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Acta Cryst. (2009). E65, o2088-o2089    [ doi:10.1107/S1600536809030311 ]

19[beta],28-Epoxy-18[alpha]-olean-3[beta]-ol

R. C. Santos, R. M. A. Pinto, A. Matos Beja, J. A. R. Salvador and J. A. Paixão

Abstract top

The title triterpene, C30H50O2, is an 18[alpha]-oleanane derivative prepared by the Wagner-Meerwein rearrangement of betulin with Bi(OTf)3.xH2O (OTF is trifluoromethanesulfonate). There are two symmetry-independent molecules in the asymmetric unit that show no significant differences concerning bond lengths and angles. The conformation of the six-membered rings is close to a chair form, while the five-membered epoxide rings adopt envelope conformations. All rings are trans-fused. In the crystal, molecules are held together by O-H...O hydrogen bonds. A quantum-mechanical ab initio Roothan Hartree-Fock calculation on the isolated molecule gives values for bond lengths and valency angles close to the experimental values. The calculations also reproduce well the molecular conformation with calculated puckering parameters that match well the observed values.

Comment top

Terpenes were among those natural products wherein rearrangements were earliest detected and studied (King et al., 1968). Rearrangements involving the formation of a carbocation and 1,2-migrations of hydrogen or alkyl groups from one carbon to a neighboring carbon are designated as Wagner–Meerwein rearrangements (Hanson, 1991). This group of transformations constitutes a particularly important field of research in organic chemistry and has been widely reported in triterpenoid chemistry. Recently, we have reported the use of bismuth(III) salts as catalysts for the Wagner-Meerwein rearrangement of lupane derivatives with expansion of ring E and formation of an additional O-containing ring (Salvador et al., 2009). Using this procedure, the Wagner-Meerwein rearrangement of betulin afforded the title compound in high yield.

In this communication we report the molecular structure of the 19β,28-Epoxy-18α-olean-3β-ol (I), determined by single-crystal X-ray diffraction, and compare it with that of the free molecule as given by quantum mechanical ab initio calculation.

The structure of compound (I) with the corresponding atomic numbering scheme is shown in Fig. 1. A l l bond lengths and valency angles have typical values for this type of compounds. All rings are fused trans as shown by the angle between the least-squares planes of the rings [molecule A: rings A and B: 16.27 (12)°, B and C: 9.60 (12)°, C and D: 0.40 (12)°, D and E: 15.59 (13)°; molecule B: rings A and B: 13.68 (15)°, B and C: 10.74 (14)°, C and D: 2.78 (13)°, D and E: 13.54 (16)°]. Rings A to E have conformations close to chair as shown by the Cremer & Pople (1975) parameters [Molecule A: ring A: Q = 0.571 (3) Å, θ = 2.1 (3)° and φ = 79 (6)°; B: Q = 0.575 (3) Å, θ = 9.2 (3)° and φ = 17.5 (16)°; C: Q = 0.599 (3) Å, θ = 6.2 (3)° and φ = 336 (2)°; D: Q = 0.521 (3) Å, θ = 168.4 (3)° and φ = 243.2 (14)°; E: Q = 0.661 (3) Å, θ = 21.6 (3)° and φ = 59.1 (7)°; Molecule B: ring A: Q = 0.553 (4) Å, θ = 4.6 (4)° and φ = 61 (5)°; B: Q = 0.569 (3) Å, θ = 7.5 (3)° and φ = 11 (2)°; C: Q = 0.585 (3) Å, θ = 4.2 (3)° and φ = 30 (3)°; D: Q = 0.537 (3) Å, θ = 170.0 (3)° and φ = 236.5 (17)°; E: Q = 0.656 (3) Å, θ = 18.9 (3)° and φ = 61.6 (10)°; The epoxyde-ring has a C18-envelope conformation [molecule A: q2 = 0.461 (3)Å and φ2 = 255.3 (3)° and asymmetry parameters (Duax & Norton, 1975) ΔCs(C18A) = ΔCs(C28A,O19A) = 2.1 (2)° molecule B: q2 = 0.468 (3)Å and φ2 = 254.6 (4)° and asymmetry parameters (Duax & Norton, 1975) ΔCs(C18B) = ΔCs(C28B,O19B) = 1.6 (3)°].

The molecules are hydrogen bonded involving the hydroxyl and epoxyde groups. The hydroxyl group of molecule A acts as a donor towards a neighbour hydroxyl group of a neighbour A molecule acting as an acceptor forming a chain of hydrogen bonds running along the a axis. The hydroxyl group of molecule B acts as a donor towards the epoxyde group of a neighbour A molecule.

In order to gain some insight on how the crystal packing of (I) might affect the molecular geometry we have performed a quantum chemical calculation on the equilibrium geometry of the free molecule. These calculations were performed with the computer program GAMMESS (Schmidt et al., 1993). A molecular orbital Roothan Hartree-Fock method was used with an extended 6–31 G(d,p) basis set. Tight conditions for convergence of both the self-consistent field cycles and maximum density and energy gradient variations were imposed (10-6atomic units). The program was run on the Milipeia cluster of UC-LCA (using 16 Opteron cores, 2.2 GHz runing Linux).

