided a 79% yield of the two diastereomeric cycloadducts in a 104:1 ratio. Evaporative recrystallization of the column-purified product in THF provided major diastereomer (VII), giving colourless crystals suitable for X-ray analysis.
Both diastereomeric ratios were back-calculated from the corresponding enantiomeric excesses obtained through cleavage of the chiral auxiliary under reductive conditions (LiAlH4, AlCl3), giving an enantiomeric mixture of cycloadduct alcohols that can be resolved using a Chiralcel OJ-H high-performance liquid chromatography column.
Standard SADI restraints were used for the dimensions of the disordered solvent (THF), which was refined at half-occupancy. H atoms were positioned geometrically and refined using a riding model with C—H distances of 0.98 Å (CH3), 0.99 Å (CH2), 1.00 Å (CH) or 0.95 Å (aromatic CH). Uiso(H) were set at 1.2 times Ueq(C) for all except the methyl H atoms, where Uiso(H) = 1.5Ueq(C).
For both compounds, data collection: COLLECT (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).
C24H29NO3S2·0.5C4H8O | Dx = 1.335 Mg m−3 |
Mr = 479.65 | Melting point: 199 K |
Trigonal, P3221 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 32 2" | Cell parameters from 19735 reflections |
a = 12.0797 (17) Å | θ = 2.0–27.5° |
c = 28.326 (6) Å | µ = 0.25 mm−1 |
V = 3579.5 (10) Å3 | T = 150 K |
Z = 6 | Plate, colourless |
F(000) = 1536 | 0.35 × 0.22 × 0.15 mm |
Nonius KappaCCD diffractometer | 4207 independent reflections |
Radiation source: fine-focus sealed tube | 3310 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ϕ scans, and ω scans with κ offsets | θmax = 25.0°, θmin = 2.9° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −14→14 |
Tmin = 0.916, Tmax = 0.963 | k = −11→11 |
8354 measured reflections | l = −33→33 |
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ^2^(Fo^2^) + (0.0432P)^2^] where P = (Fo^2^ + 2Fc^2^)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4207 reflections | Δρmax = 0.19 e Å−3 |
318 parameters | Δρmin = −0.31 e Å−3 |
4 restraints | Absolute structure: Flack (1983), 1788 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (7) |
C24H29NO3S2·0.5C4H8O | Z = 6 |
Mr = 479.65 | Mo Kα radiation |
Trigonal, P3221 | µ = 0.25 mm−1 |
a = 12.0797 (17) Å | T = 150 K |
c = 28.326 (6) Å | 0.35 × 0.22 × 0.15 mm |
V = 3579.5 (10) Å3 |
Nonius KappaCCD diffractometer | 4207 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 3310 reflections with I > 2σ(I) |
Tmin = 0.916, Tmax = 0.963 | Rint = 0.041 |
8354 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.084 | Δρmax = 0.19 e Å−3 |
S = 1.01 | Δρmin = −0.31 e Å−3 |
4207 reflections | Absolute structure: Flack (1983), 1788 Friedel pairs |
318 parameters | Absolute structure parameter: −0.03 (7) |
4 restraints |
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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.60309 (17) | 0.69194 (15) | 0.12342 (5) | 0.0322 (5) | |
S1 | 0.62469 (6) | 0.60943 (6) | 0.15376 (2) | 0.02461 (16) | |
N1 | 0.52685 (17) | 0.57178 (19) | 0.20119 (6) | 0.0208 (5) | |
C1 | 0.5534 (2) | 0.4517 (2) | 0.13028 (8) | 0.0260 (6) | |
H1A | 0.5087 | 0.4462 | 0.1003 | 0.031* | |
H1B | 0.6198 | 0.4283 | 0.1239 | 0.031* | |
O2 | 0.75321 (16) | 0.65168 (16) | 0.16832 (6) | 0.0321 (4) | |
S2 | 0.33154 (8) | 0.91996 (7) | 0.31771 (2) | 0.0390 (2) | |
C2 | 0.4595 (2) | 0.3623 (2) | 0.16665 (8) | 0.0221 (6) | |
O3 | 0.39805 (16) | 0.62130 (17) | 0.24296 (6) | 0.0281 (4) | |
C3 | 0.3339 (3) | 0.2492 (3) | 0.14789 (9) | 0.0357 (7) | |
H3A | 0.3505 | 0.1991 | 0.1241 | 0.043* | |
H3B | 0.2779 | 0.2786 | 0.1339 | 0.043* | |
C4 | 0.2753 (3) | 0.1710 (3) | 0.19347 (10) | 0.0436 (8) | |
H4A | 0.1946 | 0.1690 | 0.2017 | 0.052* | |
H4B | 0.2578 | 0.0822 | 0.1897 | 0.052* | |
C5 | 0.3773 (3) | 0.2418 (2) | 0.23128 (9) | 0.0345 (7) | |
H5A | 0.3715 | 0.1878 | 0.2590 | 0.041* | |
C6 | 0.5030 (3) | 0.2946 (2) | 0.20299 (9) | 0.0282 (6) | |
C7 | 0.3740 (3) | 0.3634 (2) | 0.24425 (9) | 0.0334 (7) | |
H7A | 0.4341 | 0.4104 | 0.2703 | 0.040* | |
H7B | 0.2869 | 0.3436 | 0.2534 | 0.040* | |
C8 | 0.4166 (2) | 0.4394 (2) | 0.19764 (8) | 0.0236 (6) | |
H8A | 0.3424 | 0.4407 | 0.1826 | 0.028* | |
C9 | 0.6237 (3) | 0.3820 (3) | 0.23148 (9) | 0.0376 (8) | |
H9A | 0.6310 | 0.3341 | 0.2581 | 0.056* | |
H9B | 0.6182 | 0.4552 | 0.2435 | 0.056* | |
H9C | 0.6990 | 0.4125 | 0.2111 | 0.056* | |
C10 | 0.5244 (3) | 0.1911 (3) | 0.18097 (9) | 0.0387 (8) | |
H10A | 0.5978 | 0.2308 | 0.1595 | 0.058* | |
H10B | 0.4480 | 0.1308 | 0.1633 | 0.058* | |
H10C | 0.5412 | 0.1453 | 0.2060 | 0.058* | |
C11 | 0.5041 (2) | 0.6601 (2) | 0.22510 (8) | 0.0215 (6) | |
C12 | 0.6077 (2) | 0.7928 (2) | 0.23004 (8) | 0.0234 (6) | |
C13 | 0.6085 (2) | 0.8955 (2) | 0.25049 (8) | 0.0231 (6) | |
C14 | 0.7498 (2) | 0.9844 (2) | 0.24120 (8) | 0.0237 (6) | |
H14A | 0.7692 | 1.0548 | 0.2183 | 0.028* | |
C15 | 0.8422 (2) | 1.0227 (2) | 0.28271 (8) | 0.0234 (6) | |
H15A | 0.8345 | 1.0793 | 0.3066 | 0.028* | |
C16 | 0.9761 (2) | 1.0750 (2) | 0.26124 (9) | 0.0267 (6) | |
H16A | 1.0433 | 1.1187 | 0.2854 | 0.032* | |
H16B | 0.9906 | 1.1355 | 0.2352 | 0.032* | |
C17 | 0.9743 (2) | 0.9525 (3) | 0.24244 (9) | 0.0287 (7) | |
H17A | 0.9913 | 0.9586 | 0.2081 | 0.034* | |
H17B | 1.0384 | 0.9383 | 0.2590 | 0.034* | |
C18 | 0.8373 (2) | 0.8452 (2) | 0.25365 (8) | 0.0240 (6) | |
H18A | 0.8250 | 0.7570 | 0.2537 | 0.029* | |
C19 | 0.7505 (2) | 0.8655 (2) | 0.21943 (8) | 0.0221 (6) | |
H19A | 0.7743 | 0.8727 | 0.1853 | 0.027* | |
C20 | 0.8139 (3) | 0.8906 (2) | 0.30137 (8) | 0.0259 (6) | |
H20A | 0.8749 | 0.8971 | 0.3261 | 0.031* | |
H20B | 0.7249 | 0.8374 | 0.3127 | 0.031* | |
C21 | 0.5224 (2) | 0.9252 (2) | 0.27616 (8) | 0.0238 (6) | |
C22 | 0.3957 (3) | 0.8448 (3) | 0.28677 (8) | 0.0304 (7) | |
H22A | 0.3493 | 0.7573 | 0.2779 | 0.036* | |
C23 | 0.4727 (3) | 1.0620 (3) | 0.31785 (8) | 0.0291 (6) | |
H23A | 0.4850 | 1.1383 | 0.3323 | 0.035* | |
C24 | 0.5655 (3) | 1.0508 (3) | 0.29432 (9) | 0.0309 (7) | |
H24A | 0.6503 | 1.1197 | 0.2904 | 0.037* | |
O31 | 0.4857 (5) | 0.3920 (5) | 0.01939 (16) | 0.0602 (14) | 0.50 |
C32 | 0.3989 (9) | 0.4359 (10) | 0.0075 (6) | 0.096 (6) | 0.50 |
H32A | 0.3277 | 0.4022 | 0.0305 | 0.115* | 0.50 |
H32B | 0.3625 | 0.4046 | −0.0243 | 0.115* | 0.50 |
C33 | 0.4687 (16) | 0.5782 (14) | 0.0082 (8) | 0.084 (7) | 0.50 |
H33A | 0.4517 | 0.6108 | 0.0378 | 0.101* | 0.50 |
H33B | 0.4443 | 0.6127 | −0.0190 | 0.101* | 0.50 |
C34 | 0.6067 (13) | 0.6130 (13) | 0.0051 (13) | 0.051 (4) | 0.50 |
H34A | 0.6497 | 0.6712 | −0.0218 | 0.061* | 0.50 |
H34B | 0.6530 | 0.6546 | 0.0346 | 0.061* | 0.50 |
C35 | 0.6007 (13) | 0.4869 (16) | −0.0020 (6) | 0.054 (4) | 0.50 |
H35A | 0.6006 | 0.4691 | −0.0362 | 0.065* | 0.50 |
H35B | 0.6755 | 0.4880 | 0.0128 | 0.065* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0450 (12) | 0.0249 (11) | 0.0283 (9) | 0.0187 (10) | 0.0033 (8) | 0.0076 (8) |
S1 | 0.0238 (4) | 0.0212 (4) | 0.0264 (3) | 0.0094 (3) | 0.0036 (3) | −0.0015 (3) |
N1 | 0.0170 (11) | 0.0187 (12) | 0.0228 (10) | 0.0060 (10) | 0.0044 (8) | −0.0026 (9) |
C1 | 0.0289 (16) | 0.0247 (14) | 0.0252 (14) | 0.0141 (13) | −0.0006 (12) | −0.0050 (11) |
O2 | 0.0179 (10) | 0.0315 (11) | 0.0447 (10) | 0.0107 (8) | 0.0006 (8) | −0.0082 (9) |
