Buy article online - an online subscription or single-article purchase is required to access this article.
The structures of methyl 3β-acetoxy-12-oxo-18β-olean-28-oate [C33H52O5, (I)] and methyl 3β-acetoxy-12,19-dioxoolean-9(11),13(18)-dien-28-oate [C33H46O6, (II)] are described. In (I), all rings are in the chair conformation, rings D and E are cis and the other rings trans-fused. In compound (II), only rings A and E are in the chair conformation, ring B has a distorted chair conformation, ring C a distorted half-boat and ring D an insignificantly distorted half-chair conformation.
Supporting information
CCDC references: 150337; 150338
Die Herstellung der Titel Verbindungen, (I) und (II), wurde von Zaprutko (2000) beschrieben.
In beiden Verbindungen wurden alle H-Atome aus Differenz-Fourier-Synthesen ermittelt, ausgenommen die H-Atome der C33A– und C32B-Methylgruppen von (I). Letztere wurden geometrisch berechnet. Alle H-Atome wurden mit Hilfe des Reitermodells verfeinert; Uiso(H) = 1,2Uäq(C). Die H-Atome der Methylgruppen wurden als starre, rotierende Gruppen verfeinert. Bei der Bestimmung der absoluten Konfiguration von (I) bzw. (II) wurden 4353 bzw. 2445 Friedel-Reflexenpaare ausgewertet. Der Ursprung für Verbindung (II) wurde nach der Methode von Flack & Schwarzenbach (1988) festgelegt. Die minimalen H···H Atom-Abstände betragen 1,95 [Molekül A, (I)] bzw. 1,98 Å [Molekül B, (I); (II)].
For both compounds, data collection: KM-4 Software (Kuma Diffraction, 1991); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (I); ORTEPII (Johnson, 1976) for (II). For both compounds, software used to prepare material for publication: SHELXL97.
(I) Methyl 3
β-acetoxy-12-oxo-18
β-olean-28-oate
top
Crystal data top
C33H52O5 | Dx = 1.121 Mg m−3 |
Mr = 528.75 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 46 reflections |
a = 7.0662 (16) Å | θ = 12.6–26.3° |
b = 22.083 (3) Å | µ = 0.58 mm−1 |
c = 40.141 (5) Å | T = 293 K |
V = 6263.7 (18) Å3 | Needle, colourless |
Z = 8 | 0.50 × 0.14 × 0.09 mm |
F(000) = 2320 | |
Data collection top
Kuma Diffraction KM-4 diffractometer | Rint = 0.017 |
Radiation source: fine-focus sealed tube | θmax = 65.1°, θmin = 2.2° |
Graphite monochromator | h = −7→7 |
ω/2θ scans | k = 0→25 |
10738 measured reflections | l = 0→47 |
10265 independent reflections | 2 standard reflections every 100 reflections |
7013 reflections with I > 2σ(I) | intensity decay: 11.3% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0813P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.130 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.20 e Å−3 |
10265 reflections | Δρmin = −0.18 e Å−3 |
704 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00025 (6) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.0 (2) |
Crystal data top
C33H52O5 | V = 6263.7 (18) Å3 |
Mr = 528.75 | Z = 8 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 7.0662 (16) Å | µ = 0.58 mm−1 |
b = 22.083 (3) Å | T = 293 K |
c = 40.141 (5) Å | 0.50 × 0.14 × 0.09 mm |
Data collection top
Kuma Diffraction KM-4 diffractometer | Rint = 0.017 |
10738 measured reflections | 2 standard reflections every 100 reflections |
10265 independent reflections | intensity decay: 11.3% |
7013 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | Δρmax = 0.20 e Å−3 |
S = 1.08 | Δρmin = −0.18 e Å−3 |
10265 reflections | Absolute structure: Flack (1983) |
704 parameters | Absolute structure parameter: 0.0 (2) |
0 restraints | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.4257 (2) | 0.25620 (7) | 0.05032 (4) | 0.0597 (4) | |
O2a | 0.3864 (3) | 0.28635 (10) | 0.10255 (5) | 0.0936 (6) | |
O3A | 0.1264 (3) | −0.10117 (9) | 0.12945 (5) | 0.0889 (6) | |
O4A | 0.2997 (5) | −0.25256 (14) | 0.05773 (8) | 0.1321 (10) | |
O5A | 0.5927 (5) | −0.27344 (12) | 0.04357 (7) | 0.1301 (10) | |
C1A | 0.2323 (3) | 0.10562 (11) | 0.07847 (6) | 0.0621 (6) | |
H1A | 0.1033 | 0.0916 | 0.0813 | 0.075* | |
H1B | 0.2931 | 0.1047 | 0.1001 | 0.075* | |
C2A | 0.2287 (3) | 0.17072 (11) | 0.06593 (6) | 0.0631 (6) | |
H2A | 0.1599 | 0.1727 | 0.0451 | 0.076* | |
H2B | 0.1641 | 0.1962 | 0.0820 | 0.076* | |
C3A | 0.4284 (3) | 0.19339 (11) | 0.06084 (6) | 0.0549 (5) | |
H3A | 0.4949 | 0.1911 | 0.0822 | 0.066* | |
C4A | 0.5409 (3) | 0.15687 (10) | 0.03526 (5) | 0.0522 (5) | |
C5A | 0.5349 (3) | 0.09001 (10) | 0.04694 (5) | 0.0511 (5) | |
H5A | 0.6008 | 0.0903 | 0.0684 | 0.061* | |
C6A | 0.6486 (3) | 0.04619 (11) | 0.02571 (6) | 0.0609 (6) | |
H6A | 0.5788 | 0.0371 | 0.0055 | 0.073* | |
H6B | 0.7672 | 0.0651 | 0.0194 | 0.073* | |
C7A | 0.6892 (3) | −0.01221 (11) | 0.04423 (7) | 0.0643 (6) | |
H7A | 0.7717 | −0.0033 | 0.0629 | 0.077* | |
H7B | 0.7568 | −0.0394 | 0.0295 | 0.077* | |
C8A | 0.5109 (3) | −0.04485 (10) | 0.05735 (6) | 0.0557 (6) | |
C9A | 0.3806 (3) | 0.00212 (10) | 0.07449 (6) | 0.0534 (5) | |
H9A | 0.4515 | 0.0153 | 0.0942 | 0.064* | |
C10A | 0.3368 (3) | 0.06210 (11) | 0.05500 (6) | 0.0538 (5) | |
C11A | 0.2026 (3) | −0.02887 (11) | 0.08859 (7) | 0.0661 (7) | |
H11A | 0.1407 | −0.0007 | 0.1036 | 0.079* | |
H11B | 0.1163 | −0.0364 | 0.0703 | 0.079* | |
C12A | 0.2329 (3) | −0.08725 (11) | 0.10683 (7) | 0.0636 (6) | |
C13A | 0.3850 (4) | −0.12913 (11) | 0.09435 (6) | 0.0608 (6) | |
H13A | 0.3361 | −0.1436 | 0.0729 | 0.073* | |
C14A | 0.5676 (3) | −0.09381 (11) | 0.08484 (6) | 0.0580 (6) | |
C15A | 0.7142 (4) | −0.13912 (12) | 0.07077 (7) | 0.0721 (7) | |
H15A | 0.6760 | −0.1506 | 0.0484 | 0.087* | |
H15B | 0.8357 | −0.1189 | 0.0691 | 0.087* | |
C16A | 0.7382 (4) | −0.19603 (13) | 0.09144 (9) | 0.0846 (9) | |
H16A | 0.7911 | −0.1853 | 0.1129 | 0.102* | |
H16B | 0.8271 | −0.2228 | 0.0804 | 0.102* | |
C17A | 0.5495 (4) | −0.22991 (12) | 0.09680 (8) | 0.0802 (8) | |
C18A | 0.4098 (4) | −0.18741 (11) | 0.11504 (7) | 0.0700 (7) | |
H18A | 0.2869 | −0.2080 | 0.1147 | 0.084* | |
C19A | 0.4607 (4) | −0.17893 (13) | 0.15148 (7) | 0.0811 (8) | |
H19A | 0.3668 | −0.1529 | 0.1617 | 0.097* | |
H19B | 0.5818 | −0.1584 | 0.1528 | 0.097* | |
C20A | 0.4725 (6) | −0.23781 (15) | 0.17136 (8) | 0.0984 (11) | |
C21A | 0.6193 (6) | −0.27842 (17) | 0.15384 (10) | 0.1151 (13) | |
H21A | 0.7432 | −0.2599 | 0.1560 | 0.138* | |
H21B | 0.6235 | −0.3173 | 0.1651 | 0.138* | |
C22A | 0.5790 (6) | −0.28859 (14) | 0.11809 (10) | 0.1107 (13) | |
H22A | 0.4660 | −0.3133 | 0.1163 | 0.133* | |
H22B | 0.6829 | −0.3115 | 0.1086 | 0.133* | |
C23A | 0.7467 (3) | 0.17965 (12) | 0.03700 (7) | 0.0652 (6) | |
H23A | 0.7488 | 0.2228 | 0.0341 | 0.078* | |
H23B | 0.8197 | 0.1609 | 0.0197 | 0.078* | |
H23C | 0.7998 | 0.1695 | 0.0583 | 0.078* | |
C24A | 0.4685 (4) | 0.16767 (12) | −0.00013 (6) | 0.0657 (6) | |
H24A | 0.3332 | 0.1638 | −0.0005 | 0.079* | |
H24B | 0.5234 | 0.1383 | −0.0149 | 0.079* | |
H24C | 0.5033 | 0.2077 | −0.0072 | 0.079* | |
C25A | 0.2121 (4) | 0.05261 (12) | 0.02414 (7) | 0.0697 (7) | |
H25A | 0.1172 | 0.0227 | 0.0289 | 0.084* | |
H25B | 0.2890 | 0.0390 | 0.0059 | 0.084* | |
H25C | 0.1520 | 0.0901 | 0.0183 | 0.084* | |
C26A | 0.4139 (4) | −0.07485 (13) | 0.02723 (6) | 0.0738 (7) | |
H26A | 0.4191 | −0.0480 | 0.0085 | 0.089* | |
H26B | 0.2842 | −0.0833 | 0.0326 | 0.089* | |
H26C | 0.4779 | −0.1119 | 0.0219 | 0.089* | |
C27A | 0.6512 (4) | −0.06277 (12) | 0.11610 (7) | 0.0683 (7) | |
H27A | 0.7329 | −0.0906 | 0.1275 | 0.082* | |
H27B | 0.5502 | −0.0507 | 0.1307 | 0.082* | |
H27C | 0.7222 | −0.0277 | 0.1095 | 0.082* | |