The ab-initio calculations reproduce well the observed experimental bond length and valency angles of the molecule. Also, the calculated conformation of the rings are very close to the experimental values, with the exception of ring C for which the calculations gave a conformation closer to the ideal chair than experiment.

Related literature top

For terpene rearrangements, see: King et al. (1968). For Wagner–Meerwein rearrangements, see: Hanson (1991). For the synthesis of 18α-oleanane derivatives, see: Salvador et al. (2009). For the cytotoxic activity of 18α-oleanane derivatives, see: Urban et al. (2007); Thibeault et al. (2007). For puckering parameters, see: Cremer & Pople (1975) and for asymmetry parameters, see: Duax & Norton (1975). For the program GAMMESS used to perform the quantum chemical calculation on the equilibrium geometry of the free molecul, see: Schmidt et al. (1993).

Experimental top

The synthesis of the 19β,28-epoxy-18α-olean-3β-ol was efficiently acomplished by Wagner-Meerwein rearrangement of commercially available betulin with Bi(OTf)3.xH2O in CH2Cl2 at reflux (Salvador et al., 2009). The product of this reaction was isolated in 95% yield and identified as the title compound from IR, 1H and 13C NMR spectroscopy data (Salvador et al.,2009). Recrystallization from ethanol at room temperature gave colourless single crystals suitable for X-ray diffraction analysis.

Refinement top

All hydrogen atoms were refined as riding on their parent atoms using SHELXL97 defaults except for that of the hydroxyl group which had its coordinates freely refined with Uiso= 1.5 Ueq of the O atoms.