S2 | 0.0400 (5) | 0.0405 (5) | 0.0433 (4) | 0.0252 (4) | 0.0084 (4) | −0.0032 (4) |
C2 | 0.0196 (14) | 0.0179 (13) | 0.0256 (13) | 0.0070 (12) | 0.0041 (11) | −0.0012 (11) |
O3 | 0.0198 (10) | 0.0269 (11) | 0.0351 (11) | 0.0099 (9) | 0.0052 (9) | −0.0035 (9) |
C3 | 0.0295 (17) | 0.0261 (17) | 0.0422 (17) | 0.0069 (14) | 0.0008 (14) | −0.0128 (14) |
C4 | 0.0345 (19) | 0.0233 (17) | 0.0572 (19) | 0.0027 (15) | 0.0126 (16) | −0.0094 (15) |
C5 | 0.0431 (19) | 0.0220 (16) | 0.0334 (15) | 0.0125 (14) | 0.0099 (14) | 0.0021 (13) |
C6 | 0.0339 (17) | 0.0228 (15) | 0.0303 (14) | 0.0161 (14) | 0.0042 (13) | 0.0016 (12) |
C7 | 0.0351 (18) | 0.0240 (16) | 0.0334 (16) | 0.0090 (14) | 0.0119 (14) | −0.0001 (13) |
C8 | 0.0182 (14) | 0.0174 (15) | 0.0279 (14) | 0.0035 (12) | −0.0001 (11) | −0.0046 (11) |
C9 | 0.0433 (19) | 0.0416 (19) | 0.0338 (16) | 0.0256 (16) | −0.0045 (15) | 0.0029 (14) |
C10 | 0.049 (2) | 0.0316 (17) | 0.0431 (17) | 0.0258 (16) | 0.0092 (15) | 0.0035 (14) |
C11 | 0.0248 (15) | 0.0228 (15) | 0.0207 (13) | 0.0148 (12) | −0.0042 (11) | −0.0044 (11) |
C12 | 0.0259 (16) | 0.0220 (15) | 0.0240 (13) | 0.0134 (13) | −0.0002 (12) | −0.0012 (12) |
C13 | 0.0222 (15) | 0.0277 (16) | 0.0209 (13) | 0.0137 (13) | −0.0036 (11) | −0.0017 (12) |
C14 | 0.0268 (16) | 0.0201 (15) | 0.0244 (14) | 0.0119 (13) | −0.0004 (12) | 0.0020 (11) |
C15 | 0.0250 (15) | 0.0186 (14) | 0.0242 (13) | 0.0092 (12) | −0.0013 (11) | −0.0029 (11) |
C16 | 0.0229 (16) | 0.0211 (15) | 0.0317 (14) | 0.0077 (13) | −0.0016 (12) | −0.0009 (12) |
C17 | 0.0216 (15) | 0.0295 (17) | 0.0343 (15) | 0.0124 (13) | −0.0008 (13) | −0.0027 (13) |
C18 | 0.0230 (15) | 0.0201 (14) | 0.0280 (14) | 0.0101 (12) | 0.0021 (11) | 0.0026 (11) |
C19 | 0.0232 (15) | 0.0206 (13) | 0.0212 (13) | 0.0099 (13) | −0.0012 (11) | −0.0028 (11) |
C20 | 0.0263 (16) | 0.0254 (15) | 0.0248 (13) | 0.0120 (13) | −0.0034 (12) | 0.0000 (12) |
C21 | 0.0239 (16) | 0.0265 (16) | 0.0251 (13) | 0.0157 (13) | −0.0013 (11) | −0.0006 (12) |
C22 | 0.0316 (17) | 0.0285 (16) | 0.0348 (15) | 0.0178 (14) | 0.0046 (13) | −0.0058 (13) |
C23 | 0.0392 (17) | 0.0277 (16) | 0.0294 (15) | 0.0235 (14) | −0.0038 (13) | −0.0065 (12) |
C24 | 0.0328 (16) | 0.0275 (17) | 0.0355 (15) | 0.0173 (14) | −0.0033 (13) | −0.0037 (13) |
O31 | 0.061 (4) | 0.053 (3) | 0.048 (3) | 0.014 (3) | −0.001 (3) | 0.007 (3) |
C32 | 0.051 (6) | 0.158 (14) | 0.066 (11) | 0.043 (7) | −0.008 (5) | 0.040 (11) |
C33 | 0.076 (11) | 0.163 (17) | 0.062 (10) | 0.096 (12) | 0.012 (8) | 0.025 (9) |
C34 | 0.074 (9) | 0.051 (7) | 0.028 (12) | 0.032 (3) | 0.010 (6) | −0.006 (5) |
C35 | 0.045 (6) | 0.080 (10) | 0.027 (5) | 0.022 (6) | 0.018 (5) | −0.005 (6) |
O1—S1 | 1.4354 (17) | C13—C21 | 1.454 (3) |
S1—O2 | 1.4313 (18) | C13—C14 | 1.517 (3) |
S1—N1 | 1.6944 (18) | C14—C15 | 1.525 (3) |
S1—C1 | 1.782 (2) | C14—C19 | 1.567 (3) |
N1—C11 | 1.402 (3) | C14—H14A | 1.0000 |
N1—C8 | 1.487 (3) | C15—C16 | 1.537 (3) |
C1—C2 | 1.513 (3) | C15—C20 | 1.548 (3) |
C1—H1A | 0.9900 | C15—H15A | 1.0000 |
C1—H1B | 0.9900 | C16—C17 | 1.563 (3) |
S2—C22 | 1.702 (2) | C16—H16A | 0.9900 |
S2—C23 | 1.710 (3) | C16—H16B | 0.9900 |
C2—C3 | 1.542 (3) | C17—C18 | 1.541 (3) |
C2—C8 | 1.546 (3) | C17—H17A | 0.9900 |
C2—C6 | 1.560 (3) | C17—H17B | 0.9900 |
O3—C11 | 1.232 (3) | C18—C19 | 1.535 (3) |
C3—C4 | 1.546 (4) | C18—C20 | 1.537 (3) |
C3—H3A | 0.9900 | C18—H18A | 1.0000 |
C3—H3B | 0.9900 | C19—H19A | 1.0000 |
C4—C5 | 1.531 (4) | C20—H20A | 0.9900 |
C4—H4A | 0.9900 | C20—H20B | 0.9900 |
C4—H4B | 0.9900 | C21—C22 | 1.374 (4) |
C5—C7 | 1.533 (3) | C21—C24 | 1.431 (3) |
C5—C6 | 1.545 (4) | C22—H22A | 0.9500 |
C5—H5A | 1.0000 | C23—C24 | 1.367 (4) |
C6—C10 | 1.531 (4) | C23—H23A | 0.9500 |
C6—C9 | 1.534 (3) | C24—H24A | 0.9500 |
C7—C8 | 1.543 (3) | O31—C35 | 1.422 (12) |
C7—H7A | 0.9900 | O31—C32 | 1.431 (12) |
C7—H7B | 0.9900 | C32—C33 | 1.489 (14) |
C8—H8A | 1.0000 | C32—H32A | 0.9900 |
C9—H9A | 0.9800 | C32—H32B | 0.9900 |
C9—H9B | 0.9800 | C33—C34 | 1.504 (11) |
C9—H9C | 0.9800 | C33—H33A | 0.9900 |
C10—H10A | 0.9800 | C33—H33B | 0.9900 |
C10—H10B | 0.9800 | C34—C35 | 1.502 (12) |
C10—H10C | 0.9800 | C34—H34A | 0.9900 |
C11—C12 | 1.466 (4) | C34—H34B | 0.9900 |
C12—C13 | 1.365 (3) | C35—H35A | 0.9900 |
C12—C19 | 1.524 (3) | C35—H35B | 0.9900 |
O2—S1—O1 | 117.80 (11) | C13—C14—C15 | 118.3 (2) |
O2—S1—N1 | 110.72 (10) | C13—C14—C19 | 86.51 (19) |
O1—S1—N1 | 108.45 (10) | C15—C14—C19 | 104.01 (19) |
O2—S1—C1 | 110.29 (11) | C13—C14—H14A | 114.7 |
O1—S1—C1 | 111.15 (11) | C15—C14—H14A | 114.7 |
N1—S1—C1 | 96.30 (11) | C19—C14—H14A | 114.7 |
C11—N1—C8 | 116.10 (18) | C14—C15—C16 | 106.25 (19) |
C11—N1—S1 | 123.68 (16) | C14—C15—C20 | 101.5 (2) |
C8—N1—S1 | 111.38 (14) | C16—C15—C20 | 101.7 (2) |
C2—C1—S1 | 107.33 (16) | C14—C15—H15A | 115.2 |
C2—C1—H1A | 110.2 | C16—C15—H15A | 115.2 |
S1—C1—H1A | 110.2 | C20—C15—H15A | 115.2 |
C2—C1—H1B | 110.2 | C15—C16—C17 | 103.43 (19) |
S1—C1—H1B | 110.2 | C15—C16—H16A | 111.1 |
H1A—C1—H1B | 108.5 | C17—C16—H16A | 111.1 |
C22—S2—C23 | 92.56 (14) | C15—C16—H16B | 111.1 |
C1—C2—C3 | 116.88 (19) | C17—C16—H16B | 111.1 |
C1—C2—C8 | 108.33 (19) | H16A—C16—H16B | 109.0 |
C3—C2—C8 | 104.6 (2) | C18—C17—C16 | 103.1 (2) |
C1—C2—C6 | 119.6 (2) | C18—C17—H17A | 111.2 |
C3—C2—C6 | 101.7 (2) | C16—C17—H17A | 111.2 |
C8—C2—C6 | 104.09 (19) | C18—C17—H17B | 111.2 |
C2—C3—C4 | 101.6 (2) | C16—C17—H17B | 111.2 |
C2—C3—H3A | 111.5 | H17A—C17—H17B | 109.1 |
C4—C3—H3A | 111.5 | C19—C18—C20 | 103.7 (2) |
C2—C3—H3B | 111.5 | C19—C18—C17 | 105.5 (2) |
C4—C3—H3B | 111.5 | C20—C18—C17 | 101.2 (2) |
H3A—C3—H3B | 109.3 | C19—C18—H18A | 115.0 |
C5—C4—C3 | 104.4 (2) | C20—C18—H18A | 115.0 |
C5—C4—H4A | 110.9 | C17—C18—H18A | 115.0 |
C3—C4—H4A | 110.9 | C12—C19—C18 | 116.75 (19) |
C5—C4—H4B | 110.9 | C12—C19—C14 | 85.83 (18) |
C3—C4—H4B | 110.9 | C18—C19—C14 | 102.42 (18) |
H4A—C4—H4B | 108.9 | C12—C19—H19A | 115.7 |
C4—C5—C7 | 107.7 (2) | C18—C19—H19A | 115.7 |
C4—C5—C6 | 102.6 (2) | C14—C19—H19A | 115.7 |
C7—C5—C6 | 102.7 (2) | C18—C20—C15 | 94.70 (18) |
C4—C5—H5A | 114.2 | C18—C20—H20A | 112.8 |
C7—C5—H5A | 114.2 | C15—C20—H20A | 112.8 |
C6—C5—H5A | 114.2 | C18—C20—H20B | 112.8 |
C10—C6—C9 | 106.6 (2) | C15—C20—H20B | 112.8 |
C10—C6—C5 | 114.0 (2) | H20A—C20—H20B | 110.2 |
C9—C6—C5 | 114.3 (2) | C22—C21—C24 | 110.9 (2) |
C10—C6—C2 | 113.5 (2) | C22—C21—C13 | 128.0 (2) |
C9—C6—C2 | 116.1 (2) | C24—C21—C13 | 121.1 (2) |
C5—C6—C2 | 92.3 (2) | C21—C22—S2 | 112.2 (2) |
C5—C7—C8 | 101.8 (2) | C21—C22—H22A | 123.9 |
C5—C7—H7A | 111.4 | S2—C22—H22A | 123.9 |
C8—C7—H7A | 111.4 | C24—C23—S2 | 110.8 (2) |
C5—C7—H7B | 111.4 | C24—C23—H23A | 124.6 |
C8—C7—H7B | 111.4 | S2—C23—H23A | 124.6 |
H7A—C7—H7B | 109.3 | C23—C24—C21 | 113.5 (3) |
N1—C8—C7 | 115.79 (19) | C23—C24—H24A | 123.3 |
N1—C8—C2 | 107.22 (18) | C21—C24—H24A | 123.3 |
C7—C8—C2 | 103.9 (2) | C35—O31—C32 | 101.7 (10) |
N1—C8—H8A | 109.9 | O31—C32—C33 | 109.1 (10) |
C7—C8—H8A | 109.9 | O31—C32—H32A | 109.9 |
C2—C8—H8A | 109.9 | C33—C32—H32A | 109.9 |
C6—C9—H9A | 109.5 | O31—C32—H32B | 109.9 |
C6—C9—H9B | 109.5 | C33—C32—H32B | 109.9 |
H9A—C9—H9B | 109.5 | H32A—C32—H32B | 108.3 |
C6—C9—H9C | 109.5 | C32—C33—C34 | 103.4 (9) |
H9A—C9—H9C | 109.5 | C32—C33—H33A | 111.1 |