C28A | 0.4645 (7) | −0.25178 (14) | 0.06431 (9) | 0.0943 (10) | |
C29A | 0.5409 (8) | −0.2239 (2) | 0.20643 (9) | 0.1384 (18) | |
H29A | 0.4473 | −0.2001 | 0.2178 | 0.166* | |
H29B | 0.6574 | −0.2016 | 0.2053 | 0.166* | |
H29C | 0.5612 | −0.2611 | 0.2183 | 0.166* | |
C30A | 0.2818 (7) | −0.26909 (17) | 0.17396 (10) | 0.1212 (14) | |
H30A | 0.2941 | −0.3049 | 0.1873 | 0.145* | |
H30B | 0.2386 | −0.2800 | 0.1521 | 0.145* | |
H30C | 0.1921 | −0.2421 | 0.1841 | 0.145* | |
C31A | 0.4065 (4) | 0.29817 (12) | 0.07359 (7) | 0.0661 (7) | |
C32A | 0.4179 (5) | 0.36040 (12) | 0.06009 (8) | 0.0867 (8) | |
H32A | 0.3032 | 0.3697 | 0.0483 | 0.104* | |
H32B | 0.5234 | 0.3633 | 0.0451 | 0.104* | |
H32C | 0.4344 | 0.3886 | 0.0781 | 0.104* | |
C33A | 0.5246 (10) | −0.2989 (2) | 0.01258 (12) | 0.176 (3) | |
H33A | 0.4199 | −0.3254 | 0.0170 | 0.211* | |
H33B | 0.6245 | −0.3214 | 0.0021 | 0.211* | |
H33C | 0.4844 | −0.2669 | −0.0019 | 0.211* | |
O1B | 1.0702 (5) | −0.96338 (11) | 0.20038 (7) | 0.1455 (13) | |
O2B | 1.3473 (8) | −0.9789 (2) | 0.17819 (14) | 0.217 (2) | |
O3B | 0.8790 (4) | −0.63328 (9) | 0.08424 (4) | 0.0903 (6) | |
O4B | 0.5450 (3) | −0.49440 (11) | 0.15137 (6) | 0.0981 (7) | |
O5B | 0.6756 (3) | −0.45695 (14) | 0.19632 (6) | 0.1219 (10) | |
C1B | 0.9359 (5) | −0.83188 (12) | 0.14611 (7) | 0.0833 (9) | |
H1C | 0.8521 | −0.8300 | 0.1270 | 0.100* | |
H1D | 1.0617 | −0.8205 | 0.1387 | 0.100* | |
C2B | 0.9410 (6) | −0.89676 (15) | 0.15921 (8) | 0.1056 (12) | |
H2C | 0.8139 | −0.9096 | 0.1649 | 0.127* | |
H2D | 0.9885 | −0.9235 | 0.1420 | 0.127* | |
C3B | 1.0661 (6) | −0.90107 (15) | 0.18949 (9) | 0.1022 (12) | |
H3B | 1.1947 | −0.8890 | 0.1832 | 0.123* | |
C4B | 1.0022 (5) | −0.86193 (14) | 0.21843 (7) | 0.0832 (8) | |
C5B | 0.9868 (4) | −0.79626 (12) | 0.20480 (6) | 0.0688 (7) | |
H5B | 1.1162 | −0.7863 | 0.1980 | 0.083* | |
C6B | 0.9407 (4) | −0.74945 (14) | 0.23099 (6) | 0.0761 (8) | |
H6C | 1.0131 | −0.7579 | 0.2510 | 0.091* | |
H6D | 0.8074 | −0.7519 | 0.2366 | 0.091* | |
C7B | 0.9860 (4) | −0.68606 (13) | 0.21889 (6) | 0.0702 (7) | |
H7C | 1.1222 | −0.6823 | 0.2166 | 0.084* | |
H7D | 0.9458 | −0.6573 | 0.2357 | 0.084* | |
C8B | 0.8935 (3) | −0.66890 (11) | 0.18572 (5) | 0.0557 (6) | |
C9B | 0.9194 (3) | −0.72118 (11) | 0.16055 (6) | 0.0585 (6) | |
H9B | 1.0563 | −0.7229 | 0.1568 | 0.070* | |
C10B | 0.8674 (4) | −0.78592 (12) | 0.17275 (6) | 0.0659 (6) | |
C11B | 0.8373 (5) | −0.70527 (12) | 0.12670 (6) | 0.0743 (8) | |
H11C | 0.8891 | −0.7334 | 0.1105 | 0.089* | |
H11D | 0.7018 | −0.7122 | 0.1276 | 0.089* | |
C12B | 0.8692 (4) | −0.64224 (12) | 0.11391 (6) | 0.0637 (6) | |
C13B | 0.8714 (3) | −0.59156 (11) | 0.13928 (5) | 0.0562 (6) | |
H13B | 0.7407 | −0.5902 | 0.1474 | 0.067* | |
C14B | 0.9870 (3) | −0.61032 (11) | 0.17036 (5) | 0.0543 (6) | |
C15B | 0.9898 (3) | −0.55760 (12) | 0.19551 (6) | 0.0647 (6) | |
H15C | 0.8690 | −0.5565 | 0.2070 | 0.078* | |
H15D | 1.0867 | −0.5656 | 0.2120 | 0.078* | |
C16B | 1.0263 (3) | −0.49614 (12) | 0.18039 (6) | 0.0636 (6) | |
H16C | 1.1538 | −0.4952 | 0.1714 | 0.076* | |
H16D | 1.0183 | −0.4656 | 0.1977 | 0.076* | |
C17B | 0.8864 (4) | −0.48045 (11) | 0.15269 (7) | 0.0643 (6) | |
C18B | 0.9039 (4) | −0.52792 (11) | 0.12487 (6) | 0.0630 (6) | |
H18B | 0.7985 | −0.5204 | 0.1096 | 0.076* | |
C19B | 1.0857 (4) | −0.51840 (12) | 0.10450 (6) | 0.0738 (7) | |
H19C | 1.1939 | −0.5266 | 0.1187 | 0.089* | |
H19D | 1.0879 | −0.5474 | 0.0864 | 0.089* | |
C20B | 1.1057 (6) | −0.45480 (14) | 0.09005 (8) | 0.0910 (9) | |
C21B | 1.0982 (5) | −0.40955 (13) | 0.11831 (8) | 0.0905 (9) | |
H21C | 1.1032 | −0.3689 | 0.1092 | 0.109* | |
H21D | 1.2084 | −0.4150 | 0.1324 | 0.109* | |
C22B | 0.9190 (5) | −0.41604 (13) | 0.13955 (8) | 0.0849 (8) | |
H22C | 0.8105 | −0.4040 | 0.1263 | 0.102* | |
H22D | 0.9275 | −0.3885 | 0.1583 | 0.102* | |
C23B | 1.1585 (6) | −0.86436 (18) | 0.24507 (10) | 0.1200 (13) | |
H23D | 1.1865 | −0.9058 | 0.2503 | 0.144* | |
H23E | 1.1162 | −0.8439 | 0.2648 | 0.144* | |
H23F | 1.2704 | −0.8449 | 0.2367 | 0.144* | |
C24B | 0.8185 (6) | −0.88593 (15) | 0.23389 (8) | 0.0976 (11) | |
H24D | 0.7261 | −0.8920 | 0.2167 | 0.117* | |
H24E | 0.7712 | −0.8571 | 0.2497 | 0.117* | |
H24F | 0.8431 | −0.9237 | 0.2449 | 0.117* | |
C25B | 0.6539 (4) | −0.79569 (14) | 0.17764 (8) | 0.0847 (8) | |
H25D | 0.6264 | −0.8382 | 0.1770 | 0.102* | |
H25E | 0.5858 | −0.7755 | 0.1602 | 0.102* | |
H25F | 0.6162 | −0.7794 | 0.1988 | 0.102* | |
C26B | 0.6806 (4) | −0.65751 (13) | 0.19327 (7) | 0.0748 (7) | |
H26D | 0.6374 | −0.6862 | 0.2095 | 0.090* | |
H26E | 0.6084 | −0.6621 | 0.1732 | 0.090* | |
H26F | 0.6646 | −0.6172 | 0.2018 | 0.090* | |
C27B | 1.1964 (3) | −0.62222 (12) | 0.16039 (6) | 0.0638 (6) | |
H27D | 1.2632 | −0.5844 | 0.1592 | 0.077* | |
H27E | 1.2003 | −0.6418 | 0.1390 | 0.077* | |
H27F | 1.2549 | −0.6478 | 0.1768 | 0.077* | |
C28B | 0.6841 (4) | −0.47899 (13) | 0.16603 (8) | 0.0745 (8) | |
C29B | 1.2974 (7) | −0.45016 (19) | 0.07301 (10) | 0.1288 (16) | |
H29D | 1.3134 | −0.4101 | 0.0642 | 0.155* | |
H29E | 1.3041 | −0.4791 | 0.0552 | 0.155* | |
H29F | 1.3958 | −0.4583 | 0.0889 | 0.155* | |
C30B | 0.9489 (8) | −0.44198 (17) | 0.06432 (9) | 0.1265 (15) | |
H30D | 0.9646 | −0.4019 | 0.0555 | 0.152* | |
H30E | 0.8274 | −0.4451 | 0.0749 | 0.152* | |
H30F | 0.9570 | −0.4709 | 0.0465 | 0.152* | |
C31B | 1.2227 (13) | −0.9967 (3) | 0.19477 (13) | 0.177 (3) | |
C32B | 1.2024 (15) | −1.0577 (2) | 0.20881 (12) | 0.264 (6) | |
H32D | 1.1164 | −1.0808 | 0.1953 | 0.317* | |
H32E | 1.1539 | −1.0549 | 0.2311 | 0.317* | |
H32F | 1.3236 | −1.0773 | 0.2092 | 0.317* | |
C33B | 0.4868 (5) | −0.4520 (2) | 0.21064 (12) | 0.148 (2) | |
H33D | 0.4050 | −0.4314 | 0.1953 | 0.177* | |
H33E | 0.4932 | −0.4296 | 0.2311 | 0.177* | |
H33F | 0.4378 | −0.4918 | 0.2150 | 0.177* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0501 (9) | 0.0643 (10) | 0.0648 (9) | 0.0060 (7) | −0.0004 (7) | 0.0012 (8) |
O2A | 0.0986 (16) | 0.1079 (15) | 0.0744 (13) | 0.0301 (13) | 0.0023 (12) | −0.0154 (11) |
O3A | 0.0547 (11) | 0.1003 (13) | 0.1117 (14) | 0.0184 (10) | 0.0265 (11) | 0.0398 (12) |
O4A | 0.117 (2) | 0.143 (2) | 0.137 (2) | −0.0057 (19) | 0.0102 (19) | −0.0380 (18) |
O5A | 0.137 (2) | 0.1236 (19) | 0.129 (2) | −0.0030 (18) | 0.0503 (19) | −0.0352 (17) |
C1A | 0.0342 (12) | 0.0722 (15) | 0.0800 (16) | 0.0129 (11) | 0.0142 (11) | 0.0147 (13) |
C2A | 0.0370 (13) | 0.0738 (16) | 0.0784 (16) | 0.0141 (11) | 0.0121 (11) | 0.0097 (13) |
C3A | 0.0388 (12) | 0.0664 (14) | 0.0597 (13) | 0.0082 (10) | 0.0028 (10) | 0.0058 (11) |
C4A | 0.0326 (11) | 0.0668 (14) | 0.0572 (12) | 0.0027 (9) | 0.0035 (9) | 0.0075 (11) |
C5A | 0.0279 (11) | 0.0666 (14) | 0.0589 (12) | 0.0058 (9) | 0.0033 (9) | 0.0055 (11) |
C6A | 0.0382 (12) | 0.0686 (15) | 0.0760 (16) | 0.0053 (10) | 0.0157 (11) | 0.0062 (12) |
C7A | 0.0394 (13) | 0.0680 (15) | 0.0856 (17) | 0.0121 (11) | 0.0198 (11) | 0.0062 (13) |
C8A | 0.0394 (12) | 0.0600 (14) | 0.0677 (14) | 0.0043 (10) | 0.0086 (11) | 0.0045 (11) |
C9A | 0.0282 (11) | 0.0647 (14) | 0.0674 (14) | 0.0057 (10) | 0.0066 (10) | 0.0092 (11) |
C10A | 0.0299 (11) | 0.0657 (14) | 0.0658 (13) | 0.0049 (10) | 0.0052 (10) | 0.0116 (11) |
C11A | 0.0349 (12) | 0.0725 (15) | 0.0910 (18) | 0.0068 (10) | 0.0138 (12) | 0.0166 (14) |
C12A | 0.0384 (13) | 0.0742 (16) | 0.0781 (17) | 0.0016 (11) | 0.0044 (12) | 0.0118 (13) |
C13A | 0.0489 (14) | 0.0612 (14) | 0.0723 (14) | 0.0050 (11) | 0.0062 (11) | 0.0074 (12) |