The absolute configuration was known from the synthetic route, but could not be determined from the X-ray data. Thus, Friedel pairs were merged for refinement.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEPII plot of one of the two molecules in the asymmetric unit. Displacement ellipsoids are drawn at the 50% level.
19β,28-Epoxy-18α-olean-3β-ol top
Crystal data top
C30H50O2F(000) = 984
Mr = 442.70Dx = 1.130 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 9126 reflections
a = 13.2824 (2) Åθ = 2.5–27.5°
b = 12.6702 (2) ŵ = 0.07 mm−1
c = 15.5236 (3) ÅT = 293 K
β = 94.999 (1)°Block, clear colourless
V = 2602.54 (8) Å30.40 × 0.25 × 0.18 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6510 independent reflections
Radiation source: fine-focus sealed tube5427 reflections with I > 2σ(I)
graphiteRint = 0.039
φ and ω scansθmax = 27.9°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −17→17
Tmin = 0.930, Tmax = 0.998k = −16→16
63144 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0834P)2 + 0.4115P]
where P = (Fo2 + 2Fc2)/3
6510 reflections(Δ/σ)max = 0.001
593 parametersΔρmax = 0.28 e Å−3
1 restraintΔρmin = −0.19 e Å−3
Crystal data top
C30H50O2V = 2602.54 (8) Å3
Mr = 442.70Z = 4
Monoclinic, P21Mo Kα radiation
a = 13.2824 (2) ŵ = 0.07 mm−1
b = 12.6702 (2) ÅT = 293 K
c = 15.5236 (3) Å0.40 × 0.25 × 0.18 mm
β = 94.999 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6510 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		5427 reflections with I > 2σ(I)
Tmin = 0.930, Tmax = 0.998Rint = 0.039
63144 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.140Δρmax = 0.28 e Å−3
S = 1.02Δρmin = −0.19 e Å−3
6510 reflectionsAbsolute structure: ?
593 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
C1A1.21538 (19)1.06069 (19)0.31109 (18)0.0404 (5)
H1A11.17451.12330.29930.049*
H1A21.22661.05310.37340.049*
C2A1.3177 (2)1.0762 (2)0.27390 (19)0.0436 (6)
H2A11.30711.08870.21210.052*
H2A21.35151.13740.30040.052*
C3A1.38282 (17)0.9802 (2)0.29068 (16)0.0380 (5)
H3A1.39190.96990.35340.046*
C4A1.33528 (17)0.8782 (2)0.25066 (16)0.0362 (5)
C23A1.3342 (2)0.8791 (3)0.15174 (18)0.0536 (7)
H23A1.40240.88020.13570.080*
H23B1.29910.94070.12910.080*
H23C1.30060.81700.12850.080*
C24A1.40181 (19)0.7852 (2)0.2846 (2)0.0509 (7)
H24A1.37670.72100.25780.076*
H24B1.40020.77980.34620.076*
H24C1.47010.79670.27100.076*
C5A1.22947 (16)0.86733 (18)0.28626 (14)0.0309 (4)
H5A1.24470.86260.34910.037*
C6A1.17428 (18)0.7645 (2)0.26226 (18)0.0408 (6)
H6A11.14490.76810.20290.049*
H6A21.22180.70620.26690.049*
C7A1.09128 (18)0.74588 (19)0.32233 (19)0.0410 (5)
H7A11.12210.73850.38100.049*
H7A21.05750.67990.30650.049*
C8A1.01189 (16)0.83426 (18)0.32031 (15)0.0331 (5)
C26A0.94773 (19)0.8264 (3)0.23252 (17)0.0479 (6)
H26A0.99150.82660.18650.072*
H26B0.90250.88550.22600.072*
H26C0.90930.76210.23060.072*
C9A1.06731 (16)0.94255 (17)0.33170 (15)0.0321 (4)
H9A1.09970.94080.39090.038*
C10A1.15646 (17)0.96339 (19)0.27366 (15)0.0331 (5)
C25A1.1193 (2)0.9870 (3)0.17901 (18)0.0508 (7)
H25A1.05521.02240.17690.076*
H25B1.11200.92210.14720.076*
H25C1.16751.03140.15380.076*
C11A0.99067 (19)1.0334 (2)0.3321 (2)0.0445 (6)
H11A1.02681.09940.34230.053*
H11B0.95301.03770.27580.053*
C12A0.91727 (19)1.0190 (2)0.4008 (2)0.0430 (6)
H12A0.86701.07470.39490.052*