H9B—C9—H9C | 109.5 | C34—C33—H33A | 111.1 |
C6—C10—H10A | 109.5 | C32—C33—H33B | 111.1 |
C6—C10—H10B | 109.5 | C34—C33—H33B | 111.1 |
H10A—C10—H10B | 109.5 | H33A—C33—H33B | 109.1 |
C6—C10—H10C | 109.5 | C35—C34—C33 | 103.8 (6) |
H10A—C10—H10C | 109.5 | C35—C34—H34A | 111.0 |
H10B—C10—H10C | 109.5 | C33—C34—H34A | 111.0 |
O3—C11—N1 | 118.1 (2) | C35—C34—H34B | 111.0 |
O3—C11—C12 | 122.3 (2) | C33—C34—H34B | 111.0 |
N1—C11—C12 | 119.5 (2) | H34A—C34—H34B | 109.0 |
C13—C12—C11 | 130.4 (2) | O31—C35—C34 | 107.0 (9) |
C13—C12—C19 | 93.9 (2) | O31—C35—H35A | 110.3 |
C11—C12—C19 | 135.5 (2) | C34—C35—H35A | 110.3 |
C12—C13—C21 | 139.1 (3) | O31—C35—H35B | 110.3 |
C12—C13—C14 | 93.7 (2) | C34—C35—H35B | 110.3 |
C21—C13—C14 | 127.0 (2) | H35A—C35—H35B | 108.6 |
O2—S1—N1—C11 | 88.8 (2) | N1—C11—C12—C13 | 178.4 (2) |
O1—S1—N1—C11 | −41.9 (2) | O3—C11—C12—C19 | 169.1 (2) |
C1—S1—N1—C11 | −156.72 (19) | N1—C11—C12—C19 | −7.9 (4) |
O2—S1—N1—C8 | −125.26 (16) | C11—C12—C13—C21 | 2.5 (5) |
O1—S1—N1—C8 | 104.06 (17) | C19—C12—C13—C21 | −173.2 (3) |
C1—S1—N1—C8 | −10.75 (18) | C11—C12—C13—C14 | 177.7 (3) |
O2—S1—C1—C2 | 106.05 (18) | C19—C12—C13—C14 | 2.10 (19) |
O1—S1—C1—C2 | −121.40 (18) | C12—C13—C14—C15 | −106.1 (2) |
N1—S1—C1—C2 | −8.80 (19) | C21—C13—C14—C15 | 70.0 (3) |
S1—C1—C2—C3 | 142.6 (2) | C12—C13—C14—C19 | −2.04 (19) |
S1—C1—C2—C8 | 24.9 (2) | C21—C13—C14—C19 | 174.1 (2) |
S1—C1—C2—C6 | −94.0 (2) | C13—C14—C15—C16 | 162.6 (2) |
C1—C2—C3—C4 | 171.7 (2) | C19—C14—C15—C16 | 69.0 (2) |
C8—C2—C3—C4 | −68.6 (2) | C13—C14—C15—C20 | 56.6 (3) |
C6—C2—C3—C4 | 39.5 (2) | C19—C14—C15—C20 | −37.0 (2) |
C2—C3—C4—C5 | −4.3 (3) | C14—C15—C16—C17 | −72.8 (2) |
C3—C4—C5—C7 | 75.2 (3) | C20—C15—C16—C17 | 33.0 (2) |
C3—C4—C5—C6 | −32.7 (3) | C15—C16—C17—C18 | 2.2 (2) |
C4—C5—C6—C10 | −62.5 (3) | C16—C17—C18—C19 | 70.7 (2) |
C7—C5—C6—C10 | −174.1 (2) | C16—C17—C18—C20 | −37.0 (2) |
C4—C5—C6—C9 | 174.6 (2) | C13—C12—C19—C18 | 99.8 (2) |
C7—C5—C6—C9 | 62.9 (3) | C11—C12—C19—C18 | −75.4 (3) |
C4—C5—C6—C2 | 54.5 (2) | C13—C12—C19—C14 | −2.04 (19) |
C7—C5—C6—C2 | −57.1 (2) | C11—C12—C19—C14 | −177.3 (3) |
C1—C2—C6—C10 | −70.6 (3) | C20—C18—C19—C12 | −60.2 (3) |
C3—C2—C6—C10 | 59.8 (3) | C17—C18—C19—C12 | −166.12 (19) |
C8—C2—C6—C10 | 168.3 (2) | C20—C18—C19—C14 | 31.4 (2) |
C1—C2—C6—C9 | 53.4 (3) | C17—C18—C19—C14 | −74.5 (2) |
C3—C2—C6—C9 | −176.2 (2) | C13—C14—C19—C12 | 1.83 (17) |
C8—C2—C6—C9 | −67.7 (3) | C15—C14—C19—C12 | 120.17 (19) |
C1—C2—C6—C5 | 171.9 (2) | C13—C14—C19—C18 | −114.66 (19) |
C3—C2—C6—C5 | −57.6 (2) | C15—C14—C19—C18 | 3.7 (2) |
C8—C2—C6—C5 | 50.8 (2) | C19—C18—C20—C15 | −53.0 (2) |
C4—C5—C7—C8 | −65.1 (3) | C17—C18—C20—C15 | 56.2 (2) |
C6—C5—C7—C8 | 42.8 (3) | C14—C15—C20—C18 | 54.6 (2) |
C11—N1—C8—C7 | −69.3 (3) | C16—C15—C20—C18 | −54.9 (2) |
S1—N1—C8—C7 | 141.92 (19) | C12—C13—C21—C22 | −2.8 (5) |
C11—N1—C8—C2 | 175.32 (19) | C14—C13—C21—C22 | −176.9 (2) |
S1—N1—C8—C2 | 26.6 (2) | C12—C13—C21—C24 | 176.8 (3) |
C5—C7—C8—N1 | −126.1 (2) | C14—C13—C21—C24 | 2.8 (4) |
C5—C7—C8—C2 | −8.8 (3) | C24—C21—C22—S2 | 0.1 (3) |
C1—C2—C8—N1 | −32.7 (3) | C13—C21—C22—S2 | 179.8 (2) |
C3—C2—C8—N1 | −158.00 (19) | C23—S2—C22—C21 | −0.3 (2) |
C6—C2—C8—N1 | 95.7 (2) | C22—S2—C23—C24 | 0.5 (2) |
C1—C2—C8—C7 | −155.7 (2) | S2—C23—C24—C21 | −0.5 (3) |
C3—C2—C8—C7 | 78.9 (2) | C22—C21—C24—C23 | 0.3 (3) |
C6—C2—C8—C7 | −27.4 (3) | C13—C21—C24—C23 | −179.4 (2) |
C8—N1—C11—O3 | 3.1 (3) | C35—O31—C32—C33 | −35.6 (13) |
S1—N1—C11—O3 | 147.63 (18) | O31—C32—C33—C34 | 18 (2) |
C8—N1—C11—C12 | −179.8 (2) | C32—C33—C34—C35 | 6 (3) |
S1—N1—C11—C12 | −35.3 (3) | C32—O31—C35—C34 | 38.8 (19) |
O3—C11—C12—C13 | −4.7 (4) | C33—C34—C35—O31 | −28 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2i | 1.0 | 2.59 | 3.516 (3) | 154 |
C1—H1B···O3ii | 0.99 | 2.45 | 3.422 (3) | 168 |
C14—H14A···O1iii | 1.00 | 2.66 | 3.500 (3) | 141 |
C1—H1A···O31 | 0.99 | 2.36 | 3.235 (14) | 147 |
Symmetry codes: (i) x−y, −y+1, −z+1/3; (ii) x−y+1, −y+1, −z+1/3; (iii) x−y+1, −y+2, −z+1/3. |
C27H33NO3S | Dx = 1.266 Mg m−3 |
Mr = 451.60 | Melting point: 186 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 43635 reflections |
a = 11.687 (2) Å | θ = 1.7–27.5° |
b = 12.849 (3) Å | µ = 0.17 mm−1 |
c = 31.547 (6) Å | T = 150 K |
V = 4737.2 (16) Å3 | Block, colourless |
Z = 8 | 0.40 × 0.35 × 0.17 mm |
F(000) = 1936 |
Nonius KappaCCD diffractometer | 9673 independent reflections |
Radiation source: fine-focus sealed tube | 7676 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ϕ scans, and ω scans with κ offsets | θmax = 26.4°, θmin = 2.6° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −14→14 |
Tmin = 0.937, Tmax = 0.972 | k = −16→16 |
44242 measured reflections | l = −39→39 |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.052P)2 + 0.1513P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
9673 reflections | Δρmax = 0.19 e Å−3 |
583 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 4291 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (5) |
C27H33NO3S | V = 4737.2 (16) Å3 |
Mr = 451.60 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.687 (2) Å | µ = 0.17 mm−1 |
b = 12.849 (3) Å | T = 150 K |
c = 31.547 (6) Å | 0.40 × 0.35 × 0.17 mm |
Nonius KappaCCD diffractometer | 9673 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 7676 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.972 | Rint = 0.068 |
44242 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.096 | Δρmax = 0.19 e Å−3 |
S = 1.03 | Δρmin = −0.31 e Å−3 |
9673 reflections | Absolute structure: Flack (1983), 4291 Friedel pairs |
583 parameters | Absolute structure parameter: −0.02 (5) |
0 restraints |
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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. To verify the positions of the C27 methyl hydrogen atoms, they were refined to reliable, stable positions with Uavg = 0.0478. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.81519 (13) | 0.82842 (12) | 0.87280 (5) | 0.0391 (4) | |
S1 | 0.70189 (5) | 0.78856 (4) | 0.868799 (17) | 0.02823 (13) | |
C1 | 0.70490 (19) | 0.65036 (16) | 0.86702 (7) | 0.0305 (5) | |
H1A | 0.6520 | 0.6244 | 0.8449 | 0.037* | |
H1B | 0.7831 | 0.6256 | 0.8604 | 0.037* | |
N1 | 0.63077 (14) | 0.79703 (13) | 0.91532 (5) | 0.0228 (4) | |
O2 | 0.63070 (14) | 0.83102 (13) | 0.83626 (5) | 0.0404 (4) | |
C2 | 0.66810 (18) | 0.61133 (17) | 0.91030 (7) | 0.0264 (5) | |
C3 | 0.6002 (2) | 0.50883 (17) | 0.91136 (8) | 0.0341 (6) | |
H3A | 0.6413 | 0.4526 | 0.8962 | 0.041* | |
H3B | 0.5232 | 0.5175 | 0.8988 | 0.041* | |
O3 | 0.47143 (12) | 0.86942 (11) | 0.94353 (5) | 0.0292 (4) | |
C4 | 0.5927 (2) | 0.48613 (19) | 0.95972 (8) | 0.0401 (6) | |
H4A | 0.5124 | 0.4884 | 0.9697 | 0.048* | |
H4B | 0.6257 | 0.4171 | 0.9665 | 0.048* | |
C5 | 0.6638 (2) | 0.57418 (17) | 0.97980 (8) | 0.0358 (6) | |
H5A | 0.6931 | 0.5580 | 1.0088 | 0.043* | |
C6 | 0.7588 (2) | 0.59377 (17) | 0.94655 (7) | 0.0320 (5) | |
C7 | 0.5918 (2) | 0.67435 (18) | 0.97728 (7) | 0.0329 (5) | |
H7A | 0.6295 | 0.7326 | 0.9924 | 0.040* | |
H7B | 0.5144 | 0.6637 | 0.9892 | 0.040* | |
C8 | 0.58690 (18) | 0.69448 (16) | 0.92906 (6) | 0.0262 (5) | |
H8A | 0.5073 | 0.6838 | 0.9183 | 0.031* | |
C9 | 0.8369 (2) | 0.68475 (19) | 0.95728 (8) | 0.0401 (6) | |