C14A | 0.0359 (12) | 0.0634 (14) | 0.0747 (15) | 0.0101 (10) | 0.0052 (10) | 0.0055 (12) |
C15A | 0.0496 (15) | 0.0681 (16) | 0.0986 (19) | 0.0117 (12) | 0.0170 (13) | 0.0055 (14) |
C16A | 0.0672 (18) | 0.0720 (17) | 0.115 (2) | 0.0252 (14) | 0.0206 (17) | 0.0088 (16) |
C17A | 0.083 (2) | 0.0625 (16) | 0.095 (2) | 0.0167 (14) | 0.0212 (17) | 0.0101 (15) |
C18A | 0.0642 (16) | 0.0632 (15) | 0.0825 (17) | 0.0107 (13) | 0.0125 (14) | 0.0120 (13) |
C19A | 0.083 (2) | 0.0771 (18) | 0.0831 (18) | 0.0253 (15) | 0.0107 (16) | 0.0130 (15) |
C20A | 0.115 (3) | 0.093 (2) | 0.088 (2) | 0.042 (2) | 0.0201 (19) | 0.0302 (18) |
C21A | 0.133 (3) | 0.099 (2) | 0.113 (3) | 0.057 (2) | 0.032 (2) | 0.037 (2) |
C22A | 0.133 (3) | 0.0743 (19) | 0.125 (3) | 0.042 (2) | 0.044 (3) | 0.0238 (19) |
C23A | 0.0353 (12) | 0.0735 (15) | 0.0869 (17) | 0.0009 (11) | 0.0056 (12) | 0.0073 (14) |
C24A | 0.0556 (15) | 0.0772 (16) | 0.0645 (14) | 0.0057 (12) | 0.0054 (12) | 0.0087 (12) |
C25A | 0.0398 (13) | 0.0808 (17) | 0.0883 (19) | 0.0024 (12) | −0.0069 (12) | 0.0206 (15) |
C26A | 0.0710 (17) | 0.0796 (17) | 0.0708 (16) | 0.0046 (14) | 0.0036 (14) | 0.0011 (13) |
C27A | 0.0458 (14) | 0.0744 (16) | 0.0846 (17) | 0.0132 (12) | −0.0063 (13) | 0.0085 (14) |
C28A | 0.111 (3) | 0.0692 (18) | 0.102 (2) | 0.0039 (19) | 0.030 (2) | −0.0028 (17) |
C29A | 0.174 (5) | 0.144 (3) | 0.097 (3) | 0.059 (3) | 0.011 (3) | 0.039 (3) |
C30A | 0.136 (4) | 0.097 (2) | 0.131 (3) | 0.021 (2) | 0.047 (3) | 0.035 (2) |
C31A | 0.0447 (14) | 0.0794 (17) | 0.0742 (17) | 0.0138 (12) | −0.0075 (12) | −0.0082 (15) |
C32A | 0.0756 (19) | 0.0739 (18) | 0.111 (2) | 0.0113 (15) | −0.0145 (18) | −0.0104 (17) |
C33A | 0.214 (7) | 0.174 (5) | 0.138 (4) | −0.038 (4) | 0.062 (4) | −0.071 (4) |
O1B | 0.208 (3) | 0.0907 (16) | 0.138 (2) | 0.059 (2) | 0.077 (2) | 0.0451 (15) |
O2B | 0.222 (5) | 0.183 (4) | 0.245 (5) | 0.125 (4) | 0.059 (4) | 0.015 (4) |
O3B | 0.1343 (19) | 0.0833 (12) | 0.0534 (10) | −0.0002 (12) | −0.0190 (11) | −0.0017 (9) |
O4B | 0.0534 (12) | 0.1265 (17) | 0.1146 (16) | 0.0142 (11) | −0.0160 (12) | −0.0260 (14) |
O5B | 0.0444 (11) | 0.190 (3) | 0.1316 (19) | 0.0092 (13) | 0.0064 (12) | −0.0880 (19) |
C1B | 0.111 (2) | 0.0700 (17) | 0.0686 (16) | 0.0094 (16) | 0.0210 (16) | 0.0042 (14) |
C2B | 0.153 (4) | 0.077 (2) | 0.087 (2) | 0.014 (2) | 0.043 (2) | 0.0032 (17) |
C3B | 0.122 (3) | 0.087 (2) | 0.097 (2) | 0.033 (2) | 0.045 (2) | 0.0322 (18) |
C4B | 0.082 (2) | 0.092 (2) | 0.0756 (17) | 0.0147 (16) | 0.0221 (16) | 0.0261 (16) |
C5B | 0.0556 (15) | 0.0864 (18) | 0.0644 (14) | 0.0110 (13) | 0.0122 (12) | 0.0168 (13) |
C6B | 0.0701 (18) | 0.104 (2) | 0.0542 (13) | 0.0061 (16) | 0.0054 (12) | 0.0122 (14) |
C7B | 0.0651 (17) | 0.0930 (18) | 0.0524 (13) | 0.0092 (14) | −0.0009 (12) | 0.0021 (13) |
C8B | 0.0390 (12) | 0.0743 (15) | 0.0539 (12) | 0.0102 (10) | 0.0016 (10) | −0.0018 (11) |
C9B | 0.0525 (13) | 0.0707 (15) | 0.0523 (12) | 0.0088 (11) | 0.0019 (10) | 0.0009 (11) |
C10B | 0.0612 (15) | 0.0751 (16) | 0.0613 (14) | 0.0073 (12) | 0.0080 (12) | 0.0031 (12) |
C11B | 0.093 (2) | 0.0700 (16) | 0.0604 (15) | 0.0053 (14) | −0.0125 (14) | −0.0062 (13) |
C12B | 0.0638 (16) | 0.0725 (16) | 0.0549 (14) | 0.0098 (13) | −0.0156 (12) | −0.0040 (12) |
C13B | 0.0465 (13) | 0.0673 (14) | 0.0548 (12) | 0.0134 (10) | −0.0086 (10) | −0.0058 (11) |
C14B | 0.0384 (12) | 0.0707 (15) | 0.0538 (12) | 0.0104 (10) | −0.0027 (10) | −0.0038 (11) |
C15B | 0.0488 (13) | 0.0893 (18) | 0.0561 (13) | 0.0050 (13) | −0.0043 (11) | −0.0122 (13) |
C16B | 0.0470 (13) | 0.0759 (16) | 0.0681 (14) | 0.0080 (11) | −0.0040 (11) | −0.0176 (13) |
C17B | 0.0493 (14) | 0.0690 (15) | 0.0748 (15) | 0.0144 (11) | −0.0054 (12) | −0.0095 (13) |
C18B | 0.0569 (15) | 0.0693 (15) | 0.0627 (14) | 0.0140 (12) | −0.0094 (12) | −0.0084 (12) |
C19B | 0.0850 (19) | 0.0716 (16) | 0.0646 (15) | 0.0106 (14) | 0.0024 (14) | −0.0058 (13) |
C20B | 0.122 (3) | 0.0780 (19) | 0.0726 (18) | 0.0064 (18) | 0.0084 (19) | 0.0082 (15) |
C21B | 0.104 (2) | 0.0674 (17) | 0.100 (2) | 0.0031 (17) | 0.0026 (19) | 0.0027 (16) |
C22B | 0.082 (2) | 0.0723 (18) | 0.101 (2) | 0.0164 (15) | −0.0075 (17) | −0.0126 (16) |
C23B | 0.113 (3) | 0.128 (3) | 0.120 (3) | 0.024 (2) | −0.004 (2) | 0.052 (2) |
C24B | 0.113 (3) | 0.092 (2) | 0.088 (2) | 0.0030 (19) | 0.0430 (19) | 0.0227 (18) |
C25B | 0.0649 (18) | 0.089 (2) | 0.100 (2) | −0.0082 (14) | −0.0044 (16) | 0.0065 (17) |
C26B | 0.0444 (14) | 0.0880 (19) | 0.0920 (19) | 0.0102 (12) | 0.0111 (13) | −0.0032 (15) |
C27B | 0.0422 (13) | 0.0803 (16) | 0.0690 (15) | 0.0136 (11) | 0.0028 (11) | 0.0070 (13) |
C28B | 0.0537 (17) | 0.0815 (18) | 0.088 (2) | 0.0179 (13) | −0.0095 (14) | −0.0208 (16) |
C29B | 0.162 (4) | 0.109 (3) | 0.115 (3) | −0.014 (3) | 0.051 (3) | 0.012 (2) |
C30B | 0.193 (5) | 0.094 (2) | 0.093 (2) | 0.013 (3) | −0.030 (3) | 0.019 (2) |
C31B | 0.284 (9) | 0.137 (4) | 0.109 (3) | 0.119 (6) | 0.061 (4) | 0.028 (3) |
C32B | 0.542 (16) | 0.124 (4) | 0.126 (3) | 0.168 (7) | 0.090 (6) | 0.046 (3) |
C33B | 0.0498 (19) | 0.228 (5) | 0.165 (4) | 0.006 (3) | 0.020 (2) | −0.098 (4) |
Geometric parameters (Å, º) top
O1A—C31A | 1.323 (3) | O1B—C31B | 1.324 (7) |
O1A—C3A | 1.450 (3) | O1B—C3B | 1.444 (4) |
O2A—C31A | 1.200 (3) | O2B—C31B | 1.171 (8) |
O3A—C12A | 1.218 (3) | O3B—C12B | 1.209 (3) |
O4A—C28A | 1.194 (5) | O4B—C28B | 1.195 (3) |
O5A—C28A | 1.320 (4) | O5B—C28B | 1.311 (3) |
O5A—C33A | 1.448 (5) | O5B—C33B | 1.457 (4) |
C1A—C2A | 1.524 (4) | C1B—C2B | 1.527 (4) |
C1A—C10A | 1.535 (3) | C1B—C10B | 1.552 (4) |
C2A—C3A | 1.511 (3) | C2B—C3B | 1.506 (6) |
C3A—C4A | 1.529 (3) | C3B—C4B | 1.517 (4) |
C4A—C24A | 1.529 (3) | C4B—C24B | 1.533 (5) |
C4A—C23A | 1.540 (3) | C4B—C23B | 1.538 (5) |
C4A—C5A | 1.550 (3) | C4B—C5B | 1.554 (4) |
C5A—C6A | 1.519 (3) | C5B—C6B | 1.510 (4) |
C5A—C10A | 1.563 (3) | C5B—C10B | 1.555 (4) |
C6A—C7A | 1.516 (3) | C6B—C7B | 1.516 (4) |
C7A—C8A | 1.544 (3) | C7B—C8B | 1.531 (3) |
C8A—C26A | 1.540 (4) | C8B—C9B | 1.545 (3) |
C8A—C9A | 1.548 (3) | C8B—C26B | 1.555 (3) |
C8A—C14A | 1.596 (3) | C8B—C14B | 1.578 (3) |
C9A—C11A | 1.540 (3) | C9B—C11B | 1.519 (3) |
C9A—C10A | 1.569 (3) | C9B—C10B | 1.555 (4) |
C10A—C25A | 1.534 (3) | C10B—C25B | 1.536 (4) |
C11A—C12A | 1.498 (4) | C11B—C12B | 1.501 (4) |
C12A—C13A | 1.504 (3) | C12B—C13B | 1.513 (3) |
C13A—C18A | 1.542 (3) | C13B—C18B | 1.537 (4) |
C13A—C14A | 1.555 (3) | C13B—C14B | 1.548 (3) |
C14A—C27A | 1.547 (3) | C14B—C15B | 1.541 (3) |
C14A—C15A | 1.547 (3) | C14B—C27B | 1.555 (3) |
C15A—C16A | 1.515 (4) | C15B—C16B | 1.509 (4) |
C16A—C17A | 1.544 (5) | C16B—C17B | 1.528 (4) |
C17A—C28A | 1.515 (5) | C17B—C28B | 1.527 (4) |
C17A—C18A | 1.546 (4) | C17B—C22B | 1.535 (4) |
C17A—C22A | 1.566 (4) | C17B—C18B | 1.537 (3) |
C18A—C19A | 1.518 (4) | C18B—C19B | 1.537 (4) |
C19A—C20A | 1.528 (4) | C19B—C20B | 1.526 (4) |
C20A—C30A | 1.518 (6) | C20B—C21B | 1.513 (4) |
C20A—C29A | 1.520 (5) | C20B—C29B | 1.521 (6) |
C20A—C21A | 1.541 (5) | C20B—C30B | 1.541 (5) |
C21A—C22A | 1.480 (6) | C21B—C22B | 1.533 (5) |
C31A—C32A | 1.479 (4) | C31B—C32B | 1.468 (7) |
| | | |
C31A—O1A—C3A | 117.76 (19) | C31B—O1B—C3B | 119.6 (4) |
C28A—O5A—C33A | 117.0 (4) | C28B—O5B—C33B | 115.8 (3) |
C2A—C1A—C10A | 113.33 (19) | C2B—C1B—C10B | 112.6 (2) |
C3A—C2A—C1A | 109.97 (18) | C3B—C2B—C1B | 110.6 (3) |
O1A—C3A—C2A | 110.10 (18) | O1B—C3B—C2B | 108.4 (3) |