H12B0.95371.02570.45740.052*
C13A0.86364 (16)0.91191 (19)0.39464 (15)0.0333 (5)
H13A0.82480.90890.33800.040*
C14A0.94152 (16)0.81979 (18)0.39779 (15)0.0330 (4)
C27A1.00401 (19)0.8173 (2)0.48636 (16)0.0434 (6)
H27A0.95950.82340.53160.065*
H27B1.05090.87510.49000.065*
H27C1.04040.75190.49250.065*
C15A0.88247 (19)0.7147 (2)0.38937 (19)0.0433 (6)
H15A0.84520.71190.33280.052*
H15B0.93030.65670.39290.052*
C16A0.8090 (2)0.6995 (2)0.4580 (2)0.0475 (6)
H16A0.84730.68870.51340.057*
H16B0.76980.63610.44470.057*
C17A0.73689 (17)0.7918 (2)0.46578 (16)0.0391 (5)
C18A0.78804 (17)0.90099 (19)0.46337 (15)0.0348 (5)
H18A0.82140.91780.52050.042*
C19A0.69298 (17)0.9692 (2)0.44596 (16)0.0390 (5)
H19A0.71061.03870.42400.047*
C20A0.63477 (19)0.9810 (3)0.52715 (17)0.0464 (6)
C29A0.5409 (2)1.0501 (3)0.5060 (2)0.0584 (8)
H29A0.56151.11910.48890.088*
H29B0.50391.05580.55620.088*
H29C0.49881.01850.45960.088*
C30A0.7016 (3)1.0367 (3)0.5986 (2)0.0630 (9)
H30A0.75230.98850.62280.095*
H30B0.66081.05990.64300.095*
H30C0.73381.09650.57470.095*
C21A0.6028 (2)0.8707 (3)0.5547 (2)0.0594 (8)
H21A0.58430.87430.61370.071*
H21B0.54300.84980.51830.071*
C22A0.6834 (2)0.7858 (3)0.54953 (19)0.0522 (7)
H22A0.65220.71700.55330.063*
H22B0.73320.79320.59870.063*
C28A0.65841 (19)0.8003 (2)0.38829 (19)0.0474 (6)
H28A0.68620.77520.33630.057*
H28B0.59920.75850.39770.057*
O3A1.48053 (13)1.00257 (17)0.26184 (14)0.0501 (5)
H3A11.52400.97070.29230.075*
O19A0.63221 (13)0.91049 (17)0.38001 (12)0.0462 (4)
C1B−0.2473 (3)0.2089 (3)0.1513 (3)0.0712 (11)
H1B1−0.25250.19060.09040.085*
H1B2−0.20030.15990.18130.085*
C2B−0.3505 (3)0.1957 (3)0.1856 (3)0.0715 (10)
H2B1−0.39910.24090.15320.086*
H2B2−0.37290.12320.17760.086*
C3B−0.3458 (2)0.2240 (3)0.2808 (2)0.0570 (8)
H3B−0.29840.17560.31250.068*
C4B−0.3095 (2)0.3373 (2)0.29996 (19)0.0486 (6)
C23B−0.3896 (2)0.4190 (3)0.2711 (3)0.0698 (9)
H23D−0.41150.40820.21110.105*
H23E−0.36160.48850.27880.105*
H23F−0.44620.41170.30500.105*
C24B−0.2904 (3)0.3460 (4)0.3991 (2)0.0769 (11)
H24D−0.27400.41770.41470.115*
H24E−0.23520.30080.41900.115*
H24F−0.35010.32500.42530.115*
C5B−0.20754 (18)0.3516 (2)0.25790 (17)0.0408 (5)
H5B−0.16170.30120.28900.049*
C6B−0.1576 (2)0.4583 (3)0.2765 (2)0.0610 (8)
H6B1−0.16250.47710.33650.073*
H6B2−0.19240.51190.24060.073*
C7B−0.0463 (2)0.4541 (3)0.2579 (2)0.0583 (8)
H7B1−0.01130.40450.29760.070*
H7B2−0.01650.52310.26930.070*
C8B−0.02884 (19)0.4216 (2)0.16479 (19)0.0418 (5)
C26B−0.0611 (3)0.5157 (3)0.1055 (3)0.0720 (11)
H26D−0.05210.49770.04660.108*
H26E−0.02030.57610.12230.108*
H26F−0.13090.53180.11080.108*
C9B−0.09107 (18)0.3195 (2)0.14203 (15)0.0388 (5)
H9B−0.05950.26510.18030.047*
C10B−0.20469 (19)0.3209 (2)0.16231 (17)0.0444 (6)
C25B−0.2713 (2)0.3952 (4)0.0998 (2)0.0739 (11)
H25D−0.24620.39440.04360.111*
H25E−0.26850.46590.12220.111*
H25F−0.34000.37080.09530.111*
C11B−0.0740 (2)0.2824 (3)0.05069 (18)0.0598 (9)
H11C−0.11280.21860.03760.072*
H11D−0.09790.33610.00930.072*
C12B0.0367 (2)0.2607 (3)0.0419 (2)0.0569 (8)
H12C0.04500.2402−0.01720.068*
H12D0.05830.20180.07900.068*
C13B0.10390 (18)0.3549 (2)0.06550 (15)0.0394 (5)
H13B0.08290.41110.02440.047*
C14B0.08792 (18)0.39761 (19)0.15696 (16)0.0372 (5)
C27B0.1273 (2)0.3165 (3)0.22556 (17)0.0516 (7)
H27D0.19140.28970.21150.077*
H27E0.07990.25930.22670.077*