H9A | 0.8795 | 0.6691 | 0.9833 | 0.060* | |
H9B | 0.7908 | 0.7476 | 0.9616 | 0.060* | |
H9C | 0.8908 | 0.6962 | 0.9339 | 0.060* | |
C10 | 0.8372 (2) | 0.49984 (19) | 0.93830 (9) | 0.0431 (6) | |
H10A | 0.8834 | 0.5128 | 0.9129 | 0.065* | |
H10B | 0.7904 | 0.4374 | 0.9340 | 0.065* | |
H10C | 0.8877 | 0.4894 | 0.9627 | 0.065* | |
C11 | 0.56299 (18) | 0.88439 (16) | 0.92545 (6) | 0.0236 (5) | |
C12 | 0.61030 (17) | 0.98763 (16) | 0.91705 (6) | 0.0232 (5) | |
C13 | 0.56549 (18) | 1.08492 (16) | 0.92125 (6) | 0.0243 (5) | |
C14 | 0.68049 (17) | 1.13723 (16) | 0.91663 (6) | 0.0245 (5) | |
H14A | 0.6879 | 1.1865 | 0.8922 | 0.029* | |
C15 | 0.73742 (18) | 1.17224 (17) | 0.95815 (7) | 0.0286 (5) | |
H15A | 0.6948 | 1.2273 | 0.9740 | 0.034* | |
C16 | 0.86076 (18) | 1.20032 (19) | 0.94685 (8) | 0.0367 (6) | |
H16A | 0.9001 | 1.2342 | 0.9710 | 0.044* | |
H16B | 0.8638 | 1.2470 | 0.9219 | 0.044* | |
C17 | 0.91466 (18) | 1.09233 (18) | 0.93672 (8) | 0.0353 (6) | |
H17A | 0.9386 | 1.0882 | 0.9067 | 0.042* | |
H17B | 0.9818 | 1.0787 | 0.9550 | 0.042* | |
C18 | 0.81748 (18) | 1.01510 (18) | 0.94609 (7) | 0.0294 (5) | |
H18A | 0.8426 | 0.9422 | 0.9522 | 0.035* | |
C19 | 0.73200 (17) | 1.02632 (16) | 0.90952 (7) | 0.0250 (5) | |
H19A | 0.7636 | 1.0129 | 0.8806 | 0.030* | |
C20 | 0.7550 (2) | 1.07006 (17) | 0.98262 (7) | 0.0313 (5) | |
H20A | 0.8035 | 1.0787 | 1.0081 | 0.038* | |
H20B | 0.6820 | 1.0358 | 0.9903 | 0.038* | |
C21 | 0.45561 (17) | 1.13654 (16) | 0.92709 (6) | 0.0223 (5) | |
C22 | 0.35456 (18) | 1.08700 (17) | 0.93909 (7) | 0.0275 (5) | |
H22A | 0.3556 | 1.0148 | 0.9456 | 0.033* | |
C23 | 0.25308 (18) | 1.14160 (16) | 0.94155 (7) | 0.0272 (5) | |
H23A | 0.1856 | 1.1062 | 0.9501 | 0.033* | |
C24 | 0.24691 (18) | 1.24753 (17) | 0.93178 (6) | 0.0252 (5) | |
C25 | 0.34828 (17) | 1.29767 (17) | 0.92094 (6) | 0.0267 (5) | |
H25A | 0.3472 | 1.3701 | 0.9149 | 0.032* | |
C26 | 0.45045 (18) | 1.24384 (16) | 0.91889 (6) | 0.0269 (5) | |
H26A | 0.5186 | 1.2802 | 0.9118 | 0.032* | |
C27 | 0.13450 (17) | 1.30333 (18) | 0.93233 (7) | 0.0304 (5) | |
H27A | 0.1469 | 1.3773 | 0.9264 | 0.046* | |
H27B | 0.0990 | 1.2956 | 0.9603 | 0.046* | |
H27C | 0.0841 | 1.2736 | 0.9107 | 0.046* | |
O31 | 0.34129 (15) | 0.59886 (15) | 0.86620 (7) | 0.0638 (6) | |
S31 | 0.23370 (6) | 0.62631 (5) | 0.88508 (2) | 0.04078 (17) | |
C31 | 0.2371 (2) | 0.75909 (18) | 0.90151 (7) | 0.0337 (5) | |
H31A | 0.1979 | 0.7675 | 0.9291 | 0.040* | |
H31B | 0.3172 | 0.7833 | 0.9045 | 0.040* | |
N31 | 0.13308 (15) | 0.64214 (14) | 0.84736 (5) | 0.0265 (4) | |
O32 | 0.1911 (2) | 0.56063 (14) | 0.91745 (6) | 0.0692 (7) | |
C32 | 0.17624 (18) | 0.82052 (16) | 0.86750 (6) | 0.0269 (5) | |
C33 | 0.1095 (2) | 0.91680 (18) | 0.88247 (8) | 0.0366 (6) | |
H33A | 0.0414 | 0.8967 | 0.8993 | 0.044* | |
H33B | 0.1584 | 0.9634 | 0.8997 | 0.044* | |
O33 | −0.04204 (13) | 0.58735 (12) | 0.82572 (5) | 0.0352 (4) | |
C34 | 0.0750 (2) | 0.9685 (2) | 0.84054 (9) | 0.0456 (7) | |
H34A | −0.0093 | 0.9697 | 0.8373 | 0.055* | |
H34B | 0.1044 | 1.0407 | 0.8389 | 0.055* | |
C35 | 0.1307 (2) | 0.8996 (2) | 0.80669 (8) | 0.0407 (6) | |
H35A | 0.1418 | 0.9350 | 0.7788 | 0.049* | |
C36 | 0.2439 (2) | 0.86511 (18) | 0.82844 (7) | 0.0325 (5) | |
C37 | 0.0622 (2) | 0.79756 (18) | 0.80405 (7) | 0.0376 (6) | |
H37A | −0.0204 | 0.8111 | 0.7998 | 0.045* | |
H37B | 0.0906 | 0.7524 | 0.7809 | 0.045* | |
C38 | 0.08545 (18) | 0.74915 (17) | 0.84772 (7) | 0.0272 (5) | |
H38A | 0.0141 | 0.7509 | 0.8652 | 0.033* | |
C39 | 0.3137 (2) | 0.7869 (2) | 0.80242 (8) | 0.0444 (6) | |
H39A | 0.3353 | 0.8184 | 0.7753 | 0.067* | |
H39B | 0.2676 | 0.7245 | 0.7972 | 0.067* | |
H39C | 0.3829 | 0.7677 | 0.8181 | 0.067* | |
C40 | 0.3246 (2) | 0.9547 (2) | 0.83956 (9) | 0.0447 (7) | |
H40A | 0.3852 | 0.9293 | 0.8584 | 0.067* | |
H40B | 0.2815 | 1.0099 | 0.8539 | 0.067* | |
H40C | 0.3589 | 0.9824 | 0.8135 | 0.067* | |
C41 | 0.0557 (2) | 0.56291 (17) | 0.83499 (7) | 0.0266 (5) | |
C42 | 0.10053 (18) | 0.45719 (17) | 0.83037 (7) | 0.0256 (5) | |
C43 | 0.04976 (18) | 0.36382 (17) | 0.82181 (6) | 0.0258 (5) | |
C44 | 0.16350 (17) | 0.30849 (17) | 0.81514 (7) | 0.0272 (5) | |
H44A | 0.1809 | 0.2518 | 0.8359 | 0.033* | |
C45 | 0.20066 (18) | 0.28688 (17) | 0.76923 (7) | 0.0306 (5) | |
H45A | 0.1525 | 0.2352 | 0.7536 | 0.037* | |
C46 | 0.32879 (18) | 0.26056 (19) | 0.77134 (8) | 0.0381 (6) | |
H46A | 0.3561 | 0.2312 | 0.7442 | 0.046* | |
H46B | 0.3449 | 0.2104 | 0.7944 | 0.046* | |
C47 | 0.3854 (2) | 0.3682 (2) | 0.78050 (9) | 0.0430 (6) | |
H47A | 0.4287 | 0.3667 | 0.8075 | 0.052* | |
H47B | 0.4377 | 0.3886 | 0.7573 | 0.052* | |
C48 | 0.28339 (19) | 0.44268 (18) | 0.78337 (7) | 0.0315 (5) | |
H48A | 0.3024 | 0.5179 | 0.7794 | 0.038* | |
C49 | 0.22163 (18) | 0.41645 (17) | 0.82486 (7) | 0.0286 (5) | |
H49A | 0.2704 | 0.4184 | 0.8509 | 0.034* | |
C50 | 0.2030 (2) | 0.39671 (18) | 0.74987 (7) | 0.0331 (5) | |
H50A | 0.2364 | 0.3979 | 0.7210 | 0.040* | |
H50B | 0.1268 | 0.4303 | 0.7498 | 0.040* | |
C51 | −0.06397 (19) | 0.31822 (17) | 0.81778 (6) | 0.0263 (5) | |
C52 | −0.16743 (18) | 0.37249 (18) | 0.82097 (7) | 0.0308 (5) | |
H52A | −0.1665 | 0.4453 | 0.8261 | 0.037* | |
C53 | −0.27067 (19) | 0.32178 (18) | 0.81681 (7) | 0.0331 (5) | |
H53A | −0.3395 | 0.3606 | 0.8191 | 0.040* | |
C54 | −0.27698 (18) | 0.21476 (18) | 0.80924 (6) | 0.0294 (5) | |
C55 | −0.17470 (19) | 0.16141 (18) | 0.80577 (7) | 0.0311 (5) | |
H55A | −0.1760 | 0.0887 | 0.8004 | 0.037* | |
C56 | −0.07091 (19) | 0.21139 (17) | 0.80990 (7) | 0.0299 (5) | |
H56A | −0.0023 | 0.1722 | 0.8073 | 0.036* | |
C57 | −0.3900 (2) | 0.1602 (2) | 0.80431 (8) | 0.0407 (6) | |
H57A | −0.4180 | 0.1696 | 0.7753 | 0.061* | |
H57B | −0.4453 | 0.1898 | 0.8243 | 0.061* | |
H57C | −0.3803 | 0.0859 | 0.8101 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0289 (8) | 0.0299 (9) | 0.0586 (11) | −0.0047 (7) | 0.0163 (8) | −0.0051 (8) |
S1 | 0.0301 (3) | 0.0258 (3) | 0.0287 (3) | 0.0023 (2) | 0.0071 (2) | 0.0004 (2) |
C1 | 0.0336 (12) | 0.0285 (12) | 0.0294 (11) | −0.0011 (10) | 0.0041 (10) | −0.0037 (10) |
N1 | 0.0233 (9) | 0.0186 (9) | 0.0266 (9) | 0.0012 (8) | 0.0026 (7) | 0.0015 (7) |
O2 | 0.0521 (10) | 0.0441 (10) | 0.0251 (8) | 0.0144 (9) | 0.0014 (7) | 0.0071 (7) |
C2 | 0.0277 (11) | 0.0225 (11) | 0.0290 (11) | 0.0023 (9) | 0.0008 (9) | −0.0024 (9) |
C3 | 0.0341 (13) | 0.0242 (12) | 0.0439 (15) | 0.0002 (11) | 0.0007 (11) | −0.0054 (11) |
O3 | 0.0263 (8) | 0.0240 (8) | 0.0373 (9) | −0.0007 (7) | 0.0088 (7) | 0.0008 (7) |
C4 | 0.0499 (16) | 0.0267 (13) | 0.0437 (15) | −0.0008 (12) | 0.0022 (12) | 0.0065 (11) |
C5 | 0.0468 (15) | 0.0252 (12) | 0.0354 (13) | 0.0033 (11) | −0.0043 (11) | 0.0055 (10) |
C6 | 0.0350 (13) | 0.0270 (12) | 0.0341 (12) | 0.0045 (11) | −0.0061 (10) | 0.0020 (10) |
C7 | 0.0436 (14) | 0.0252 (12) | 0.0300 (12) | 0.0026 (11) | 0.0071 (10) | 0.0028 (9) |
C8 | 0.0267 (12) | 0.0207 (12) | 0.0311 (12) | 0.0002 (9) | 0.0021 (9) | 0.0002 (9) |
C9 | 0.0386 (14) | 0.0371 (15) | 0.0444 (14) | −0.0009 (12) | −0.0143 (11) | 0.0032 (11) |
C10 | 0.0407 (14) | 0.0337 (14) | 0.0548 (16) | 0.0135 (12) | −0.0066 (13) | 0.0024 (12) |
C11 | 0.0226 (11) | 0.0254 (12) | 0.0228 (11) | 0.0011 (10) | −0.0005 (9) | 0.0011 (9) |