O1A—C3A—C4A | 108.42 (17) | O1B—C3B—C4B | 108.5 (2) |
C2A—C3A—C4A | 113.7 (2) | C2B—C3B—C4B | 114.1 (3) |
C3A—C4A—C24A | 111.58 (18) | C3B—C4B—C24B | 111.4 (3) |
C3A—C4A—C23A | 106.7 (2) | C3B—C4B—C23B | 107.4 (3) |
C24A—C4A—C23A | 107.9 (2) | C24B—C4B—C23B | 108.3 (2) |
C3A—C4A—C5A | 106.57 (17) | C3B—C4B—C5B | 106.4 (2) |
C24A—C4A—C5A | 114.9 (2) | C24B—C4B—C5B | 113.9 (3) |
C23A—C4A—C5A | 108.87 (18) | C23B—C4B—C5B | 109.1 (3) |
C6A—C5A—C4A | 114.99 (17) | C6B—C5B—C4B | 114.1 (2) |
C6A—C5A—C10A | 109.79 (18) | C6B—C5B—C10B | 111.0 (2) |
C4A—C5A—C10A | 117.58 (17) | C4B—C5B—C10B | 117.8 (2) |
C7A—C6A—C5A | 111.53 (19) | C5B—C6B—C7B | 111.3 (2) |
C6A—C7A—C8A | 114.20 (18) | C6B—C7B—C8B | 114.6 (2) |
C26A—C8A—C7A | 107.2 (2) | C7B—C8B—C9B | 109.45 (19) |
C26A—C8A—C9A | 111.9 (2) | C7B—C8B—C26B | 106.5 (2) |
C7A—C8A—C9A | 108.91 (18) | C9B—C8B—C26B | 111.3 (2) |
C26A—C8A—C14A | 111.31 (19) | C7B—C8B—C14B | 111.3 (2) |
C7A—C8A—C14A | 110.31 (19) | C9B—C8B—C14B | 107.89 (17) |
C9A—C8A—C14A | 107.22 (18) | C26B—C8B—C14B | 110.4 (2) |
C11A—C9A—C8A | 110.56 (19) | C11B—C9B—C8B | 111.5 (2) |
C11A—C9A—C10A | 113.42 (17) | C11B—C9B—C10B | 113.8 (2) |
C8A—C9A—C10A | 117.46 (18) | C8B—C9B—C10B | 116.94 (19) |
C25A—C10A—C1A | 107.74 (19) | C25B—C10B—C1B | 107.6 (3) |
C25A—C10A—C5A | 113.65 (19) | C25B—C10B—C5B | 114.0 (2) |
C1A—C10A—C5A | 108.10 (19) | C1B—C10B—C5B | 107.7 (2) |
C25A—C10A—C9A | 113.6 (2) | C25B—C10B—C9B | 113.7 (2) |
C1A—C10A—C9A | 108.48 (18) | C1B—C10B—C9B | 108.1 (2) |
C5A—C10A—C9A | 105.04 (16) | C5B—C10B—C9B | 105.5 (2) |
C12A—C11A—C9A | 116.46 (19) | C12B—C11B—C9B | 117.6 (2) |
O3A—C12A—C11A | 119.6 (2) | O3B—C12B—C11B | 119.8 (2) |
O3A—C12A—C13A | 122.3 (2) | O3B—C12B—C13B | 122.8 (2) |
C11A—C12A—C13A | 117.9 (2) | C11B—C12B—C13B | 117.2 (2) |
C12A—C13A—C18A | 114.5 (2) | C12B—C13B—C18B | 115.12 (19) |
C12A—C13A—C14A | 111.49 (19) | C12B—C13B—C14B | 110.48 (19) |
C18A—C13A—C14A | 117.2 (2) | C18B—C13B—C14B | 118.0 (2) |
C27A—C14A—C15A | 109.1 (2) | C15B—C14B—C13B | 109.42 (18) |
C27A—C14A—C13A | 109.9 (2) | C15B—C14B—C27B | 106.5 (2) |
C15A—C14A—C13A | 108.7 (2) | C13B—C14B—C27B | 109.90 (19) |
C27A—C14A—C8A | 110.89 (19) | C15B—C14B—C8B | 111.62 (18) |
C15A—C14A—C8A | 110.73 (19) | C13B—C14B—C8B | 108.26 (19) |
C13A—C14A—C8A | 107.51 (18) | C27B—C14B—C8B | 111.13 (18) |
C16A—C15A—C14A | 114.3 (2) | C16B—C15B—C14B | 114.72 (19) |
C15A—C16A—C17A | 112.4 (2) | C15B—C16B—C17B | 112.7 (2) |
C28A—C17A—C16A | 112.2 (3) | C28B—C17B—C16B | 110.8 (2) |
C28A—C17A—C18A | 110.4 (3) | C28B—C17B—C22B | 104.0 (2) |
C16A—C17A—C18A | 108.9 (2) | C16B—C17B—C22B | 111.3 (2) |
C28A—C17A—C22A | 105.0 (3) | C28B—C17B—C18B | 110.1 (2) |
C16A—C17A—C22A | 111.2 (3) | C16B—C17B—C18B | 108.81 (19) |
C18A—C17A—C22A | 109.2 (2) | C22B—C17B—C18B | 111.7 (2) |
C19A—C18A—C13A | 116.3 (2) | C17B—C18B—C13B | 109.8 (2) |
C19A—C18A—C17A | 112.3 (2) | C17B—C18B—C19B | 111.1 (2) |
C13A—C18A—C17A | 108.9 (2) | C13B—C18B—C19B | 116.7 (2) |
C18A—C19A—C20A | 114.3 (3) | C20B—C19B—C18B | 113.9 (2) |
C30A—C20A—C29A | 108.1 (3) | C21B—C20B—C29B | 108.9 (3) |
C30A—C20A—C19A | 112.0 (3) | C21B—C20B—C19B | 108.6 (2) |
C29A—C20A—C19A | 109.2 (3) | C29B—C20B—C19B | 108.4 (3) |
C30A—C20A—C21A | 111.4 (3) | C21B—C20B—C30B | 110.9 (3) |
C29A—C20A—C21A | 109.1 (3) | C29B—C20B—C30B | 109.1 (3) |
C19A—C20A—C21A | 107.1 (3) | C19B—C20B—C30B | 110.9 (3) |
C22A—C21A—C20A | 113.6 (3) | C20B—C21B—C22B | 112.6 (3) |
C21A—C22A—C17A | 115.4 (3) | C21B—C22B—C17B | 113.7 (2) |
O4A—C28A—O5A | 121.6 (4) | O4B—C28B—O5B | 121.7 (3) |
O4A—C28A—C17A | 125.6 (3) | O4B—C28B—C17B | 126.3 (3) |
O5A—C28A—C17A | 112.7 (4) | O5B—C28B—C17B | 112.1 (2) |
O2A—C31A—O1A | 123.0 (3) | O2B—C31B—O1B | 121.5 (5) |
O2A—C31A—C32A | 124.3 (3) | O2B—C31B—C32B | 126.8 (6) |
O1A—C31A—C32A | 112.7 (2) | O1B—C31B—C32B | 111.4 (7) |
| | | |
C10A—C1A—C2A—C3A | −57.8 (3) | C10B—C1B—C2B—C3B | −57.3 (4) |
C31A—O1A—C3A—C2A | 81.8 (2) | C31B—O1B—C3B—C2B | 105.4 (5) |
C31A—O1A—C3A—C4A | −153.3 (2) | C31B—O1B—C3B—C4B | −130.2 (5) |
C1A—C2A—C3A—O1A | −177.49 (19) | C1B—C2B—C3B—O1B | −178.5 (3) |
C1A—C2A—C3A—C4A | 60.7 (3) | C1B—C2B—C3B—C4B | 60.5 (4) |
O1A—C3A—C4A—C24A | −52.2 (2) | O1B—C3B—C4B—C24B | −51.4 (4) |
C2A—C3A—C4A—C24A | 70.6 (3) | C2B—C3B—C4B—C24B | 69.5 (3) |
O1A—C3A—C4A—C23A | 65.4 (2) | O1B—C3B—C4B—C23B | 67.1 (4) |
C2A—C3A—C4A—C23A | −171.77 (19) | C2B—C3B—C4B—C23B | −172.0 (3) |
O1A—C3A—C4A—C5A | −178.32 (17) | O1B—C3B—C4B—C5B | −176.2 (3) |
C2A—C3A—C4A—C5A | −55.5 (2) | C2B—C3B—C4B—C5B | −55.2 (4) |
C3A—C4A—C5A—C6A | −176.78 (19) | C3B—C4B—C5B—C6B | −175.0 (3) |
C24A—C4A—C5A—C6A | 59.1 (2) | C24B—C4B—C5B—C6B | 61.9 (4) |
C23A—C4A—C5A—C6A | −62.0 (3) | C23B—C4B—C5B—C6B | −59.3 (3) |
C3A—C4A—C5A—C10A | 51.5 (2) | C3B—C4B—C5B—C10B | 52.2 (3) |
C24A—C4A—C5A—C10A | −72.6 (2) | C24B—C4B—C5B—C10B | −71.0 (3) |
C3A—C4A—C5A—C10A | 166.3 (2) | C23B—C4B—C5B—C10B | 167.8 (2) |
C4A—C5A—C6A—C7A | 161.30 (19) | C4B—C5B—C6B—C7B | 162.6 (2) |
C10A—C5A—C6A—C7A | −63.4 (2) | C10B—C5B—C6B—C7B | −61.4 (3) |
C5A—C6A—C7A—C8A | 55.9 (3) | C5B—C6B—C7B—C8B | 54.2 (3) |
C6A—C7A—C8A—C26A | 75.0 (3) | C6B—C7B—C8B—C9B | −46.1 (3) |
C6A—C7A—C8A—C9A | −46.2 (3) | C6B—C7B—C8B—C26B | 74.3 (3) |
C6A—C7A—C8A—C14A | −163.6 (2) | C6B—C7B—C8B—C14B | −165.3 (2) |
C26A—C8A—C9A—C11A | 62.8 (3) | C7B—C8B—C9B—C11B | −177.5 (2) |
C7A—C8A—C9A—C11A | −178.8 (2) | C26B—C8B—C9B—C11B | 65.0 (3) |
C14A—C8A—C9A—C11A | −59.5 (2) | C14B—C8B—C9B—C11B | −56.2 (3) |
C26A—C8A—C9A—C10A | −69.5 (3) | C7B—C8B—C9B—C10B | 49.0 (3) |
C7A—C8A—C9A—C10A | 48.8 (3) | C26B—C8B—C9B—C10B | −68.4 (3) |
C14A—C8A—C9A—C10A | 168.17 (18) | C14B—C8B—C9B—C10B | 170.34 (19) |
C2A—C1A—C10A—C25A | −72.1 (3) | C2B—C1B—C10B—C25B | −72.2 (4) |
C2A—C1A—C10A—C5A | 51.1 (3) | C2B—C1B—C10B—C5B | 51.1 (4) |
C2A—C1A—C10A—C9A | 164.47 (19) | C2B—C1B—C10B—C9B | 164.6 (3) |
C6A—C5A—C10A—C25A | −64.5 (2) | C6B—C5B—C10B—C25B | −65.8 (3) |
C4A—C5A—C10A—C25A | 69.5 (3) | C4B—C5B—C10B—C25B | 68.5 (3) |
C6A—C5A—C10A—C1A | 175.99 (18) | C6B—C5B—C10B—C1B | 174.9 (2) |
C4A—C5A—C10A—C1A | −50.0 (3) | C4B—C5B—C10B—C1B | −50.9 (3) |
C6A—C5A—C10A—C9A | 60.3 (2) | C6B—C5B—C10B—C9B | 59.6 (3) |
C4A—C5A—C10A—C9A | −165.69 (18) | C4B—C5B—C10B—C9B | −166.1 (2) |
C11A—C9A—C10A—C25A | −62.2 (3) | C11B—C9B—C10B—C25B | −62.2 (3) |
C8A—C9A—C10A—C25A | 68.9 (2) | C8B—C9B—C10B—C25B | 70.2 (3) |
C11A—C9A—C10A—C1A | 57.6 (3) | C11B—C9B—C10B—C1B | 57.2 (3) |
C8A—C9A—C10A—C1A | −171.35 (19) | C8B—C9B—C10B—C1B | −170.4 (2) |
C11A—C9A—C10A—C5A | 173.0 (2) | C11B—C9B—C10B—C5B | 172.2 (2) |
C8A—C9A—C10A—C5A | −55.9 (2) | C8B—C9B—C10B—C5B | −55.4 (3) |
C8A—C9A—C11A—C12A | 44.2 (3) | C8B—C9B—C11B—C12B | 41.1 (3) |
C10A—C9A—C11A—C12A | 178.6 (2) | C10B—C9B—C11B—C12B | 176.0 (2) |
C9A—C11A—C12A—O3A | 149.4 (3) | C9B—C11B—C12B—O3B | 150.1 (3) |
C9A—C11A—C12A—C13A | −35.8 (3) | C9B—C11B—C12B—C13B | −34.8 (4) |
O3A—C12A—C13A—C18A | −6.8 (4) | O3B—C12B—C13B—C18B | −4.9 (4) |
C11A—C12A—C13A—C18A | 178.6 (2) | C11B—C12B—C13B—C18B | −179.8 (2) |
O3A—C12A—C13A—C14A | −142.7 (2) | O3B—C12B—C13B—C14B | −141.6 (3) |
C11A—C12A—C13A—C14A | 42.6 (3) | C11B—C12B—C13B—C14B | 43.5 (3) |
C12A—C13A—C14A—C27A | 63.2 (3) | C12B—C13B—C14B—C15B | 179.1 (2) |
C18A—C13A—C14A—C27A | −71.5 (3) | C18B—C13B—C14B—C15B | 43.7 (3) |
C12A—C13A—C14A—C15A | −177.5 (2) | C12B—C13B—C14B—C27B | 62.5 (3) |
C18A—C13A—C14A—C15A | 47.8 (3) | C18B—C13B—C14B—C27B | −72.9 (3) |