H27F0.13500.34970.28130.077*
C15B0.1532 (2)0.4977 (2)0.1723 (2)0.0571 (8)
H15C0.12880.55150.13120.069*
H15D0.14530.52440.22990.069*
C16B0.2653 (2)0.4786 (3)0.1634 (2)0.0636 (9)
H16C0.29250.43470.21110.076*
H16D0.30050.54570.16780.076*
C17B0.2866 (2)0.4255 (2)0.07837 (19)0.0492 (6)
C18B0.21616 (19)0.3323 (2)0.05480 (15)0.0396 (5)
H18B0.23840.27030.08910.048*
C19B0.2399 (2)0.3173 (3)−0.03868 (18)0.0620 (9)
H19B0.18680.2753−0.07030.074*
C20B0.3440 (3)0.2659 (4)−0.0460 (2)0.0688 (10)
C29B0.3596 (4)0.2538 (6)−0.1423 (3)0.115 (2)
H29D0.35690.3220−0.16940.173*
H29E0.30730.2097−0.16950.173*
H29F0.42420.2221−0.14820.173*
C30B0.3482 (4)0.1572 (4)−0.0041 (4)0.0938 (14)
H30D0.39970.1158−0.02770.141*
H30E0.28400.1228−0.01550.141*
H30F0.36350.16440.05720.141*
C21B0.4246 (2)0.3413 (4)−0.0031 (2)0.0659 (9)
H21C0.48820.30360.00680.079*
H21D0.43470.3992−0.04230.079*
C22B0.3958 (2)0.3857 (3)0.0823 (2)0.0608 (8)
H22C0.44110.44350.09950.073*
H22D0.40510.33130.12620.073*
C28B0.2655 (3)0.4934 (3)−0.0014 (3)0.0750 (11)
H28C0.21040.54180.00620.090*
H28D0.32500.5341−0.01220.090*
O3B−0.4427 (2)0.2113 (2)0.3131 (2)0.0794 (8)
H3B1−0.45990.14930.30900.119*
O19B0.2390 (2)0.4238 (3)−0.07185 (16)0.0825 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0370 (12)0.0286 (11)0.0573 (15)−0.0037 (9)0.0131 (11)0.0015 (10)
C2A0.0405 (13)0.0349 (12)0.0575 (15)−0.0081 (10)0.0151 (11)0.0023 (11)
C3A0.0307 (11)0.0408 (13)0.0431 (12)−0.0083 (10)0.0061 (9)0.0012 (10)
C4A0.0303 (10)0.0366 (12)0.0424 (12)−0.0021 (9)0.0068 (9)−0.0029 (10)
C23A0.0501 (15)0.0683 (19)0.0447 (14)−0.0031 (14)0.0178 (12)−0.0087 (13)
C24A0.0324 (12)0.0425 (14)0.079 (2)0.0015 (11)0.0106 (12)0.0039 (13)
C5A0.0277 (10)0.0303 (11)0.0350 (11)−0.0034 (9)0.0039 (8)−0.0024 (9)
C6A0.0332 (11)0.0328 (12)0.0571 (15)−0.0037 (9)0.0087 (10)−0.0124 (11)
C7A0.0317 (11)0.0273 (11)0.0655 (16)−0.0036 (9)0.0124 (11)−0.0051 (11)
C8A0.0259 (10)0.0328 (11)0.0406 (11)−0.0017 (8)0.0022 (8)−0.0032 (9)
C26A0.0348 (12)0.0666 (18)0.0418 (13)−0.0087 (12)0.0005 (9)−0.0081 (12)
C9A0.0286 (10)0.0286 (11)0.0392 (11)−0.0003 (8)0.0041 (8)0.0003 (9)
C10A0.0316 (10)0.0313 (11)0.0368 (11)0.0005 (9)0.0043 (8)0.0042 (9)
C25A0.0412 (13)0.0647 (19)0.0463 (14)0.0044 (13)0.0030 (11)0.0171 (13)
C11A0.0365 (12)0.0308 (12)0.0681 (17)0.0038 (10)0.0145 (12)0.0092 (12)
C12A0.0349 (12)0.0298 (12)0.0662 (17)−0.0004 (10)0.0155 (11)−0.0025 (11)
C13A0.0276 (10)0.0326 (11)0.0399 (12)−0.0002 (9)0.0044 (8)0.0012 (9)
C14A0.0276 (10)0.0288 (10)0.0426 (12)−0.0007 (8)0.0038 (8)0.0003 (9)
C27A0.0361 (11)0.0497 (15)0.0440 (13)0.0024 (11)0.0018 (9)0.0052 (12)
C15A0.0370 (12)0.0317 (12)0.0622 (16)−0.0041 (10)0.0096 (11)−0.0029 (11)
C16A0.0417 (13)0.0362 (13)0.0656 (17)−0.0055 (11)0.0098 (12)0.0070 (12)
C17A0.0315 (11)0.0414 (13)0.0448 (13)−0.0054 (10)0.0059 (9)0.0024 (10)
C18A0.0293 (10)0.0360 (12)0.0392 (12)−0.0017 (9)0.0039 (9)−0.0002 (9)
C19A0.0319 (11)0.0438 (13)0.0414 (12)0.0010 (10)0.0043 (9)0.0001 (11)
C20A0.0374 (12)0.0576 (17)0.0452 (14)0.0042 (12)0.0104 (10)−0.0046 (12)
C29A0.0428 (14)0.074 (2)0.0596 (18)0.0124 (15)0.0118 (13)−0.0085 (16)
C30A0.0633 (19)0.079 (2)0.0469 (16)0.0099 (17)0.0034 (14)−0.0166 (15)
C21A0.0505 (15)0.069 (2)0.0625 (18)−0.0006 (15)0.0262 (13)0.0029 (16)
C22A0.0479 (14)0.0561 (17)0.0547 (16)−0.0056 (13)0.0173 (12)0.0106 (13)