C12 | 0.0233 (11) | 0.0223 (12) | 0.0239 (11) | −0.0042 (9) | 0.0018 (9) | 0.0003 (9) |
C13 | 0.0242 (11) | 0.0255 (11) | 0.0233 (11) | −0.0010 (10) | 0.0001 (9) | 0.0024 (9) |
C14 | 0.0265 (11) | 0.0203 (11) | 0.0267 (11) | −0.0007 (9) | 0.0046 (9) | 0.0012 (9) |
C15 | 0.0253 (12) | 0.0249 (12) | 0.0358 (12) | −0.0006 (10) | 0.0021 (10) | −0.0063 (9) |
C16 | 0.0274 (12) | 0.0300 (14) | 0.0525 (15) | −0.0057 (11) | 0.0007 (11) | −0.0027 (11) |
C17 | 0.0228 (12) | 0.0329 (14) | 0.0502 (15) | −0.0023 (11) | 0.0001 (11) | −0.0011 (11) |
C18 | 0.0249 (12) | 0.0260 (12) | 0.0374 (13) | 0.0012 (10) | −0.0013 (10) | −0.0002 (10) |
C19 | 0.0247 (11) | 0.0214 (11) | 0.0289 (11) | −0.0019 (9) | 0.0043 (9) | −0.0004 (9) |
C20 | 0.0314 (12) | 0.0328 (13) | 0.0295 (12) | −0.0020 (11) | −0.0036 (10) | −0.0043 (10) |
C21 | 0.0220 (11) | 0.0228 (11) | 0.0222 (11) | −0.0016 (9) | −0.0019 (8) | −0.0004 (9) |
C22 | 0.0279 (12) | 0.0201 (11) | 0.0343 (12) | −0.0017 (10) | 0.0042 (10) | −0.0001 (9) |
C23 | 0.0243 (11) | 0.0239 (12) | 0.0334 (12) | −0.0040 (10) | 0.0050 (9) | 0.0005 (9) |
C24 | 0.0256 (11) | 0.0256 (11) | 0.0246 (11) | 0.0014 (10) | −0.0034 (9) | −0.0006 (9) |
C25 | 0.0286 (12) | 0.0194 (11) | 0.0322 (12) | 0.0011 (10) | −0.0028 (9) | 0.0026 (10) |
C26 | 0.0275 (12) | 0.0242 (11) | 0.0290 (11) | −0.0036 (10) | 0.0001 (10) | 0.0024 (9) |
C27 | 0.0262 (11) | 0.0282 (13) | 0.0367 (12) | 0.0022 (10) | −0.0015 (9) | 0.0006 (10) |
O31 | 0.0364 (10) | 0.0484 (12) | 0.1067 (17) | 0.0185 (9) | −0.0333 (11) | −0.0334 (11) |
S31 | 0.0509 (4) | 0.0242 (3) | 0.0473 (4) | 0.0014 (3) | −0.0262 (3) | −0.0016 (3) |
C31 | 0.0390 (13) | 0.0290 (13) | 0.0331 (12) | −0.0010 (11) | −0.0095 (11) | −0.0028 (10) |
N31 | 0.0276 (10) | 0.0218 (10) | 0.0302 (10) | 0.0020 (8) | −0.0061 (8) | −0.0035 (8) |
O32 | 0.1203 (18) | 0.0377 (11) | 0.0497 (12) | −0.0267 (12) | −0.0399 (12) | 0.0164 (9) |
C32 | 0.0290 (11) | 0.0254 (11) | 0.0263 (11) | 0.0019 (9) | −0.0055 (10) | −0.0027 (9) |
C33 | 0.0378 (13) | 0.0279 (13) | 0.0442 (14) | 0.0027 (11) | −0.0023 (11) | −0.0083 (11) |
O33 | 0.0241 (9) | 0.0283 (9) | 0.0530 (10) | 0.0034 (7) | −0.0067 (7) | −0.0076 (8) |
C34 | 0.0451 (16) | 0.0261 (14) | 0.0655 (19) | 0.0037 (12) | −0.0179 (14) | −0.0020 (12) |
C35 | 0.0491 (15) | 0.0366 (15) | 0.0366 (14) | −0.0011 (13) | −0.0129 (12) | 0.0083 (11) |
C36 | 0.0367 (13) | 0.0313 (13) | 0.0296 (12) | −0.0031 (11) | −0.0018 (10) | 0.0014 (10) |
C37 | 0.0416 (13) | 0.0319 (14) | 0.0391 (13) | 0.0018 (12) | −0.0153 (11) | 0.0014 (11) |
C38 | 0.0256 (12) | 0.0241 (12) | 0.0319 (12) | 0.0037 (9) | −0.0007 (10) | −0.0053 (9) |
C39 | 0.0442 (15) | 0.0507 (17) | 0.0384 (14) | −0.0015 (14) | 0.0081 (12) | −0.0072 (12) |
C40 | 0.0434 (15) | 0.0394 (15) | 0.0513 (16) | −0.0125 (13) | 0.0004 (13) | 0.0061 (12) |
C41 | 0.0268 (12) | 0.0261 (12) | 0.0269 (11) | 0.0000 (10) | −0.0011 (10) | −0.0026 (9) |
C42 | 0.0268 (12) | 0.0241 (12) | 0.0258 (11) | 0.0030 (10) | −0.0018 (9) | −0.0031 (9) |
C43 | 0.0296 (12) | 0.0258 (12) | 0.0219 (11) | 0.0025 (10) | −0.0008 (9) | 0.0003 (9) |
C44 | 0.0287 (12) | 0.0243 (12) | 0.0287 (11) | 0.0024 (10) | −0.0043 (9) | −0.0008 (9) |
C45 | 0.0319 (12) | 0.0245 (12) | 0.0354 (12) | 0.0052 (11) | −0.0031 (10) | −0.0069 (10) |
C46 | 0.0341 (13) | 0.0343 (14) | 0.0458 (14) | 0.0075 (11) | 0.0046 (11) | −0.0072 (11) |
C47 | 0.0271 (13) | 0.0420 (16) | 0.0600 (17) | 0.0027 (12) | 0.0037 (12) | −0.0097 (13) |
C48 | 0.0269 (12) | 0.0270 (13) | 0.0407 (13) | 0.0009 (10) | 0.0043 (10) | −0.0027 (10) |
C49 | 0.0294 (12) | 0.0265 (12) | 0.0298 (12) | 0.0046 (10) | −0.0062 (10) | −0.0030 (9) |
C50 | 0.0355 (13) | 0.0353 (14) | 0.0285 (12) | 0.0033 (11) | 0.0038 (10) | −0.0032 (10) |
C51 | 0.0302 (12) | 0.0260 (12) | 0.0226 (11) | −0.0015 (10) | −0.0014 (9) | 0.0005 (9) |
C52 | 0.0317 (12) | 0.0283 (12) | 0.0325 (12) | 0.0023 (11) | 0.0010 (10) | −0.0042 (10) |
C53 | 0.0273 (12) | 0.0354 (14) | 0.0367 (13) | 0.0003 (11) | 0.0016 (10) | −0.0039 (10) |
C54 | 0.0309 (12) | 0.0335 (13) | 0.0237 (11) | −0.0047 (11) | −0.0022 (9) | −0.0015 (10) |
C55 | 0.0369 (14) | 0.0238 (12) | 0.0326 (12) | −0.0012 (11) | 0.0001 (10) | −0.0008 (9) |
C56 | 0.0283 (11) | 0.0277 (12) | 0.0338 (12) | 0.0033 (11) | 0.0000 (10) | 0.0024 (10) |
C57 | 0.0354 (13) | 0.0442 (16) | 0.0426 (14) | −0.0056 (12) | −0.0019 (11) | −0.0037 (12) |
O1—S1 | 1.4253 (16) | O31—S31 | 1.435 (2) |
S1—O2 | 1.4296 (16) | S31—O32 | 1.415 (2) |
S1—N1 | 1.6902 (17) | S31—N31 | 1.6852 (18) |
S1—C1 | 1.777 (2) | S31—C31 | 1.784 (2) |
C1—C2 | 1.517 (3) | C31—C32 | 1.510 (3) |
C1—H1A | 0.9900 | C31—H31A | 0.9900 |
C1—H1B | 0.9900 | C31—H31B | 0.9900 |
N1—C11 | 1.410 (3) | N31—C41 | 1.417 (3) |
N1—C8 | 1.479 (3) | N31—C38 | 1.483 (3) |
C2—C3 | 1.538 (3) | C32—C38 | 1.535 (3) |
C2—C8 | 1.547 (3) | C32—C33 | 1.537 (3) |
C2—C6 | 1.575 (3) | C32—C36 | 1.572 (3) |
C3—C4 | 1.556 (3) | C33—C34 | 1.534 (4) |
C3—H3A | 0.9900 | C33—H33A | 0.9900 |
C3—H3B | 0.9900 | C33—H33B | 0.9900 |
O3—C11 | 1.228 (2) | O33—C41 | 1.220 (3) |
C4—C5 | 1.540 (3) | C34—C35 | 1.532 (4) |
C4—H4A | 0.9900 | C34—H34A | 0.9900 |
C4—H4B | 0.9900 | C34—H34B | 0.9900 |
C5—C7 | 1.539 (3) | C35—C37 | 1.539 (3) |
C5—C6 | 1.548 (3) | C35—C36 | 1.555 (3) |
C5—H5A | 1.0000 | C35—H35A | 1.0000 |
C6—C9 | 1.522 (3) | C36—C40 | 1.529 (3) |
C6—C10 | 1.538 (3) | C36—C39 | 1.533 (3) |
C7—C8 | 1.544 (3) | C37—C38 | 1.536 (3) |
C7—H7A | 0.9900 | C37—H37A | 0.9900 |
C7—H7B | 0.9900 | C37—H37B | 0.9900 |
C8—H8A | 1.0000 | C38—H38A | 1.0000 |
C9—H9A | 0.9800 | C39—H39A | 0.9800 |
C9—H9B | 0.9800 | C39—H39B | 0.9800 |
C9—H9C | 0.9800 | C39—H39C | 0.9800 |
C10—H10A | 0.9800 | C40—H40A | 0.9800 |
C10—H10B | 0.9800 | C40—H40B | 0.9800 |
C10—H10C | 0.9800 | C40—H40C | 0.9800 |
C11—C12 | 1.461 (3) | C41—C42 | 1.463 (3) |
C12—C13 | 1.362 (3) | C42—C43 | 1.365 (3) |
C12—C19 | 1.525 (3) | C42—C49 | 1.519 (3) |
C13—C21 | 1.457 (3) | C43—C51 | 1.458 (3) |
C13—C14 | 1.510 (3) | C43—C44 | 1.522 (3) |
C14—C15 | 1.536 (3) | C44—C45 | 1.537 (3) |
C14—C19 | 1.563 (3) | C44—C49 | 1.575 (3) |
C14—H14A | 1.0000 | C44—H44A | 1.0000 |
C15—C16 | 1.528 (3) | C45—C46 | 1.537 (3) |
C15—C20 | 1.537 (3) | C45—C50 | 1.538 (3) |
C15—H15A | 1.0000 | C45—H45A | 1.0000 |
C16—C17 | 1.557 (3) | C46—C47 | 1.560 (3) |
C16—H16A | 0.9900 | C46—H46A | 0.9900 |
C16—H16B | 0.9900 | C46—H46B | 0.9900 |
C17—C18 | 1.537 (3) | C47—C48 | 1.532 (3) |
C17—H17A | 0.9900 | C47—H47A | 0.9900 |
C17—H17B | 0.9900 | C47—H47B | 0.9900 |
C18—C19 | 1.533 (3) | C48—C49 | 1.532 (3) |
C18—C20 | 1.536 (3) | C48—C50 | 1.532 (3) |
C18—H18A | 1.0000 | C48—H48A | 1.0000 |
C19—H19A | 1.0000 | C49—H49A | 1.0000 |
C20—H20A | 0.9900 | C50—H50A | 0.9900 |
C20—H20B | 0.9900 | C50—H50B | 0.9900 |
C21—C22 | 1.394 (3) | C51—C56 | 1.397 (3) |
C21—C26 | 1.404 (3) | C51—C52 | 1.399 (3) |
C22—C23 | 1.380 (3) | C52—C53 | 1.378 (3) |
C22—H22A | 0.9500 | C52—H52A | 0.9500 |
C23—C24 | 1.398 (3) | C53—C54 | 1.398 (3) |
C23—H23A | 0.9500 | C53—H53A | 0.9500 |
C24—C25 | 1.391 (3) | C54—C55 | 1.382 (3) |
C24—C27 | 1.497 (3) | C54—C57 | 1.503 (3) |
C25—C26 | 1.381 (3) | C55—C56 | 1.379 (3) |
C25—H25A | 0.9500 | C55—H55A | 0.9500 |
C26—H26A | 0.9500 | C56—H56A | 0.9500 |
C27—H27A | 0.9800 | C57—H57A | 0.9800 |