C12A—C13A—C14A—C8A | −57.6 (3) | C12B—C13B—C14B—C8B | −59.1 (2) |
C18A—C13A—C14A—C8A | 167.7 (2) | C18B—C13B—C14B—C8B | 165.55 (19) |
C26A—C8A—C14A—C27A | −175.7 (2) | C7B—C8B—C14B—C15B | −52.9 (2) |
C7A—C8A—C14A—C27A | 65.4 (2) | C9B—C8B—C14B—C15B | −173.03 (18) |
C9A—C8A—C14A—C27A | −53.1 (2) | C26B—C8B—C14B—C15B | 65.2 (2) |
C26A—C8A—C14A—C15A | 63.0 (3) | C7B—C8B—C14B—C13B | −173.40 (18) |
C7A—C8A—C14A—C15A | −55.9 (3) | C9B—C8B—C14B—C13B | 66.5 (2) |
C9A—C8A—C14A—C15A | −174.4 (2) | C26B—C8B—C14B—C13B | −55.3 (2) |
C26A—C8A—C14A—C13A | −55.6 (2) | C7B—C8B—C14B—C27B | 65.8 (2) |
C7A—C8A—C14A—C13A | −174.52 (19) | C9B—C8B—C14B—C27B | −54.3 (2) |
C9A—C8A—C14A—C13A | 67.0 (2) | C26B—C8B—C14B—C27B | −176.1 (2) |
C27A—C14A—C15A—C16A | 72.8 (3) | C13B—C14B—C15B—C16B | −44.3 (3) |
C13A—C14A—C15A—C16A | −47.0 (3) | C27B—C14B—C15B—C16B | 74.5 (2) |
C8A—C14A—C15A—C16A | −164.8 (2) | C8B—C14B—C15B—C16B | −164.07 (19) |
C14A—C15A—C16A—C17A | 55.9 (3) | C14B—C15B—C16B—C17B | 55.5 (3) |
C15A—C16A—C17A—C28A | 62.5 (3) | C15B—C16B—C17B—C28B | 60.9 (3) |
C15A—C16A—C17A—C18A | −59.9 (3) | C15B—C16B—C17B—C22B | 176.1 (2) |
C15A—C16A—C17A—C22A | 179.8 (3) | C15B—C16B—C17B—C18B | −60.4 (3) |
C12A—C13A—C18A—C19A | −59.7 (3) | C28B—C17B—C18B—C13B | −65.3 (3) |
C14A—C13A—C18A—C19A | 73.7 (3) | C16B—C17B—C18B—C13B | 56.3 (3) |
C12A—C13A—C18A—C17A | 172.2 (2) | C22B—C17B—C18B—C13B | 179.6 (2) |
C14A—C13A—C18A—C17A | −54.5 (3) | C28B—C17B—C18B—C19B | 164.0 (2) |
C28A—C17A—C18A—C19A | 163.3 (2) | C16B—C17B—C18B—C19B | −74.3 (3) |
C16A—C17A—C18A—C19A | −73.2 (3) | C22B—C17B—C18B—C19B | 49.0 (3) |
C22A—C17A—C18A—C19A | 48.4 (4) | C12B—C13B—C18B—C17B | 175.3 (2) |
C28A—C17A—C18A—C13A | −66.4 (3) | C14B—C13B—C18B—C17B | −51.3 (3) |
C16A—C17A—C18A—C13A | 57.1 (3) | C12B—C13B—C18B—C19B | −57.1 (3) |
C22A—C17A—C18A—C13A | 178.7 (3) | C14B—C13B—C18B—C19B | 76.3 (3) |
C13A—C18A—C19A—C20A | 176.6 (2) | C17B—C18B—C19B—C20B | −54.9 (3) |
C17A—C18A—C19A—C20A | −56.9 (3) | C13B—C18B—C19B—C20B | 178.2 (2) |
C18A—C19A—C20A—C30A | −65.2 (4) | C18B—C19B—C20B—C21B | 57.4 (4) |
C18A—C19A—C20A—C29A | 175.1 (3) | C18B—C19B—C20B—C29B | 175.5 (3) |
C18A—C19A—C20A—C21A | 57.1 (4) | C18B—C19B—C20B—C30B | −64.7 (3) |
C30A—C20A—C21A—C22A | 68.0 (4) | C29B—C20B—C21B—C22B | −173.3 (3) |
C29A—C20A—C21A—C22A | −172.8 (4) | C19B—C20B—C21B—C22B | −55.4 (4) |
C19A—C20A—C21A—C22A | −54.7 (5) | C30B—C20B—C21B—C22B | 66.7 (3) |
C20A—C21A—C22A—C17A | 53.3 (5) | C20B—C21B—C22B—C17B | 53.4 (3) |
C28A—C17A—C22A—C21A | −166.5 (4) | C28B—C17B—C22B—C21B | −168.0 (2) |
C16A—C17A—C22A—C21A | 72.0 (4) | C16B—C17B—C22B—C21B | 72.7 (3) |
C18A—C17A—C22A—C21A | −48.1 (4) | C18B—C17B—C22B—C21B | −49.2 (3) |
C33A—O5A—C28A—O4A | −0.8 (6) | C33B—O5B—C28B—O4B | −0.6 (5) |
C33A—O5A—C28A—C17A | 176.3 (3) | C33B—O5B—C28B—C17B | 178.1 (4) |
C16A—C17A—C28A—O4A | −142.7 (4) | C16B—C17B—C28B—O4B | −144.8 (3) |
C18A—C17A—C28A—O4A | −21.1 (5) | C22B—C17B—C28B—O4B | 95.5 (4) |
C22A—C17A—C28A—O4A | 96.4 (4) | C18B—C17B—C28B—O4B | −24.3 (4) |
C16A—C17A—C28A—O5A | 40.4 (3) | C16B—C17B—C28B—O5B | 36.7 (3) |
C18A—C17A—C28A—O5A | 161.9 (3) | C22B—C17B—C28B—O5B | −83.0 (3) |
C22A—C17A—C28A—O5A | −80.5 (3) | C18B—C17B—C28B—O5B | 157.1 (3) |
C3A—O1A—C31A—O2A | −2.1 (3) | C3B—O1B—C31B—O2B | −7.9 (11) |
C3A—O1A—C31A—C32A | 176.4 (2) | C3B—O1B—C31B—C32B | 177.7 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11B—H11D···O2Ai | 0.97 | 2.45 | 3.336 (4) | 152 |
C13A—H13A···O4A | 0.98 | 2.50 | 3.155 (4) | 124 |
C13B—H13B···O4B | 0.98 | 2.53 | 3.187 (3) | 124 |
C19A—H19A···O3A | 0.97 | 2.42 | 3.051 (3) | 122 |
C19B—H19D···O3B | 0.97 | 2.40 | 3.038 (3) | 123 |
C27B—H27E···O2Aii | 0.96 | 2.53 | 3.357 (4) | 145 |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y−1, z. |
(II) Methyl 3
β-acetoxy-12,19-dioxoolean-9(11),13 (18)-dien-28-oate
top
Crystal data top
C33H46O6 | F(000) = 584 |
Mr = 538.70 | Dx = 1.183 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 7.9348 (8) Å | Cell parameters from 50 reflections |
b = 15.8841 (10) Å | θ = 14.8–30.2° |
c = 12.1480 (8) Å | µ = 0.64 mm−1 |
β = 99.041 (7)° | T = 293 K |
V = 1512.1 (2) Å3 | Prism, colourless |
Z = 2 | 0.53 × 0.40 × 0.20 mm |
Data collection top
Kuma Diffraction KM-4 diffractometer | 5157 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 70.2°, θmin = 3.7° |
ω/2θ scans | h = −9→8 |
Absorption correction: ψ-scan (North et al., 1968) | k = −19→19 |
Tmin = 0.769, Tmax = 0.880 | l = 0→14 |
5476 measured reflections | 2 standard reflections every 100 reflections |
5362 independent reflections | intensity decay: 1.7% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0534P)2 + 0.1609P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.092 | (Δ/σ)max = 0.007 |
S = 1.06 | Δρmax = 0.16 e Å−3 |
5362 reflections | Δρmin = −0.15 e Å−3 |
362 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0059 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.00 (15) |
Crystal data top
C33H46O6 | V = 1512.1 (2) Å3 |
Mr = 538.70 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 7.9348 (8) Å | µ = 0.64 mm−1 |
b = 15.8841 (10) Å | T = 293 K |
c = 12.1480 (8) Å | 0.53 × 0.40 × 0.20 mm |
β = 99.041 (7)° | |
Data collection top
Kuma Diffraction KM-4 diffractometer | 5157 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.023 |
Tmin = 0.769, Tmax = 0.880 | 2 standard reflections every 100 reflections |
5476 measured reflections | intensity decay: 1.7% |
5362 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.092 | Δρmax = 0.16 e Å−3 |
S = 1.06 | Δρmin = −0.15 e Å−3 |
5362 reflections | Absolute structure: Flack (1983) |
362 parameters | Absolute structure parameter: 0.00 (15) |
1 restraint | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.21451 (17) | 0.55406 (8) | 0.66832 (10) | 0.0593 (3) | |
O2 | −0.3845 (2) | 0.54561 (11) | 0.79746 (15) | 0.0908 (5) | |
O3 | −0.09466 (16) | 0.02786 (8) | 0.79924 (15) | 0.0776 (5) | |
O4 | 0.0972 (2) | −0.10255 (9) | 0.70074 (10) | 0.0794 (5) | |
O5 | 0.6296 (2) | −0.13339 (10) | 0.81373 (15) | 0.0829 (5) | |
O6 | 0.51164 (17) | −0.03240 (10) | 0.70121 (10) | 0.0673 (4) | |
C1 | −0.1905 (2) | 0.31773 (11) | 0.67054 (15) | 0.0535 (4) | |
H1A | −0.2631 | 0.2756 | 0.6291 | 0.064* | |
H1B | −0.1983 | 0.3109 | 0.7489 | 0.064* | |
C2 | −0.2544 (2) | 0.40533 (12) | 0.63256 (16) | 0.0587 (4) | |
H2A | −0.2489 | 0.4124 | 0.5539 | 0.070* | |
H2B | −0.3723 | 0.4118 | 0.6432 | 0.070* | |
C3 | −0.1461 (2) | 0.47068 (11) | 0.69874 (14) | 0.0505 (4) | |
H3A | −0.1508 | 0.4614 | 0.7780 | 0.061* | |
C4 | 0.0410 (2) | 0.46894 (10) | 0.68189 (14) | 0.0483 (3) | |
C5 | 0.10629 (19) | 0.37714 (9) | 0.70842 (12) | 0.0417 (3) | |
H5A | 0.1051 | 0.3703 | 0.7885 | 0.050* | |
C6 | 0.2918 (2) | 0.36398 (10) | 0.69473 (15) | 0.0515 (4) | |
H6A | 0.2996 | 0.3561 | 0.6165 | 0.062* | |
H6B | 0.3581 | 0.4134 | 0.7210 | 0.062* | |
C7 | 0.3637 (2) | 0.28714 (10) | 0.76072 (16) | 0.0520 (4) | |
H7A | 0.3716 | 0.2996 | 0.8395 | 0.062* | |
H7B | 0.4787 | 0.2773 | 0.7458 | 0.062* | |
C8 | 0.25957 (18) | 0.20516 (9) | 0.73558 (12) | 0.0402 (3) | |
C9 | 0.06651 (18) | 0.22143 (9) | 0.71069 (11) | 0.0391 (3) | |
C10 | −0.00415 (19) | 0.30333 (9) | 0.65292 (12) | 0.0423 (3) | |
C11 | −0.04033 (19) | 0.16081 (10) | 0.73254 (14) | 0.0482 (3) | |
H11A | −0.1567 | 0.1713 | 0.7147 | 0.058* | |
C12 | 0.0117 (2) | 0.07969 (9) | 0.78201 (14) | 0.0480 (3) | |
C13 | 0.19797 (18) | 0.06521 (9) | 0.81609 (11) | 0.0377 (3) | |