C28A0.0357 (12)0.0511 (15)0.0546 (15)−0.0044 (11)−0.0004 (10)−0.0086 (12)
O3A0.0318 (8)0.0523 (11)0.0673 (12)−0.0081 (8)0.0104 (8)0.0076 (10)
O19A0.0380 (9)0.0549 (11)0.0442 (10)0.0065 (8)−0.0049 (7)−0.0054 (8)
C1B0.064 (2)0.067 (2)0.086 (2)−0.0353 (18)0.0331 (18)−0.0368 (19)
C2B0.0626 (19)0.066 (2)0.089 (3)−0.0335 (17)0.0255 (18)−0.0284 (19)
C3B0.0506 (16)0.0530 (17)0.0701 (19)−0.0124 (14)0.0211 (14)−0.0017 (15)
C4B0.0413 (13)0.0477 (15)0.0575 (15)−0.0065 (12)0.0084 (11)−0.0075 (13)
C23B0.0454 (16)0.063 (2)0.104 (3)0.0024 (15)0.0206 (17)0.000 (2)
C24B0.0607 (19)0.112 (3)0.0605 (19)−0.023 (2)0.0180 (15)−0.017 (2)
C5B0.0352 (11)0.0368 (12)0.0504 (14)−0.0047 (10)0.0035 (10)−0.0068 (11)
C6B0.0501 (16)0.0507 (17)0.085 (2)−0.0141 (14)0.0227 (15)−0.0233 (16)
C7B0.0470 (15)0.0514 (16)0.079 (2)−0.0181 (13)0.0180 (14)−0.0327 (15)
C8B0.0379 (12)0.0282 (11)0.0590 (15)−0.0054 (9)0.0026 (10)0.0031 (11)
C26B0.0490 (16)0.0510 (18)0.117 (3)0.0050 (14)0.0129 (18)0.037 (2)
C9B0.0401 (12)0.0371 (12)0.0388 (12)−0.0108 (10)0.0009 (9)−0.0040 (10)
C10B0.0393 (12)0.0494 (15)0.0443 (13)−0.0125 (11)0.0024 (10)−0.0038 (12)
C25B0.0444 (16)0.111 (3)0.065 (2)−0.0022 (18)−0.0034 (14)0.022 (2)
C11B0.0533 (16)0.083 (2)0.0436 (14)−0.0297 (16)0.0066 (12)−0.0196 (15)
C12B0.0573 (16)0.0645 (19)0.0505 (15)−0.0237 (15)0.0146 (13)−0.0230 (14)
C13B0.0390 (12)0.0444 (13)0.0340 (11)−0.0114 (10)−0.0013 (9)0.0048 (10)
C14B0.0364 (11)0.0314 (11)0.0430 (12)−0.0055 (9)−0.0002 (9)−0.0040 (9)
C27B0.0461 (14)0.0678 (19)0.0398 (13)0.0066 (14)−0.0015 (10)0.0051 (13)
C15B0.0489 (15)0.0438 (15)0.080 (2)−0.0155 (12)0.0113 (14)−0.0201 (15)
C16B0.0478 (15)0.062 (2)0.082 (2)−0.0183 (15)0.0073 (14)−0.0259 (17)
C17B0.0407 (13)0.0497 (16)0.0568 (16)−0.0121 (12)0.0028 (11)−0.0006 (13)
C18B0.0423 (12)0.0441 (14)0.0320 (11)−0.0060 (11)0.0003 (9)0.0004 (10)
C19B0.0491 (15)0.099 (3)0.0386 (14)−0.0242 (17)0.0072 (11)−0.0054 (16)
C20B0.0576 (18)0.098 (3)0.0538 (17)−0.0161 (19)0.0226 (14)−0.0196 (18)
C29B0.083 (3)0.201 (7)0.067 (2)−0.040 (4)0.036 (2)−0.049 (3)
C30B0.090 (3)0.079 (3)0.120 (4)0.003 (2)0.045 (3)−0.023 (3)
C21B0.0448 (15)0.095 (3)0.0585 (18)−0.0074 (17)0.0080 (13)0.0002 (18)
C22B0.0371 (13)0.080 (2)0.0638 (18)−0.0079 (15)−0.0007 (12)−0.0097 (17)
C28B0.0590 (19)0.069 (2)0.098 (3)−0.0090 (17)0.0142 (19)0.035 (2)
O3B0.0670 (14)0.0738 (16)0.1036 (19)−0.0283 (13)0.0428 (14)−0.0159 (15)
O19B0.0687 (15)0.127 (3)0.0513 (13)−0.0092 (16)0.0022 (11)0.0403 (15)
Geometric parameters (Å, °) top
C1A—C2A1.535 (3)C1B—C2B1.522 (4)
C1A—C10A1.546 (3)C1B—C10B1.532 (4)
C1A—H1A10.9700C1B—H1B10.9700
C1A—H1A20.9700C1B—H1B20.9700
C2A—C3A1.503 (4)C2B—C3B1.518 (5)
C2A—H2A10.9700C2B—H2B10.9700
C2A—H2A20.9700C2B—H2B20.9700
C3A—O3A1.438 (3)C3B—O3B1.431 (4)
C3A—C4A1.544 (3)C3B—C4B1.535 (4)
C3A—H3A0.9800C3B—H3B0.9800
C4A—C23A1.534 (4)C4B—C23B1.523 (5)
C4A—C24A1.539 (4)C4B—C24B1.542 (5)
C4A—C5A1.560 (3)C4B—C5B1.565 (4)
C23A—H23A0.9600C23B—H23D0.9600
C23A—H23B0.9600C23B—H23E0.9600
C23A—H23C0.9600C23B—H23F0.9600
C24A—H24A0.9600C24B—H24D0.9600
C24A—H24B0.9600C24B—H24E0.9600
C24A—H24C0.9600C24B—H24F0.9600
C5A—C6A1.525 (3)C5B—C6B1.521 (4)
C5A—C10A1.558 (3)C5B—C10B1.538 (4)
C5A—H5A0.9800C5B—H5B0.9800
C6A—C7A1.523 (3)C6B—C7B1.532 (4)
C6A—H6A10.9700C6B—H6B10.9700