C27—H27B | 0.9800 | C57—H57B | 0.9800 |
C27—H27C | 0.9800 | C57—H57C | 0.9800 |
O1—S1—O2 | 117.85 (11) | O32—S31—O31 | 117.47 (14) |
O1—S1—N1 | 110.90 (9) | O32—S31—N31 | 109.61 (11) |
O2—S1—N1 | 108.23 (9) | O31—S31—N31 | 110.36 (11) |
O1—S1—C1 | 110.09 (11) | O32—S31—C31 | 111.64 (12) |
O2—S1—C1 | 111.73 (11) | O31—S31—C31 | 109.63 (12) |
N1—S1—C1 | 95.82 (9) | N31—S31—C31 | 96.06 (10) |
C2—C1—S1 | 107.24 (14) | C32—C31—S31 | 106.43 (15) |
C2—C1—H1A | 110.3 | C32—C31—H31A | 110.4 |
S1—C1—H1A | 110.3 | S31—C31—H31A | 110.4 |
C2—C1—H1B | 110.3 | C32—C31—H31B | 110.4 |
S1—C1—H1B | 110.3 | S31—C31—H31B | 110.4 |
H1A—C1—H1B | 108.5 | H31A—C31—H31B | 108.6 |
C11—N1—C8 | 116.61 (16) | C41—N31—C38 | 115.37 (17) |
C11—N1—S1 | 121.60 (14) | C41—N31—S31 | 123.60 (15) |
C8—N1—S1 | 111.56 (13) | C38—N31—S31 | 111.61 (13) |
C1—C2—C3 | 116.68 (18) | C31—C32—C38 | 107.59 (18) |
C1—C2—C8 | 106.85 (17) | C31—C32—C33 | 116.21 (18) |
C3—C2—C8 | 105.46 (17) | C38—C32—C33 | 104.78 (17) |
C1—C2—C6 | 120.67 (18) | C31—C32—C36 | 120.67 (19) |
C3—C2—C6 | 102.05 (17) | C38—C32—C36 | 104.29 (17) |
C8—C2—C6 | 103.53 (17) | C33—C32—C36 | 101.69 (18) |
C2—C3—C4 | 102.16 (18) | C34—C33—C32 | 102.55 (18) |
C2—C3—H3A | 111.3 | C34—C33—H33A | 111.3 |
C4—C3—H3A | 111.3 | C32—C33—H33A | 111.3 |
C2—C3—H3B | 111.3 | C34—C33—H33B | 111.3 |
C4—C3—H3B | 111.3 | C32—C33—H33B | 111.3 |
H3A—C3—H3B | 109.2 | H33A—C33—H33B | 109.2 |
C5—C4—C3 | 103.62 (19) | C35—C34—C33 | 103.82 (19) |
C5—C4—H4A | 111.0 | C35—C34—H34A | 111.0 |
C3—C4—H4A | 111.0 | C33—C34—H34A | 111.0 |
C5—C4—H4B | 111.0 | C35—C34—H34B | 111.0 |
C3—C4—H4B | 111.0 | C33—C34—H34B | 111.0 |
H4A—C4—H4B | 109.0 | H34A—C34—H34B | 109.0 |
C7—C5—C4 | 107.39 (19) | C34—C35—C37 | 108.0 (2) |
C7—C5—C6 | 102.76 (17) | C34—C35—C36 | 102.63 (19) |
C4—C5—C6 | 103.16 (19) | C37—C35—C36 | 102.91 (19) |
C7—C5—H5A | 114.1 | C34—C35—H35A | 114.0 |
C4—C5—H5A | 114.1 | C37—C35—H35A | 114.0 |
C6—C5—H5A | 114.1 | C36—C35—H35A | 114.0 |
C9—C6—C10 | 106.44 (19) | C40—C36—C39 | 106.8 (2) |
C9—C6—C5 | 113.88 (19) | C40—C36—C35 | 114.3 (2) |
C10—C6—C5 | 114.49 (19) | C39—C36—C35 | 113.8 (2) |
C9—C6—C2 | 117.08 (18) | C40—C36—C32 | 113.88 (18) |
C10—C6—C2 | 112.98 (19) | C39—C36—C32 | 116.6 (2) |
C5—C6—C2 | 91.86 (17) | C35—C36—C32 | 91.24 (17) |
C5—C7—C8 | 102.19 (17) | C38—C37—C35 | 101.81 (17) |
C5—C7—H7A | 111.3 | C38—C37—H37A | 111.4 |
C8—C7—H7A | 111.3 | C35—C37—H37A | 111.4 |
C5—C7—H7B | 111.3 | C38—C37—H37B | 111.4 |
C8—C7—H7B | 111.3 | C35—C37—H37B | 111.4 |
H7A—C7—H7B | 109.2 | H37A—C37—H37B | 109.3 |
N1—C8—C7 | 115.15 (17) | N31—C38—C32 | 107.31 (16) |
N1—C8—C2 | 106.90 (16) | N31—C38—C37 | 115.78 (18) |
C7—C8—C2 | 103.78 (17) | C32—C38—C37 | 104.18 (18) |
N1—C8—H8A | 110.2 | N31—C38—H38A | 109.8 |
C7—C8—H8A | 110.2 | C32—C38—H38A | 109.8 |
C2—C8—H8A | 110.2 | C37—C38—H38A | 109.8 |
C6—C9—H9A | 109.5 | C36—C39—H39A | 109.5 |
C6—C9—H9B | 109.5 | C36—C39—H39B | 109.5 |
H9A—C9—H9B | 109.5 | H39A—C39—H39B | 109.5 |
C6—C9—H9C | 109.5 | C36—C39—H39C | 109.5 |
H9A—C9—H9C | 109.5 | H39A—C39—H39C | 109.5 |
H9B—C9—H9C | 109.5 | H39B—C39—H39C | 109.5 |
C6—C10—H10A | 109.5 | C36—C40—H40A | 109.5 |
C6—C10—H10B | 109.5 | C36—C40—H40B | 109.5 |
H10A—C10—H10B | 109.5 | H40A—C40—H40B | 109.5 |
C6—C10—H10C | 109.5 | C36—C40—H40C | 109.5 |
H10A—C10—H10C | 109.5 | H40A—C40—H40C | 109.5 |
H10B—C10—H10C | 109.5 | H40B—C40—H40C | 109.5 |
O3—C11—N1 | 118.04 (18) | O33—C41—N31 | 118.61 (19) |
O3—C11—C12 | 123.79 (19) | O33—C41—C42 | 123.4 (2) |
N1—C11—C12 | 117.96 (18) | N31—C41—C42 | 117.74 (19) |
C13—C12—C11 | 132.08 (19) | C43—C42—C41 | 132.8 (2) |
C13—C12—C19 | 94.27 (17) | C43—C42—C49 | 94.56 (17) |
C11—C12—C19 | 132.60 (18) | C41—C42—C49 | 131.7 (2) |
C12—C13—C21 | 140.3 (2) | C42—C43—C51 | 140.0 (2) |
C12—C13—C14 | 93.26 (16) | C42—C43—C44 | 93.34 (17) |
C21—C13—C14 | 126.45 (18) | C51—C43—C44 | 126.60 (19) |
C13—C14—C15 | 115.69 (17) | C43—C44—C45 | 117.48 (17) |
C13—C14—C19 | 87.19 (15) | C43—C44—C49 | 86.47 (16) |
C15—C14—C19 | 102.86 (16) | C45—C44—C49 | 102.75 (18) |
C13—C14—H14A | 115.7 | C43—C44—H44A | 115.3 |
C15—C14—H14A | 115.7 | C45—C44—H44A | 115.3 |
C19—C14—H14A | 115.7 | C49—C44—H44A | 115.3 |
C16—C15—C14 | 106.19 (18) | C46—C45—C44 | 105.91 (18) |
C16—C15—C20 | 101.13 (18) | C46—C45—C50 | 101.65 (19) |
C14—C15—C20 | 103.63 (17) | C44—C45—C50 | 102.32 (17) |
C16—C15—H15A | 114.8 | C46—C45—H45A | 115.1 |
C14—C15—H15A | 114.8 | C44—C45—H45A | 115.1 |
C20—C15—H15A | 114.8 | C50—C45—H45A | 115.1 |
C15—C16—C17 | 102.65 (18) | C45—C46—C47 | 103.09 (18) |
C15—C16—H16A | 111.2 | C45—C46—H46A | 111.1 |
C17—C16—H16A | 111.2 | C47—C46—H46A | 111.1 |
C15—C16—H16B | 111.2 | C45—C46—H46B | 111.1 |
C17—C16—H16B | 111.2 | C47—C46—H46B | 111.1 |
H16A—C16—H16B | 109.1 | H46A—C46—H46B | 109.1 |
C18—C17—C16 | 103.71 (18) | C48—C47—C46 | 103.56 (17) |
C18—C17—H17A | 111.0 | C48—C47—H47A | 111.0 |
C16—C17—H17A | 111.0 | C46—C47—H47A | 111.0 |
C18—C17—H17B | 111.0 | C48—C47—H47B | 111.0 |
C16—C17—H17B | 111.0 | C46—C47—H47B | 111.0 |
H17A—C17—H17B | 109.0 | H47A—C47—H47B | 109.0 |
C19—C18—C20 | 102.20 (17) | C47—C48—C49 | 106.24 (19) |
C19—C18—C17 | 106.04 (18) | C47—C48—C50 | 101.29 (18) |
C20—C18—C17 | 101.47 (18) | C49—C48—C50 | 102.45 (17) |
C19—C18—H18A | 115.1 | C47—C48—H48A | 115.1 |
C20—C18—H18A | 115.1 | C49—C48—H48A | 115.1 |
C17—C18—H18A | 115.1 | C50—C48—H48A | 115.1 |
C12—C19—C18 | 117.38 (17) | C42—C49—C48 | 117.44 (18) |
C12—C19—C14 | 85.16 (15) | C42—C49—C44 | 85.63 (16) |
C18—C19—C14 | 103.22 (17) | C48—C49—C44 | 103.33 (17) |
C12—C19—H19A | 115.5 | C42—C49—H49A | 115.3 |
C18—C19—H19A | 115.5 | C48—C49—H49A | 115.3 |
C14—C19—H19A | 115.5 | C44—C49—H49A | 115.3 |
C18—C20—C15 | 94.56 (17) | C48—C50—C45 | 95.21 (17) |
C18—C20—H20A | 112.8 | C48—C50—H50A | 112.7 |
C15—C20—H20A | 112.8 | C45—C50—H50A | 112.7 |
C18—C20—H20B | 112.8 | C48—C50—H50B | 112.7 |
C15—C20—H20B | 112.8 | C45—C50—H50B | 112.7 |
H20A—C20—H20B | 110.3 | H50A—C50—H50B | 110.2 |
C22—C21—C26 | 117.5 (2) | C56—C51—C52 | 116.9 (2) |
C22—C21—C13 | 124.97 (19) | C56—C51—C43 | 117.6 (2) |
C26—C21—C13 | 117.49 (19) | C52—C51—C43 | 125.5 (2) |
C23—C22—C21 | 120.7 (2) | C53—C52—C51 | 120.9 (2) |
C23—C22—H22A | 119.6 | C53—C52—H52A | 119.5 |
C21—C22—H22A | 119.6 | C51—C52—H52A | 119.5 |
C22—C23—C24 | 121.8 (2) | C52—C53—C54 | 121.9 (2) |
C22—C23—H23A | 119.1 | C52—C53—H53A | 119.1 |
C24—C23—H23A | 119.1 | C54—C53—H53A | 119.1 |
C25—C24—C23 | 117.5 (2) | C55—C54—C53 | 117.1 (2) |
C25—C24—C27 | 121.91 (19) | C55—C54—C57 | 121.4 (2) |
C23—C24—C27 | 120.6 (2) | C53—C54—C57 | 121.5 (2) |
C26—C25—C24 | 121.1 (2) | C56—C55—C54 | 121.5 (2) |
C26—C25—H25A | 119.5 | C56—C55—H55A | 119.3 |
C24—C25—H25A | 119.5 | C54—C55—H55A | 119.3 |
C25—C26—C21 | 121.3 (2) | C55—C56—C51 | 121.7 (2) |
C25—C26—H26A | 119.3 | C55—C56—H56A | 119.2 |
C21—C26—H26A | 119.3 | C51—C56—H56A | 119.2 |
C24—C27—H27A | 109.5 | C54—C57—H57A | 109.5 |
C24—C27—H27B | 109.5 | C54—C57—H57B | 109.5 |
H27A—C27—H27B | 109.5 | H57A—C57—H57B | 109.5 |
C24—C27—H27C | 109.5 | C54—C57—H57C | 109.5 |
H27A—C27—H27C | 109.5 | H57A—C57—H57C | 109.5 |
H27B—C27—H27C | 109.5 | H57B—C57—H57C | 109.5 |
O1—S1—C1—C2 | 102.92 (16) | O32—S31—C31—C32 | −128.40 (17) |
O2—S1—C1—C2 | −124.13 (15) | O31—S31—C31—C32 | 99.65 (18) |