C14 | 0.30427 (18) | 0.14448 (9) | 0.83941 (11) | 0.0380 (3) | |
C15 | 0.49523 (19) | 0.12273 (10) | 0.85929 (14) | 0.0466 (3) | |
H15A | 0.5326 | 0.1134 | 0.7880 | 0.056* | |
H15B | 0.5588 | 0.1702 | 0.8948 | 0.056* | |
C16 | 0.5356 (2) | 0.04522 (11) | 0.93160 (14) | 0.0507 (4) | |
H16A | 0.5059 | 0.0563 | 1.0047 | 0.061* | |
H16B | 0.6574 | 0.0346 | 0.9410 | 0.061* | |
C17 | 0.4402 (2) | −0.03397 (10) | 0.88293 (12) | 0.0443 (3) | |
C18 | 0.25840 (18) | −0.01318 (9) | 0.83012 (10) | 0.0380 (3) | |
C19 | 0.1516 (2) | −0.08985 (9) | 0.79642 (12) | 0.0438 (3) | |
C20 | 0.1377 (2) | −0.15324 (10) | 0.88818 (14) | 0.0510 (4) | |
C21 | 0.3225 (3) | −0.17453 (12) | 0.94023 (18) | 0.0651 (5) | |
H21A | 0.3200 | −0.2107 | 1.0043 | 0.078* | |
H21B | 0.3754 | −0.2060 | 0.8863 | 0.078* | |
C22 | 0.4321 (2) | −0.09837 (12) | 0.97692 (15) | 0.0601 (4) | |
H22A | 0.5470 | −0.1172 | 1.0054 | 0.072* | |
H22B | 0.3874 | −0.0707 | 1.0374 | 0.072* | |
C23 | 0.1392 (3) | 0.52821 (12) | 0.7689 (2) | 0.0713 (5) | |
H23A | 0.2575 | 0.5289 | 0.7605 | 0.086* | |
H23B | 0.1283 | 0.5088 | 0.8423 | 0.086* | |
H23C | 0.0931 | 0.5840 | 0.7583 | 0.086* | |
C24 | 0.0627 (3) | 0.49946 (12) | 0.56554 (17) | 0.0660 (5) | |
H24A | −0.0007 | 0.4635 | 0.5104 | 0.079* | |
H24B | 0.1813 | 0.4979 | 0.5581 | 0.079* | |
H24C | 0.0211 | 0.5561 | 0.5551 | 0.079* | |
C25 | −0.0049 (3) | 0.29330 (12) | 0.52662 (14) | 0.0621 (4) | |
H25A | 0.1094 | 0.2987 | 0.5108 | 0.074* | |
H25B | −0.0756 | 0.3361 | 0.4872 | 0.074* | |
H25C | −0.0490 | 0.2388 | 0.5031 | 0.074* | |
C26 | 0.3089 (2) | 0.16279 (12) | 0.63033 (14) | 0.0567 (4) | |
H26A | 0.2570 | 0.1081 | 0.6208 | 0.068* | |
H26B | 0.4307 | 0.1571 | 0.6388 | 0.068* | |
H26C | 0.2697 | 0.1969 | 0.5662 | 0.068* | |
C27 | 0.2557 (2) | 0.18357 (10) | 0.94685 (13) | 0.0495 (4) | |
H27A | 0.1381 | 0.2005 | 0.9334 | 0.059* | |
H27B | 0.3264 | 0.2318 | 0.9680 | 0.059* | |
H27C | 0.2724 | 0.1427 | 1.0057 | 0.059* | |
C28 | 0.5381 (2) | −0.07352 (11) | 0.79715 (15) | 0.0524 (4) | |
C29 | 0.0445 (3) | −0.23155 (12) | 0.8402 (2) | 0.0741 (6) | |
H29A | 0.0470 | −0.2732 | 0.8977 | 0.089* | |
H29B | 0.0993 | −0.2534 | 0.7812 | 0.089* | |
H29C | −0.0718 | −0.2176 | 0.8114 | 0.089* | |
C30 | 0.0427 (3) | −0.11365 (14) | 0.97568 (16) | 0.0657 (5) | |
H30A | −0.0742 | −0.1040 | 0.9436 | 0.079* | |
H30B | 0.0955 | −0.0611 | 1.0002 | 0.079* | |
H30C | 0.0471 | −0.1511 | 1.0381 | 0.079* | |
C31 | −0.3343 (2) | 0.58312 (12) | 0.72457 (16) | 0.0591 (4) | |
C32 | −0.3974 (4) | 0.66756 (15) | 0.6834 (2) | 0.0868 (7) | |
H32A | −0.4647 | 0.6619 | 0.6109 | 0.104* | |
H32B | −0.3019 | 0.7038 | 0.6788 | 0.104* | |
H32C | −0.4661 | 0.6913 | 0.7339 | 0.104* | |
C33 | 0.6086 (3) | −0.0621 (2) | 0.6175 (2) | 0.0969 (9) | |
H33A | 0.7276 | −0.0634 | 0.6482 | 0.116* | |
H33B | 0.5911 | −0.0248 | 0.5545 | 0.116* | |
H33C | 0.5713 | −0.1177 | 0.5943 | 0.116* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0627 (7) | 0.0506 (7) | 0.0693 (7) | 0.0175 (5) | 0.0252 (6) | 0.0143 (5) |
O2 | 0.1008 (12) | 0.0907 (11) | 0.0935 (10) | 0.0298 (10) | 0.0541 (9) | 0.0193 (9) |
O3 | 0.0403 (7) | 0.0520 (7) | 0.1358 (13) | −0.0097 (5) | −0.0004 (7) | 0.0288 (8) |
O4 | 0.1217 (13) | 0.0654 (8) | 0.0466 (6) | −0.0336 (8) | −0.0010 (7) | −0.0070 (6) |
O5 | 0.0647 (9) | 0.0624 (8) | 0.1261 (13) | 0.0229 (7) | 0.0288 (8) | −0.0061 (8) |
O6 | 0.0606 (8) | 0.0871 (9) | 0.0575 (7) | 0.0111 (7) | 0.0200 (6) | −0.0093 (6) |
C1 | 0.0356 (8) | 0.0489 (9) | 0.0734 (10) | 0.0005 (6) | 0.0007 (7) | 0.0134 (8) |
C2 | 0.0385 (9) | 0.0567 (10) | 0.0788 (11) | 0.0065 (7) | 0.0027 (8) | 0.0156 (8) |
C3 | 0.0501 (9) | 0.0473 (8) | 0.0568 (8) | 0.0106 (7) | 0.0166 (7) | 0.0133 (7) |
C4 | 0.0455 (9) | 0.0412 (8) | 0.0603 (9) | 0.0018 (6) | 0.0146 (7) | 0.0045 (7) |
C5 | 0.0384 (8) | 0.0406 (7) | 0.0477 (7) | −0.0011 (6) | 0.0118 (6) | 0.0042 (6) |
C6 | 0.0386 (8) | 0.0435 (8) | 0.0757 (11) | −0.0047 (6) | 0.0190 (7) | 0.0052 (7) |
C7 | 0.0330 (8) | 0.0442 (8) | 0.0785 (11) | −0.0047 (6) | 0.0076 (7) | 0.0048 (7) |
C8 | 0.0351 (7) | 0.0389 (7) | 0.0473 (7) | −0.0008 (5) | 0.0089 (6) | −0.0005 (5) |
C9 | 0.0333 (7) | 0.0414 (7) | 0.0419 (7) | −0.0001 (5) | 0.0031 (5) | 0.0011 (5) |
C10 | 0.0383 (8) | 0.0419 (7) | 0.0460 (7) | −0.0009 (6) | 0.0040 (6) | 0.0059 (6) |
C11 | 0.0316 (7) | 0.0447 (8) | 0.0657 (9) | −0.0015 (6) | −0.0004 (6) | 0.0069 (7) |
C12 | 0.0360 (8) | 0.0399 (7) | 0.0665 (9) | −0.0034 (6) | 0.0028 (7) | 0.0055 (6) |
C13 | 0.0336 (7) | 0.0405 (7) | 0.0384 (6) | −0.0003 (5) | 0.0035 (5) | −0.0004 (5) |
C14 | 0.0309 (7) | 0.0383 (7) | 0.0438 (7) | 0.0002 (5) | 0.0023 (5) | −0.0040 (5) |
C15 | 0.0303 (7) | 0.0455 (8) | 0.0615 (8) | −0.0017 (6) | −0.0006 (6) | −0.0054 (7) |
C16 | 0.0397 (8) | 0.0528 (9) | 0.0557 (8) | 0.0064 (7) | −0.0050 (6) | −0.0050 (7) |
C17 | 0.0392 (8) | 0.0443 (7) | 0.0480 (7) | 0.0075 (6) | 0.0028 (6) | −0.0001 (6) |
C18 | 0.0383 (7) | 0.0409 (7) | 0.0344 (6) | 0.0016 (6) | 0.0047 (5) | −0.0003 (5) |
C19 | 0.0479 (8) | 0.0383 (7) | 0.0454 (7) | 0.0014 (6) | 0.0077 (6) | −0.0032 (6) |
C20 | 0.0545 (9) | 0.0414 (8) | 0.0570 (9) | 0.0005 (7) | 0.0090 (7) | 0.0062 (6) |
C21 | 0.0598 (11) | 0.0513 (10) | 0.0831 (12) | 0.0098 (8) | 0.0077 (9) | 0.0216 (9) |
C22 | 0.0523 (10) | 0.0626 (10) | 0.0615 (10) | 0.0092 (8) | −0.0033 (8) | 0.0171 (8) |
C23 | 0.0644 (13) | 0.0477 (9) | 0.1008 (15) | −0.0004 (8) | 0.0102 (11) | −0.0135 (10) |
C24 | 0.0730 (12) | 0.0517 (10) | 0.0812 (12) | 0.0084 (8) | 0.0367 (10) | 0.0200 (9) |
C25 | 0.0809 (13) | 0.0566 (10) | 0.0462 (9) | 0.0065 (9) | 0.0023 (8) | 0.0053 (7) |
C26 | 0.0595 (10) | 0.0626 (10) | 0.0516 (8) | 0.0103 (8) | 0.0196 (7) | 0.0015 (7) |
C27 | 0.0526 (9) | 0.0483 (8) | 0.0472 (8) | 0.0025 (7) | 0.0068 (7) | −0.0065 (6) |
C28 | 0.0400 (8) | 0.0497 (9) | 0.0684 (10) | 0.0034 (7) | 0.0110 (7) | −0.0092 (7) |
C29 | 0.0787 (14) | 0.0436 (9) | 0.1010 (16) | −0.0081 (9) | 0.0174 (12) | 0.0052 (9) |
C30 | 0.0632 (12) | 0.0778 (13) | 0.0594 (10) | −0.0017 (10) | 0.0198 (8) | 0.0075 (9) |
C31 | 0.0585 (10) | 0.0590 (10) | 0.0624 (10) | 0.0091 (8) | 0.0173 (8) | −0.0012 (8) |
C32 | 0.0933 (17) | 0.0647 (13) | 0.1067 (17) | 0.0278 (12) | 0.0289 (14) | 0.0013 (12) |
C33 | 0.0716 (14) | 0.151 (3) | 0.0755 (13) | 0.0003 (16) | 0.0337 (11) | −0.0333 (15) |
Geometric parameters (Å, º) top
O1—C31 | 1.337 (2) | C9—C11 | 1.337 (2) |
O1—C3 | 1.4567 (19) | C9—C10 | 1.5413 (19) |
O2—C31 | 1.187 (2) | C10—C25 | 1.542 (2) |
O3—C12 | 1.2202 (19) | C11—C12 | 1.454 (2) |
O4—C19 | 1.1918 (19) | C12—C13 | 1.489 (2) |
O5—C28 | 1.194 (2) | C13—C18 | 1.336 (2) |
O6—C28 | 1.324 (2) | C13—C14 | 1.5172 (19) |
O6—C33 | 1.447 (2) | C14—C15 | 1.536 (2) |
C1—C2 | 1.527 (2) | C14—C27 | 1.548 (2) |
C1—C10 | 1.544 (2) | C15—C16 | 1.517 (2) |
C2—C3 | 1.498 (3) | C16—C17 | 1.538 (2) |
C3—C4 | 1.530 (2) | C17—C18 | 1.520 (2) |
C4—C24 | 1.529 (2) | C17—C28 | 1.529 (2) |
C4—C23 | 1.534 (3) | C17—C22 | 1.542 (2) |
C4—C5 | 1.564 (2) | C18—C19 | 1.503 (2) |
C5—C6 | 1.522 (2) | C19—C20 | 1.519 (2) |
C5—C10 | 1.553 (2) | C20—C29 | 1.516 (3) |
C6—C7 | 1.521 (2) | C20—C30 | 1.531 (3) |
C7—C8 | 1.547 (2) | C20—C21 | 1.541 (3) |
C8—C9 | 1.536 (2) | C21—C22 | 1.515 (3) |
C8—C26 | 1.549 (2) | C31—C32 | 1.490 (3) |
C8—C14 | 1.5828 (19) | | |
| | | |
C31—O1—C3 | 116.77 (13) | C18—C13—C12 | 120.02 (13) |
C28—O6—C33 | 115.45 (18) | C18—C13—C14 | 124.89 (13) |