C6A—H6A20.9700C6B—H6B20.9700
C7A—C8A1.537 (3)C7B—C8B1.540 (4)
C7A—H7A10.9700C7B—H7B10.9700
C7A—H7A20.9700C7B—H7B20.9700
C8A—C26A1.546 (3)C8B—C26B1.543 (4)
C8A—C9A1.560 (3)C8B—C9B1.559 (3)
C8A—C14A1.597 (3)C8B—C14B1.595 (3)
C26A—H26A0.9600C26B—H26D0.9600
C26A—H26B0.9600C26B—H26E0.9600
C26A—H26C0.9600C26B—H26F0.9600
C9A—C11A1.537 (3)C9B—C11B1.529 (4)
C9A—C10A1.572 (3)C9B—C10B1.568 (3)
C9A—H9A0.9800C9B—H9B0.9800
C10A—C25A1.538 (3)C10B—C25B1.569 (5)
C25A—H25A0.9600C25B—H25D0.9600
C25A—H25B0.9600C25B—H25E0.9600
C25A—H25C0.9600C25B—H25F0.9600
C11A—C12A1.517 (4)C11B—C12B1.514 (4)
C11A—H11A0.9700C11B—H11C0.9700
C11A—H11B0.9700C11B—H11D0.9700
C12A—C13A1.532 (3)C12B—C13B1.516 (4)
C12A—H12A0.9700C12B—H12C0.9700
C12A—H12B0.9700C12B—H12D0.9700
C13A—C18A1.534 (3)C13B—C18B1.542 (4)
C13A—C14A1.558 (3)C13B—C14B1.551 (3)
C13A—H13A0.9800C13B—H13B0.9800
C14A—C27A1.543 (3)C14B—C27B1.539 (4)
C14A—C15A1.545 (3)C14B—C15B1.543 (3)
C27A—H27A0.9600C27B—H27D0.9600
C27A—H27B0.9600C27B—H27E0.9600
C27A—H27C0.9600C27B—H27F0.9600
C15A—C16A1.518 (4)C15B—C16B1.527 (4)
C15A—H15A0.9700C15B—H15C0.9700
C15A—H15B0.9700C15B—H15D0.9700
C16A—C17A1.523 (4)C16B—C17B1.529 (4)
C16A—H16A0.9700C16B—H16C0.9700
C16A—H16B0.9700C16B—H16D0.9700
C17A—C28A1.525 (4)C17B—C28B1.514 (5)
C17A—C22A1.537 (4)C17B—C18B1.532 (4)
C17A—C18A1.544 (3)C17B—C22B1.533 (4)
C18A—C19A1.534 (3)C18B—C19B1.523 (4)
C18A—H18A0.9800C18B—H18B0.9800
C19A—O19A1.452 (3)C19B—O19B1.444 (5)
C19A—C20A1.542 (3)C19B—C20B1.541 (5)
C19A—H19A0.9800C19B—H19B0.9800
C20A—C30A1.531 (4)C20B—C30B1.522 (7)
C20A—C21A1.533 (5)C20B—C29B1.535 (5)
C20A—C29A1.535 (4)C20B—C21B1.542 (5)
C29A—H29A0.9600C29B—H29D0.9600
C29A—H29B0.9600C29B—H29E0.9600
C29A—H29C0.9600C29B—H29F0.9600
C30A—H30A0.9600C30B—H30D0.9600
C30A—H30B0.9600C30B—H30E0.9600
C30A—H30C0.9600C30B—H30F0.9600
C21A—C22A1.524 (5)C21B—C22B1.519 (5)
C21A—H21A0.9700C21B—H21C0.9700
C21A—H21B0.9700C21B—H21D0.9700
C22A—H22A0.9700C22B—H22C0.9700
C22A—H22B0.9700C22B—H22D0.9700
C28A—O19A1.442 (4)C28B—O19B1.424 (5)
C28A—H28A0.9700C28B—H28C0.9700
C28A—H28B0.9700C28B—H28D0.9700
O3A—H3A10.8200O3B—H3B10.8200
C2A—C1A—C10A113.4 (2)C2B—C1B—C10B113.4 (3)
C2A—C1A—H1A1108.9C2B—C1B—H1B1108.9
C10A—C1A—H1A1108.9C10B—C1B—H1B1108.9
C2A—C1A—H1A2108.9C2B—C1B—H1B2108.9
C10A—C1A—H1A2108.9C10B—C1B—H1B2108.9
H1A1—C1A—H1A2107.7H1B1—C1B—H1B2107.7
C3A—C2A—C1A110.3 (2)C3B—C2B—C1B110.6 (3)
C3A—C2A—H2A1109.6C3B—C2B—H2B1109.5
C1A—C2A—H2A1109.6C1B—C2B—H2B1109.5
C3A—C2A—H2A2109.6C3B—C2B—H2B2109.5
C1A—C2A—H2A2109.6C1B—C2B—H2B2109.5
H2A1—C2A—H2A2108.1H2B1—C2B—H2B2108.1
O3A—C3A—C2A107.9 (2)O3B—C3B—C2B110.7 (3)
O3A—C3A—C4A112.9 (2)O3B—C3B—C4B108.3 (3)
C2A—C3A—C4A113.49 (19)C2B—C3B—C4B113.3 (3)
O3A—C3A—H3A107.4O3B—C3B—H3B108.2
C2A—C3A—H3A107.4C2B—C3B—H3B108.2
C4A—C3A—H3A107.4C4B—C3B—H3B108.2
C23A—C4A—C24A107.7 (2)C23B—C4B—C3B112.3 (3)
C23A—C4A—C3A111.4 (2)C23B—C4B—C24B107.2 (3)
C24A—C4A—C3A107.50 (19)C3B—C4B—C24B106.4 (3)
C23A—C4A—C5A115.2 (2)C23B—C4B—C5B114.0 (3)
C24A—C4A—C5A108.6 (2)C3B—C4B—C5B107.2 (2)
C3A—C4A—C5A106.31 (18)C24B—C4B—C5B109.6 (2)
C4A—C23A—H23A109.5C4B—C23B—H23D109.5
C4A—C23A—H23B109.5C4B—C23B—H23E109.5
H23A—C23A—H23B109.5H23D—C23B—H23E109.5
C4A—C23A—H23C109.5C4B—C23B—H23F109.5
H23A—C23A—H23C109.5H23D—C23B—H23F109.5
H23B—C23A—H23C109.5H23E—C23B—H23F109.5
C4A—C24A—H24A109.5C4B—C24B—H24D109.5