N1—S1—C1—C2 | −11.85 (16) | N31—S31—C31—C32 | −14.50 (17) |
O1—S1—N1—C11 | 92.08 (17) | O32—S31—N31—C41 | −35.3 (2) |
O2—S1—N1—C11 | −38.64 (18) | O31—S31—N31—C41 | 95.59 (19) |
C1—S1—N1—C11 | −153.81 (17) | C31—S31—N31—C41 | −150.86 (18) |
O1—S1—N1—C8 | −123.95 (14) | O32—S31—N31—C38 | 109.44 (17) |
O2—S1—N1—C8 | 105.34 (15) | O31—S31—N31—C38 | −119.68 (16) |
C1—S1—N1—C8 | −9.84 (16) | C31—S31—N31—C38 | −6.12 (17) |
S1—C1—C2—C3 | 146.51 (17) | S31—C31—C32—C38 | 30.1 (2) |
S1—C1—C2—C8 | 28.9 (2) | S31—C31—C32—C33 | 147.16 (17) |
S1—C1—C2—C6 | −88.8 (2) | S31—C31—C32—C36 | −89.2 (2) |
C1—C2—C3—C4 | 172.51 (19) | C31—C32—C33—C34 | 171.8 (2) |
C8—C2—C3—C4 | −69.1 (2) | C38—C32—C33—C34 | −69.6 (2) |
C6—C2—C3—C4 | 38.8 (2) | C36—C32—C33—C34 | 38.8 (2) |
C2—C3—C4—C5 | −3.6 (2) | C32—C33—C34—C35 | −2.8 (2) |
C3—C4—C5—C7 | 74.6 (2) | C33—C34—C35—C37 | 73.7 (2) |
C3—C4—C5—C6 | −33.6 (2) | C33—C34—C35—C36 | −34.6 (2) |
C7—C5—C6—C9 | 63.9 (2) | C34—C35—C36—C40 | −61.6 (3) |
C4—C5—C6—C9 | 175.46 (19) | C37—C35—C36—C40 | −173.73 (19) |
C7—C5—C6—C10 | −173.30 (19) | C34—C35—C36—C39 | 175.4 (2) |
C4—C5—C6—C10 | −61.7 (2) | C37—C35—C36—C39 | 63.3 (2) |
C7—C5—C6—C2 | −56.95 (19) | C34—C35—C36—C32 | 55.4 (2) |
C4—C5—C6—C2 | 54.62 (19) | C37—C35—C36—C32 | −56.7 (2) |
C1—C2—C6—C9 | 53.4 (3) | C31—C32—C36—C40 | −70.2 (3) |
C3—C2—C6—C9 | −175.2 (2) | C38—C32—C36—C40 | 168.91 (19) |
C8—C2—C6—C9 | −65.9 (2) | C33—C32—C36—C40 | 60.1 (2) |
C1—C2—C6—C10 | −70.8 (3) | C31—C32—C36—C39 | 54.9 (3) |
C3—C2—C6—C10 | 60.6 (2) | C38—C32—C36—C39 | −66.0 (2) |
C8—C2—C6—C10 | 169.93 (19) | C33—C32—C36—C39 | −174.77 (19) |
C1—C2—C6—C5 | 171.57 (19) | C31—C32—C36—C35 | 172.46 (19) |
C3—C2—C6—C5 | −57.10 (19) | C38—C32—C36—C35 | 51.55 (19) |
C8—C2—C6—C5 | 52.27 (18) | C33—C32—C36—C35 | −57.21 (19) |
C4—C5—C7—C8 | −66.9 (2) | C34—C35—C37—C38 | −65.9 (2) |
C6—C5—C7—C8 | 41.5 (2) | C36—C35—C37—C38 | 42.1 (2) |
C11—N1—C8—C7 | −71.3 (2) | C41—N31—C38—C32 | 172.48 (17) |
S1—N1—C8—C7 | 142.75 (15) | S31—N31—C38—C32 | 24.6 (2) |
C11—N1—C8—C2 | 173.99 (17) | C41—N31—C38—C37 | −71.7 (2) |
S1—N1—C8—C2 | 28.06 (19) | S31—N31—C38—C37 | 140.45 (17) |
C5—C7—C8—N1 | −122.93 (19) | C31—C32—C38—N31 | −35.0 (2) |
C5—C7—C8—C2 | −6.5 (2) | C33—C32—C38—N31 | −159.22 (17) |
C1—C2—C8—N1 | −36.0 (2) | C36—C32—C38—N31 | 94.31 (19) |
C3—C2—C8—N1 | −160.78 (17) | C31—C32—C38—C37 | −158.23 (18) |
C6—C2—C8—N1 | 92.41 (19) | C33—C32—C38—C37 | 77.5 (2) |
C1—C2—C8—C7 | −158.12 (18) | C36—C32—C38—C37 | −29.0 (2) |
C3—C2—C8—C7 | 77.1 (2) | C35—C37—C38—N31 | −125.1 (2) |
C6—C2—C8—C7 | −29.7 (2) | C35—C37—C38—C32 | −7.5 (2) |
C8—N1—C11—O3 | −2.3 (3) | C38—N31—C41—O33 | 0.0 (3) |
S1—N1—C11—O3 | 139.98 (16) | S31—N31—C41—O33 | 143.59 (18) |
C8—N1—C11—C12 | 172.59 (17) | C38—N31—C41—C42 | 174.63 (18) |
S1—N1—C11—C12 | −45.1 (2) | S31—N31—C41—C42 | −41.8 (3) |
O3—C11—C12—C13 | −9.0 (4) | O33—C41—C42—C43 | −10.5 (4) |
N1—C11—C12—C13 | 176.4 (2) | N31—C41—C42—C43 | 175.2 (2) |
O3—C11—C12—C19 | 156.2 (2) | O33—C41—C42—C49 | 155.5 (2) |
N1—C11—C12—C19 | −18.4 (3) | N31—C41—C42—C49 | −18.8 (3) |
C11—C12—C13—C21 | −14.9 (4) | C41—C42—C43—C51 | −8.6 (4) |
C19—C12—C13—C21 | 176.0 (3) | C49—C42—C43—C51 | −178.2 (3) |
C11—C12—C13—C14 | 166.4 (2) | C41—C42—C43—C44 | 169.8 (2) |
C19—C12—C13—C14 | −2.70 (17) | C49—C42—C43—C44 | 0.20 (17) |
C12—C13—C14—C15 | −100.3 (2) | C42—C43—C44—C45 | −102.7 (2) |
C21—C13—C14—C15 | 80.7 (3) | C51—C43—C44—C45 | 76.0 (3) |
C12—C13—C14—C19 | 2.63 (17) | C42—C43—C44—C49 | −0.19 (16) |
C21—C13—C14—C19 | −176.4 (2) | C51—C43—C44—C49 | 178.5 (2) |
C13—C14—C15—C16 | 168.01 (18) | C43—C44—C45—C46 | 164.30 (18) |
C19—C14—C15—C16 | 74.9 (2) | C49—C44—C45—C46 | 71.6 (2) |
C13—C14—C15—C20 | 61.9 (2) | C43—C44—C45—C50 | 58.2 (2) |
C19—C14—C15—C20 | −31.2 (2) | C49—C44—C45—C50 | −34.5 (2) |
C14—C15—C16—C17 | −69.9 (2) | C44—C45—C46—C47 | −72.8 (2) |
C20—C15—C16—C17 | 38.0 (2) | C50—C45—C46—C47 | 33.8 (2) |
C15—C16—C17—C18 | −3.3 (2) | C45—C46—C47—C48 | 1.0 (2) |
C16—C17—C18—C19 | 73.9 (2) | C46—C47—C48—C49 | 71.1 (2) |
C16—C17—C18—C20 | −32.5 (2) | C46—C47—C48—C50 | −35.6 (2) |
C13—C12—C19—C18 | 105.0 (2) | C43—C42—C49—C48 | 102.6 (2) |
C11—C12—C19—C18 | −64.0 (3) | C41—C42—C49—C48 | −67.2 (3) |
C13—C12—C19—C14 | 2.61 (17) | C43—C42—C49—C44 | −0.19 (17) |
C11—C12—C19—C14 | −166.4 (2) | C41—C42—C49—C44 | −170.0 (2) |
C20—C18—C19—C12 | −54.2 (2) | C47—C48—C49—C42 | −163.88 (19) |
C17—C18—C19—C12 | −160.10 (18) | C50—C48—C49—C42 | −58.0 (2) |
C20—C18—C19—C14 | 37.2 (2) | C47—C48—C49—C44 | −71.9 (2) |
C17—C18—C19—C14 | −68.7 (2) | C50—C48—C49—C44 | 34.0 (2) |
C13—C14—C19—C12 | −2.35 (15) | C43—C44—C49—C42 | 0.17 (15) |
C15—C14—C19—C12 | 113.37 (16) | C45—C44—C49—C42 | 117.56 (17) |
C13—C14—C19—C18 | −119.37 (16) | C43—C44—C49—C48 | −117.01 (17) |
C15—C14—C19—C18 | −3.65 (19) | C45—C44—C49—C48 | 0.4 (2) |
C19—C18—C20—C15 | −54.77 (19) | C47—C48—C50—C45 | 55.5 (2) |
C17—C18—C20—C15 | 54.63 (19) | C49—C48—C50—C45 | −54.19 (19) |
C16—C15—C20—C18 | −57.16 (19) | C46—C45—C50—C48 | −54.90 (19) |
C14—C15—C20—C18 | 52.72 (19) | C44—C45—C50—C48 | 54.46 (19) |
C12—C13—C21—C22 | 14.2 (4) | C42—C43—C51—C56 | −177.2 (2) |
C14—C13—C21—C22 | −167.4 (2) | C44—C43—C51—C56 | 4.8 (3) |
C12—C13—C21—C26 | −164.0 (3) | C42—C43—C51—C52 | 3.1 (4) |
C14—C13—C21—C26 | 14.4 (3) | C44—C43—C51—C52 | −174.9 (2) |
C26—C21—C22—C23 | 1.8 (3) | C56—C51—C52—C53 | 0.5 (3) |
C13—C21—C22—C23 | −176.4 (2) | C43—C51—C52—C53 | −179.8 (2) |
C21—C22—C23—C24 | 0.7 (3) | C51—C52—C53—C54 | 0.0 (3) |
C22—C23—C24—C25 | −2.4 (3) | C52—C53—C54—C55 | −0.4 (3) |
C22—C23—C24—C27 | 176.5 (2) | C52—C53—C54—C57 | −179.4 (2) |
C23—C24—C25—C26 | 1.7 (3) | C53—C54—C55—C56 | 0.5 (3) |
C27—C24—C25—C26 | −177.25 (19) | C57—C54—C55—C56 | 179.4 (2) |
C24—C25—C26—C21 | 0.8 (3) | C54—C55—C56—C51 | 0.0 (3) |
C22—C21—C26—C25 | −2.6 (3) | C52—C51—C56—C55 | −0.5 (3) |
C13—C21—C26—C25 | 175.77 (19) | C43—C51—C56—C55 | 179.76 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O31 | 0.99 | 2.58 | 3.539 (3) | 163 |
C31—H31B···O3 | 0.99 | 2.45 | 3.356 (2) | 152 |
C38—H38A···O1i | 1.00 | 2.54 | 3.412 (2) | 146 |
C1—H1B···O33ii | 0.99 | 2.37 | 3.332 (3) | 164 |
C50—H50A···O2iii | 0.99 | 2.53 | 3.446 (2) | 153 |
C9—H9A···O3iv | 0.98 | 2.59 | 3.570 (3) | 174 |
C27—H27A···O32v | 0.98 | 2.43 | 3.404 (3) | 174 |
C22—H22A···O3 | 0.95 | 2.31 | 3.115 (3) | 142 |
C52—H52A···O33 | 0.95 | 2.33 | 3.129 (3) | 141 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1/2, −y+3/2, −z+2; (v) x, y+1, z. |
Experimental details
(VI) | (VII) | |
Crystal data | ||
Chemical formula | C24H29NO3S2·0.5C4H8O | C27H33NO3S |
Mr | 479.65 | 451.60 |
Crystal system, space group | Trigonal, P3221 | Orthorhombic, P212121 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 12.0797 (17), 12.0797 (17), 28.326 (6) | 11.687 (2), 12.849 (3), 31.547 (6) |
α, β, γ (°) | 90, 90, 120 | 90, 90, 90 |
V (Å3) | 3579.5 (10) | 4737.2 (16) |
Z | 6 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.17 |
Crystal size (mm) | 0.35 × 0.22 × 0.15 | 0.40 × 0.35 × 0.17 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.916, 0.963 | 0.937, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8354, 4207, 3310 | 44242, 9673, 7676 |
Rint | 0.041 | 0.068 |