C2—C1—C10 | 111.88 (13) | C12—C13—C14 | 114.98 (12) |
C3—C2—C1 | 109.51 (14) | C13—C14—C15 | 110.40 (11) |
O1—C3—C2 | 109.54 (14) | C13—C14—C27 | 106.59 (12) |
O1—C3—C4 | 108.23 (13) | C15—C14—C27 | 109.15 (12) |
C2—C3—C4 | 113.71 (14) | C13—C14—C8 | 107.95 (11) |
C24—C4—C3 | 111.75 (15) | C15—C14—C8 | 110.75 (11) |
C24—C4—C23 | 108.87 (16) | C27—C14—C8 | 111.93 (12) |
C3—C4—C23 | 107.17 (14) | C16—C15—C14 | 112.75 (13) |
C24—C4—C5 | 113.83 (13) | C15—C16—C17 | 113.27 (12) |
C3—C4—C5 | 106.64 (12) | C18—C17—C28 | 110.60 (12) |
C23—C4—C5 | 108.32 (14) | C18—C17—C16 | 111.20 (12) |
C6—C5—C10 | 109.79 (12) | C28—C17—C16 | 109.02 (13) |
C6—C5—C4 | 113.61 (12) | C18—C17—C22 | 108.06 (13) |
C10—C5—C4 | 117.92 (12) | C28—C17—C22 | 108.46 (13) |
C7—C6—C5 | 109.99 (12) | C16—C17—C22 | 109.46 (13) |
C6—C7—C8 | 115.26 (13) | C13—C18—C19 | 123.01 (13) |
C9—C8—C7 | 112.50 (12) | C13—C18—C17 | 123.67 (13) |
C9—C8—C26 | 106.52 (12) | C19—C18—C17 | 113.32 (12) |
C7—C8—C26 | 109.41 (13) | O4—C19—C18 | 120.33 (14) |
C9—C8—C14 | 110.55 (11) | O4—C19—C20 | 123.14 (15) |
C7—C8—C14 | 108.02 (12) | C18—C19—C20 | 116.10 (12) |
C26—C8—C14 | 109.83 (12) | C29—C20—C19 | 110.43 (15) |
C11—C9—C8 | 118.93 (13) | C29—C20—C30 | 109.89 (16) |
C11—C9—C10 | 120.11 (13) | C19—C20—C30 | 109.72 (13) |
C8—C9—C10 | 120.79 (12) | C29—C20—C21 | 110.67 (15) |
C9—C10—C25 | 108.07 (12) | C19—C20—C21 | 105.82 (14) |
C9—C10—C1 | 110.47 (12) | C30—C20—C21 | 110.24 (15) |
C25—C10—C1 | 107.41 (13) | C22—C21—C20 | 114.25 (14) |
C9—C10—C5 | 107.42 (11) | C21—C22—C17 | 113.61 (14) |
C25—C10—C5 | 115.07 (13) | O5—C28—O6 | 123.35 (17) |
C1—C10—C5 | 108.38 (12) | O5—C28—C17 | 124.94 (18) |
C9—C11—C12 | 124.94 (14) | O6—C28—C17 | 111.71 (13) |
O3—C12—C11 | 120.65 (14) | O2—C31—O1 | 123.84 (17) |
O3—C12—C13 | 122.08 (14) | O2—C31—C32 | 124.62 (18) |
C11—C12—C13 | 117.17 (13) | O1—C31—C32 | 111.53 (17) |
| | | |
C10—C1—C2—C3 | −60.68 (19) | C18—C13—C14—C8 | 132.20 (13) |
C31—O1—C3—C2 | 87.89 (18) | C12—C13—C14—C8 | −51.73 (15) |
C31—O1—C3—C4 | −147.63 (16) | C9—C8—C14—C13 | 54.82 (14) |
C1—C2—C3—O1 | −175.88 (13) | C7—C8—C14—C13 | 178.30 (12) |
C1—C2—C3—C4 | 62.89 (18) | C26—C8—C14—C13 | −62.44 (15) |
O1—C3—C4—C24 | −51.67 (19) | C9—C8—C14—C15 | 175.78 (11) |
C2—C3—C4—C24 | 70.28 (18) | C7—C8—C14—C15 | −60.74 (14) |
O1—C3—C4—C23 | 67.52 (17) | C26—C8—C14—C15 | 58.52 (15) |
C2—C3—C4—C23 | −170.52 (15) | C9—C8—C14—C27 | −62.17 (15) |
O1—C3—C4—C5 | −176.66 (13) | C7—C8—C14—C27 | 61.31 (15) |
C2—C3—C4—C5 | −54.70 (17) | C26—C8—C14—C27 | −179.44 (13) |
C24—C4—C5—C6 | 55.8 (2) | C13—C14—C15—C16 | −42.27 (16) |
C3—C4—C5—C6 | 179.52 (14) | C27—C14—C15—C16 | 74.58 (15) |
C23—C4—C5—C6 | −65.42 (18) | C8—C14—C15—C16 | −161.77 (12) |
C24—C4—C5—C10 | −74.71 (18) | C14—C15—C16—C17 | 58.47 (17) |
C3—C4—C5—C10 | 48.99 (17) | C15—C16—C17—C18 | −39.23 (18) |
C23—C4—C5—C10 | 164.05 (14) | C15—C16—C17—C28 | 82.97 (16) |
C10—C5—C6—C7 | −66.45 (17) | C15—C16—C17—C22 | −158.55 (14) |
C4—C5—C6—C7 | 159.09 (13) | C12—C13—C18—C19 | 9.7 (2) |
C5—C6—C7—C8 | 53.56 (19) | C14—C13—C18—C19 | −174.43 (12) |
C6—C7—C8—C9 | −35.29 (18) | C12—C13—C18—C17 | −169.41 (13) |
C6—C7—C8—C26 | 82.89 (17) | C14—C13—C18—C17 | 6.5 (2) |
C6—C7—C8—C14 | −157.58 (13) | C28—C17—C18—C13 | −113.58 (15) |
C7—C8—C9—C11 | −152.60 (15) | C16—C17—C18—C13 | 7.69 (19) |
C26—C8—C9—C11 | 87.53 (17) | C22—C17—C18—C13 | 127.85 (15) |
C14—C8—C9—C11 | −31.75 (19) | C28—C17—C18—C19 | 67.25 (16) |
C7—C8—C9—C10 | 32.20 (18) | C16—C17—C18—C19 | −171.47 (12) |
C26—C8—C9—C10 | −87.66 (16) | C22—C17—C18—C19 | −51.32 (16) |
C14—C8—C9—C10 | 153.06 (12) | C13—C18—C19—O4 | 64.7 (2) |
C11—C9—C10—C25 | −94.47 (18) | C17—C18—C19—O4 | −116.15 (19) |
C8—C9—C10—C25 | 80.66 (16) | C13—C18—C19—C20 | −122.63 (15) |
C11—C9—C10—C1 | 22.8 (2) | C17—C18—C19—C20 | 56.54 (17) |
C8—C9—C10—C1 | −162.09 (13) | O4—C19—C20—C29 | −0.9 (3) |
C11—C9—C10—C5 | 140.80 (15) | C18—C19—C20—C29 | −173.34 (15) |
C8—C9—C10—C5 | −44.06 (16) | O4—C19—C20—C30 | −122.2 (2) |
C2—C1—C10—C9 | 169.92 (13) | C18—C19—C20—C30 | 65.38 (18) |
C2—C1—C10—C25 | −72.43 (18) | O4—C19—C20—C21 | 118.9 (2) |
C2—C1—C10—C5 | 52.47 (18) | C18—C19—C20—C21 | −53.54 (18) |
C6—C5—C10—C9 | 59.43 (15) | C29—C20—C21—C22 | 172.50 (17) |
C4—C5—C10—C9 | −168.31 (12) | C19—C20—C21—C22 | 52.9 (2) |
C6—C5—C10—C25 | −60.95 (17) | C30—C20—C21—C22 | −65.7 (2) |
C4—C5—C10—C25 | 71.31 (17) | C20—C21—C22—C17 | −56.0 (2) |
C6—C5—C10—C1 | 178.81 (12) | C18—C17—C22—C21 | 51.92 (18) |
C4—C5—C10—C1 | −48.93 (16) | C28—C17—C22—C21 | −68.01 (18) |
C8—C9—C11—C12 | 1.9 (3) | C16—C17—C22—C21 | 173.16 (14) |
C10—C9—C11—C12 | 177.13 (14) | C33—O6—C28—O5 | −3.1 (3) |
C9—C11—C12—O3 | 179.93 (19) | C33—O6—C28—C17 | 175.98 (17) |
C9—C11—C12—C13 | 3.3 (3) | C18—C17—C28—O5 | −136.23 (18) |
O3—C12—C13—C18 | 23.6 (3) | C16—C17—C28—O5 | 101.21 (19) |
C11—C12—C13—C18 | −159.91 (14) | C22—C17—C28—O5 | −17.9 (2) |
O3—C12—C13—C14 | −152.73 (17) | C18—C17—C28—O6 | 44.73 (18) |
C11—C12—C13—C14 | 23.8 (2) | C16—C17—C28—O6 | −77.83 (16) |
C18—C13—C14—C15 | 11.01 (18) | C22—C17—C28—O6 | 163.06 (14) |
C12—C13—C14—C15 | −172.91 (13) | C3—O1—C31—O2 | 1.1 (3) |
C18—C13—C14—C27 | −107.40 (15) | C3—O1—C31—C32 | −178.25 (19) |
C12—C13—C14—C27 | 68.67 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15A···O6 | 0.97 | 2.54 | 3.139 (2) | 120 |
C25—H25B···O4i | 0.96 | 2.46 | 3.204 (2) | 134 |
C33—H33A···O3ii | 0.96 | 2.58 | 3.290 (3) | 131 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C33H52O5 | C33H46O6 |
Mr | 528.75 | 538.70 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.0662 (16), 22.083 (3), 40.141 (5) | 7.9348 (8), 15.8841 (10), 12.1480 (8) |
α, β, γ (°) | 90, 90, 90 | 90, 99.041 (7), 90 |
V (Å3) | 6263.7 (18) | 1512.1 (2) |
Z | 8 | 2 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 0.58 | 0.64 |
Crystal size (mm) | 0.50 × 0.14 × 0.09 | 0.53 × 0.40 × 0.20 |
|
Data collection |
Diffractometer | Kuma Diffraction KM-4 diffractometer | Kuma Diffraction KM-4 diffractometer |
Absorption correction | – | ψ-scan (North et al., 1968) |
Tmin, Tmax | – | 0.769, 0.880 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10738, 10265, 7013 | 5476, 5362, 5157 |
Rint | 0.017 | 0.023 |
(sin θ/λ)max (Å−1) | 0.588 | 0.610 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.130, 1.08 | 0.032, 0.092, 1.06 |
No. of reflections | 10265 | 5362 |
No. of parameters | 704 | 362 |
No. of restraints | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 | 0.16, −0.15 |
Absolute structure | Flack (1983) | Flack (1983) |
Absolute structure parameter | 0.0 (2) | 0.00 (15) |
Selected geometric parameters (Å, º) for (I) topC8A—C14A | 1.596 (3) | C8B—C14B | 1.578 (3) |
C9A—C11A | 1.540 (3) | C9B—C11B | 1.519 (3) |
C17A—C22A | 1.566 (4) | C17B—C22B | 1.535 (4) |
C20A—C21A | 1.541 (5) | C20B—C21B | 1.513 (4) |
C21A—C22A | 1.480 (6) | C21B—C22B | 1.533 (5) |
| | | |
C31A—O1A—C3A | 117.76 (19) | C31B—O1B—C3B | 119.6 (4) |
O1A—C3A—C2A | 110.10 (18) | O1B—C3B—C2B | 108.4 (3) |
C6A—C5A—C10A | 109.79 (18) | C6B—C5B—C10B | 111.0 (2) |
C7A—C8A—C14A | 110.31 (19) | C7B—C8B—C14B | 111.3 (2) |
C12A—C11A—C9A | 116.46 (19) | C12B—C11B—C9B | 117.6 (2) |
C12A—C13A—C14A | 111.49 (19) | C12B—C13B—C14B | 110.48 (19) |
C27A—C14A—C15A | 109.1 (2) | C15B—C14B—C27B | 106.5 (2) |
C28A—C17A—C16A | 112.2 (3) | C28B—C17B—C16B | 110.8 (2) |
C18A—C17A—C22A | 109.2 (2) | C22B—C17B—C18B | 111.7 (2) |
C19A—C18A—C17A | 112.3 (2) | C17B—C18B—C19B | 111.1 (2) |