(sin θ/λ)max (Å−1) | 0.595 | 0.625 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.084, 1.01 | 0.041, 0.096, 1.03 |
No. of reflections | 4207 | 9673 |
No. of parameters | 318 | 583 |
No. of restraints | 4 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.31 | 0.19, −0.31 |
Absolute structure | Flack (1983), 1788 Friedel pairs | Flack (1983), 4291 Friedel pairs |
Absolute structure parameter | −0.03 (7) | −0.02 (5) |
Computer programs: COLLECT (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2i | 1.0 | 2.59 | 3.516 (3) | 154 |
C1—H1B···O3ii | 0.99 | 2.45 | 3.422 (3) | 168 |
C14—H14A···O1iii | 1.00 | 2.66 | 3.500 (3) | 141 |
C1—H1A···O31 | 0.99 | 2.36 | 3.235 (14) | 147 |
Symmetry codes: (i) x−y, −y+1, −z+1/3; (ii) x−y+1, −y+1, −z+1/3; (iii) x−y+1, −y+2, −z+1/3. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3B···O31 | 0.99 | 2.58 | 3.539 (3) | 163 |
C31—H31B···O3 | 0.99 | 2.45 | 3.356 (2) | 152 |
C38—H38A···O1i | 1.00 | 2.54 | 3.412 (2) | 146 |
C1—H1B···O33ii | 0.99 | 2.37 | 3.332 (3) | 164 |
C50—H50A···O2iii | 0.99 | 2.53 | 3.446 (2) | 153 |
C9—H9A···O3iv | 0.98 | 2.59 | 3.570 (3) | 174 |
C27—H27A···O32v | 0.98 | 2.43 | 3.404 (3) | 174 |
C22—H22A···O3 | 0.95 | 2.31 | 3.115 (3) | 142 |
C52—H52A···O33 | 0.95 | 2.33 | 3.129 (3) | 141 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1/2, −y+3/2, −z+2; (v) x, y+1, z. |
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Recently, the metal-catalyzed [2+2] cycloaddition reaction between bicyclic alkenes and alkynes has been utilized by several research groups as a means to generate cyclobutene rings. In terms of an asymmetric version of this process, both a chiral rhodium catalyst (Shibata et al., 2006) and a ruthenium-catalyzed (Villeneuve & Tam, 2004) reaction involving a chiral precursor have produced chiral [2+2] cyclobutene products. The ruthenium-catalyzed [2+2] cycloaddition between norbornene and a phenylactyleneacyl camphorsultam (chiral) yielded two diastereomers in a 131:1 ratio. The absolute stereochemistry of the major diastereomer (V) was established by single-crystal X-ray diffraction (Lough et al.,2004).
As an extension of this study, the Tam group is investigating the selectivity effect of different organic groups attached at the acetylenic position (see scheme). In this paper, we present the results of ruthenium-catalyzed [2+2] cycloadditions of norbornene, (I), with 3-thiophenylacteyleneacylcamphorsultam, (III), and 4-tolylacteyleneacylcamphorsultam, (IV). This yielded the expected complexes C24H29NO3S2.0.5C4H8O, (VI), and C27H33NO3S, (VII). Two diastereomers of (VI) were obtained in a 20:1 ratio, whereas the major stereoisomer of (VII) was obtained in a 104:1 ratio over the minor isomer. The absolute stereochemistry of the major isomers, (VI) and (VII), were established by the single-crystal X-ray diffraction analysis described here.
A view of (VI) is shown in Fig. 1. Elucidation of the X-ray structure establishes the absolute configuration of the following atoms in Fig. 1: C2-S, C5-R, C8-R, C14-S, C15-R, C18-S and C19-R. This is the same configuration as that observed for the phenyl derivative (V). There is a tetrahydrofuran (THF) solvent molecule occluded in the structure. It was modeled at half-occupancy, as it is located on a symmetry element, and was refined giving reasonable displacement parameters; this molecule is involved in the extended structure as discussed below.
There are two chemically identical molecules of (VII) in the asymmetric unit. They are very similar structurally with an r.m.s. fit of 0.207 Å (PLATON; Spek, 2009). As expected, both have the same configuration as that observed for (VI). The absolute configuration, as determined by anomalous dispersion, is as follows: C2-S, C5-R, C8-R, C14-S, C15-R, C18-S and C19-R for one molecule, and C32-S, C35-R, C38-R, C44-S, C45-R, C48-S and C49-R for the second. A structure of one of the molecules of (VII) is shown in Fig. 2. The difference in the two molecules is attributed to their spatially different orientations with respect to one another (see below). The geometric data for both structures (VI) and (VII) are in the normal ranges.
Weak C—H···O interactions in (VI) (see Table 1 for geometric parameters and symmetry codes) tie the molecules together. Perhaps the simplest method to describe the packing is using two `classical model' graph-set descriptors (Bernstein et al., 1995). Firstly, a `chain of rings' is formed between two weak interactions (C8—H8A···O2i and C1—H1B···O3ii) that link molecules together into ribbons along the a axis {motif C22(10)[R22(9)]; Fig. 3}. Secondly, adjacent ribbons are linked together via reciprocating C14—H14A···O1iii interactions, forming a two-dimensional network [motif R22(16)]. There are two further layers in the extension along the c axis, each of which is rotated by 120° with respect to the previous layer. The THF molecule of solvation was refined at half-occupancy, as it is located on a rotational axis; the O atom serves to link the layers together via another weak interaction (C1—H1A···O31).
As with (VI), it is the weak C—H···O interactions that control the geometry observed in the crystal structure of (VII) (Table 2). The nine weak interactions lead to a very extensive set of hydrogen-bonding motifs so only the key graph-set descriptors are noted here. The asymmetric unit contains two molecules, which couple together via two weak interactions (C3—H3B···O31 and C31—H31B···O3) to form an 11-membered ring, and, adjacent to this, a nine-membered ring is formed via C38—H38A···O1i and C1—H1B···O33ii interactions. This quaternary graph set, somewhat similar to (VI), has the motifs C22(10)[R22(11)R22(9)]: a `chain of rings' yielding ribbons along the a axis (Fig. 4). These a-axis ribbons are connected up and down the c axis according to the binary graph-set descriptor C22(12) via C50—H50A···O2iii and C9—H9A···O3iv interactions, thus forming parallel ribbons in the [010] plane. Finally, a full three-dimensional network is established via C27—H27A···O32v and C9—H9A···O3iv interactions, making C22(25) connections along the b axis. For completeness, the last two interactions in Table 2 can be described as motif S(7).
While there are no classical hydrogen-bonding networks in either of these structures, the weak interactions do seem to explain the observed geometry, which is understandable as even a weak hydrogen bond will be stronger than the van der Waals interactions. Unlike the previously published phenyl cycloadduct which shows partial π–π stacking between neighbouring phenyl rings (closest contact 3.64 Å) through secondary orbital overlap interactions (Lough et al., 2004), no such π-stacking interactions between either thiophenyl rings or tolyl rings are observed in these crystal structures.
In the case of the [2+2] cycloaddition, these crystal structures have unambiguously identified which are the major diastereomers formed in the asymmetric cycloaddition. The previous phenyl derivative combined with both the thiophenyl and tolyl derivatives herein reaffirm that [2+2] cycloadditions of bicyclic alkenes and alkynes catalyzed by ruthenium are exclusively exo with respect to their stereochemistry.