C19A—C20A—C21A | 107.1 (3) | C21B—C20B—C19B | 108.6 (2) |
C21A—C22A—C17A | 115.4 (3) | C21B—C22B—C17B | 113.7 (2) |
O2A—C31A—C32A | 124.3 (3) | O2B—C31B—C32B | 126.8 (6) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11B—H11D···O2Ai | 0.97 | 2.45 | 3.336 (4) | 152 |
C13A—H13A···O4A | 0.98 | 2.50 | 3.155 (4) | 124 |
C13B—H13B···O4B | 0.98 | 2.53 | 3.187 (3) | 124 |
C19A—H19A···O3A | 0.97 | 2.42 | 3.051 (3) | 122 |
C19B—H19D···O3B | 0.97 | 2.40 | 3.038 (3) | 123 |
C27B—H27E···O2Aii | 0.96 | 2.53 | 3.357 (4) | 145 |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y−1, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15A···O6 | 0.97 | 2.54 | 3.139 (2) | 120 |
C25—H25B···O4i | 0.96 | 2.46 | 3.204 (2) | 134 |
C33—H33A···O3ii | 0.96 | 2.58 | 3.290 (3) | 131 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x+1, y, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Anknüpfend an vorangehende Publikationen (Gzella, 1999, 2000) über Kristallstrukturen von 2-, 3-, 11-Monooxo- und 3,11-Dioxo-Derivaten von Oleanolsäure-methylesterabkömmlingen, wird in dieser Mitteilung über Kristallstrukturen von zwei weiteren im Titel erwähnten Triterpenketonen, (I) und (II), mit Carbonylgruppen in 12- bzw. 12- und 19-Stellung berichtet. \sch
In der unabhängigen Einheit der Elementarzelle von 3β-Acetoxy-12-oxo-18β-olean-28 − säure-methylester, (I), befinden sich zwei Moleküle A und B, die sich gering voneinander unterscheiden. Mit Hilfe der kleinsten Quadrate-Anpassung (Spek, 1998) wurde eine gewogene r.m.s. Abweichung von 0,676 Å gefunden. Die maximalen Abweichungen beziehen sich auf die Atome der Acetylgruppen und betragen 0,962 (C31), 1,137 (O2) und 1,150 Å (C32).
Bei Verbindung (I) weisen die erhöhten Verschiebungsfaktoren der Atome C31B, C32B, O1B, O2B (C3-Acetoxygruppe), C33A, O4A, O5A, C33B, O5B (C17-Estergruppe), C29A, C30A, C23B, C29B, C30B (Methylgruppen), C2B, C3B (Ring A) C21A, C22A (Ring E) auf Fehlordnung und/bzw. thermische Schwingungen der erwähnten Atome hin. Das betrifft besonders die Atome der C3-Acetoxygruppe [Uäq: 0,177 (3), 0,264 (6), 0,1455 (13) und 0,217 (2) Å2] und die Atome C33A und C33B [Uäq: 0,176 (3) und 0,148 (2) Å2]. Im Zusammenhang damit und wahrscheinlich auch infolge der nicht befriedigenden Kristallqualität treten größere Unterschiede in den geometrischen Parametern der Moleküle A und B von (I) auf (Tabelle 1, Experimentelles).
Die Atome C31, C32, O1 und O2 der β-orientierten Acetoxygruppe in C3-Stellung sind in beiden Verbindungen koplanar. Die Carbonylgruppe C31═O2 nimmt in beiden Fällen eine synperiplanare Stellung zur C3—O1 Bindung und eine Mittellage zwischen synklinaler und antiklinaler Stellung zur C2—C3 Bindung ein. Die Torsionswinkel C3—O1—C31—O2 und C2—C3···C31—O2 weisen in (I) folgende Werte auf: −2,1(3), −7,9(11) (Molekül A und B) und 71,1(2), 87,5(7)° (Molekül A und B), in (II) 1.1 (3) und 79.09 (18)°.
In (I) ist die C12═O3 Bindungslänge [Molekül A 1,218 (3) und Molekül B 1,209 (3) Å] der Carbonylgruppe im gesättigten C Ring mit entsprechenden Literaturdaten [1,211 (1) Å; Allen et al., 1987] vergleichbar. Alle Ringe weisen in (I) Sesselkonformation auf, wobei sich eine Deformation des Ringes C [Cremer & Pople (1975) Puckering-Parameter: Q = 0,580 (3) Å, θ = 23,6(3)°, ϕ = 334,3(6)°; Q = 0,566 (2) Å, θ = 23,9(3)°, ϕ = 325.2 (7)°; Molekül A und B] durch die oben erwähnte Carbonylgruppe beobachten läßt. Die Ringe D/E sind cis [Interplanarwinkel: 59,49 (13) und 59,44 (7)°; Molekül A und B], die übrigen trans verknüpft.
In den Ringen C, D und E von 3β-Acetoxy-12,19-dioxo-9(11),13 (18)-oleandien-28 − säure-methylester, (II), befinden sich zwei α,β ungesättigte Carbonylgruppen C12═O3 und C19═O4. Im zentralen Teil des Moleküls von (II) sind drei konjugierte Fragmente zu berücksichtigen und zwar das gänzlich planare C9═C11—C12═O3 [r.m.s. = 0.0003 Å], das annähernd flache O3═C12—C13═C18 [r.m.s. = 0.0733 Å] und das stark gefaltete System C13═C18—C19═O4 [r.m.s. = 0.1813 Å]. Demzufolge beteiligt sich die C19═O4 Carbonylgruppe nicht an der Konjugation des zuletzt erwähnten Systems, die C12═O3 Carbonylgruppe dagegen stark an der Konjugation des ersten, aber nur schwach an der Konjugation des zweiten Systems. Übereinstimmend damit ist die Bindungslänge C18—C19 [1,503 (2) Å] mit den Literaturdaten für die Csp2—Csp3 Bindung [1,509 (1) Å; Allen et al., 1987] vergleichbar, die Bindungslänge C11—C12 [1,454 (2) Å] um etwa 5σ kürzer und die Bindungslänge von C12—C13 [1,489 (2) Å] um etwa 11σ länger als die Literatur-Einfachbindung vom Typ (C═)Csp2—Csp2(═O) [1,465 (1) Å; Allen et al., 1987]. Auch die Atomabstände in den beiden Carbonylgruppen weisen entsprechende Unterschiede auf. In der C19═O4 Gruppe [1,1918 (19) Å] ist dieser um etwa 11σ kürzer als in der C12═O3 Gruppe [1,2202 (19) Å]. Im Fragment des Moleküls von (II) mit den Atomen O3, C12, C13, C18, C19 und O4 weichen die endständigen Sauerstoffatome O3 und O4 von der beinaheflachen Ebene der übrigen erwähnten Kohlenstoffatome um O,544 (3) und −1,011 (2) Å ab. Der Torsionswinkel O3—C12···C19—O4 beträgt 84,25 (16)° und der O3···O4 Atomenabstand 2,935 (2) Å.
Der Einfluß der hybridisierten Atome C9, C11, C12, C13, C18, C19, O3 und O4 im oben diskutierten Fragment auf die Konformation des Moleküls von (II) beschränkt sich auf die Ringe B, C und D. Der Ring B liegt in einer in Richtung zum sp2 hybridisierten C9 Atom hin deformierter Sesselform vor [Cremer & Pople Puckering-Parameter: Q = 0,542 (2) Å, θ = 24,8(2)°, ϕ = 13,5(4)°]. Der Ring C nimmt eine verzerrte Halbboot-Konformation [Cremer & Pople Puckering-Parameter: Q = 0,489 (2) Å, θ = 54,4(2)°, ϕ = 309,2(2)%], der Ring D eine gering deformierte Halbsessel-Konformation ein [Cremer & Pople Puckering-Parameter: Q = 0,458 (2) Å, θ = 125,3(3)°, ϕ = 326,3(2)°]. Der Ring E mit den sp2 hybridisierten C18 und C19 Atomen zeigt, ähnlich wie der gesättigte Ring A, Sessel-Konformation [Cremer & Pople Puckering-Parameter: Q = 0,543 (2) Å, θ = 0,9(2)°, ϕ = 212 (9)° (Ring E); Q = 0,566 (2) Å, θ = 8,3(2), ϕ = 65,0(13)° (Ring A)].
Die Atome C28, C33, O4 und O5 in (I) und C28, C33, O5 und O6 in (II) der am C17 haftenden Estergruppe sind koplanar. Aus den Torsionswinkeln C18—C17—C28—O4 [Verbindung (I): −21,1(5), −24,3(4)°, Molekül A und B] bzw. C18—C17—C28—O5 [Verbindung (II): −136,23 (18)°] geht hervor, daß die Carbonylgruppe C28═O4 in (I) eine Mittellage zwischen synperiplanarer und synklinaler, die Carbonylgruppe C28═O5 in (II) eine Mittellage zwischen antiklinaler und antiperiplanarer Stellung zur C17—C18 Bindung einnimmt.
Aus den auffallend großen Interplanarwinkeln A/B 15,90 (4), B/C 17,60 (6), C/D 20,49 (6) und D/E 25,89 (7)° von (II) kann gefolgert werden, daß das Molekül dieser Verbindung über die Ringe A bis E im Kristallnetz stark gefaltet ist.
In den Verbindungen (I) und (II) ließen sich intramolekulare kurze H···H und C—H···O Kontakte nachweisen. Im Molekül A von (I) wurden 12, im Molekül B derselben Verbindung 14 und in (II) acht H···H Kontakte aufgefunden. Die intramolekularen kurzen C—H···O Kontakte wurden in den Tabellen 2 und 3 als nicht-konventionelle Wasserstoffbrückenbindungen zusammengestellt. In den Verbindungen (I) und (II) wurden außerdem intermolekulare kurze C—H···O Kontakte beobachtet, an denen sich die Carbonylgruppen C31═O2 von (I) (beide Moleküle), C12═O3 und C19═O4 von (II) beteiligen (Tabelle 2 und 3).