C4A—C24A—H24B109.5C4B—C24B—H24E109.5
H24A—C24A—H24B109.5H24D—C24B—H24E109.5
C4A—C24A—H24C109.5C4B—C24B—H24F109.5
H24A—C24A—H24C109.5H24D—C24B—H24F109.5
H24B—C24A—H24C109.5H24E—C24B—H24F109.5
C6A—C5A—C10A110.85 (17)C6B—C5B—C10B111.1 (2)
C6A—C5A—C4A114.69 (19)C6B—C5B—C4B113.8 (2)
C10A—C5A—C4A117.16 (19)C10B—C5B—C4B117.9 (2)
C6A—C5A—H5A104.1C6B—C5B—H5B104.1
C10A—C5A—H5A104.1C10B—C5B—H5B104.1
C4A—C5A—H5A104.1C4B—C5B—H5B104.1
C7A—C6A—C5A109.95 (19)C5B—C6B—C7B110.2 (2)
C7A—C6A—H6A1109.7C5B—C6B—H6B1109.6
C5A—C6A—H6A1109.7C7B—C6B—H6B1109.6
C7A—C6A—H6A2109.7C5B—C6B—H6B2109.6
C5A—C6A—H6A2109.7C7B—C6B—H6B2109.6
H6A1—C6A—H6A2108.2H6B1—C6B—H6B2108.1
C6A—C7A—C8A114.0 (2)C6B—C7B—C8B114.4 (2)
C6A—C7A—H7A1108.8C6B—C7B—H7B1108.7
C8A—C7A—H7A1108.8C8B—C7B—H7B1108.7
C6A—C7A—H7A2108.8C6B—C7B—H7B2108.7
C8A—C7A—H7A2108.8C8B—C7B—H7B2108.7
H7A1—C7A—H7A2107.7H7B1—C7B—H7B2107.6
C7A—C8A—C26A107.2 (2)C7B—C8B—C26B107.2 (3)
C7A—C8A—C9A108.81 (17)C7B—C8B—C9B108.3 (2)
C26A—C8A—C9A112.0 (2)C26B—C8B—C9B113.1 (2)
C7A—C8A—C14A110.28 (19)C7B—C8B—C14B110.5 (2)
C26A—C8A—C14A110.04 (18)C26B—C8B—C14B108.8 (2)
C9A—C8A—C14A108.49 (17)C9B—C8B—C14B108.9 (2)
C8A—C26A—H26A109.5C8B—C26B—H26D109.5
C8A—C26A—H26B109.5C8B—C26B—H26E109.5
H26A—C26A—H26B109.5H26D—C26B—H26E109.5
C8A—C26A—H26C109.5C8B—C26B—H26F109.5
H26A—C26A—H26C109.5H26D—C26B—H26F109.5
H26B—C26A—H26C109.5H26E—C26B—H26F109.5
C11A—C9A—C8A110.67 (18)C11B—C9B—C8B110.3 (2)
C11A—C9A—C10A114.15 (19)C11B—C9B—C10B114.3 (2)
C8A—C9A—C10A117.04 (19)C8B—C9B—C10B116.5 (2)
C11A—C9A—H9A104.5C11B—C9B—H9B104.8
C8A—C9A—H9A104.5C8B—C9B—H9B104.8
C10A—C9A—H9A104.5C10B—C9B—H9B104.8
C25A—C10A—C1A108.3 (2)C1B—C10B—C5B107.6 (2)
C25A—C10A—C5A114.6 (2)C1B—C10B—C9B108.6 (2)
C1A—C10A—C5A106.66 (17)C5B—C10B—C9B107.56 (19)
C25A—C10A—C9A112.66 (19)C1B—C10B—C25B107.7 (3)
C1A—C10A—C9A107.49 (19)C5B—C10B—C25B112.6 (3)
C5A—C10A—C9A106.78 (18)C9B—C10B—C25B112.5 (2)
C10A—C25A—H25A109.5C10B—C25B—H25D109.5
C10A—C25A—H25B109.5C10B—C25B—H25E109.5
H25A—C25A—H25B109.5H25D—C25B—H25E109.5
C10A—C25A—H25C109.5C10B—C25B—H25F109.5
H25A—C25A—H25C109.5H25D—C25B—H25F109.5
H25B—C25A—H25C109.5H25E—C25B—H25F109.5
C12A—C11A—C9A112.3 (2)C12B—C11B—C9B111.2 (2)
C12A—C11A—H11A109.1C12B—C11B—H11C109.4
C9A—C11A—H11A109.1C9B—C11B—H11C109.4
C12A—C11A—H11B109.1C12B—C11B—H11D109.4
C9A—C11A—H11B109.1C9B—C11B—H11D109.4
H11A—C11A—H11B107.9H11C—C11B—H11D108.0
C11A—C12A—C13A112.7 (2)C11B—C12B—C13B113.0 (3)
C11A—C12A—H12A109.0C11B—C12B—H12C109.0
C13A—C12A—H12A109.0C13B—C12B—H12C109.0
C11A—C12A—H12B109.0C11B—C12B—H12D109.0
C13A—C12A—H12B109.0C13B—C12B—H12D109.0
H12A—C12A—H12B107.8H12C—C12B—H12D107.8
C12A—C13A—C18A111.5 (2)C12B—C13B—C18B112.5 (2)
C12A—C13A—C14A110.98 (17)C12B—C13B—C14B111.8 (2)
C18A—C13A—C14A112.58 (19)C18B—C13B—C14B111.98 (18)
C12A—C13A—H13A107.2C12B—C13B—H13B106.7
C18A—C13A—H13A107.2C18B—C13B—H13B106.7
C14A—C13A—H13A107.2C14B—C13B—H13B106.7
C27A—C14A—C15A106.7 (2)C27B—C14B—C15B106.8 (2)
C27A—C14A—C13A110.32 (19)C27B—C14B—C13B109.6 (2)
C15A—C14A—C13A108.20 (17)C15B—C14B—C13B108.0 (2)
C27A—C14A—C8A111.64 (18)C27B—C14B—C8B110.4 (2)
C15A—C14A—C8A111.18 (19)C15B—C14B—C8B111.6 (2)
C13A—C14A—C8A108.73 (18)C13B—C14B—C8B110.35 (19)
C14A—C27A—H27A109.5C14B—C27B—H27D109.5
C14A—C27A—H27B109.5C14B—C27B—H27E109.5
H27A—C27A—H27B109.5H27D—C27B—H27E109.5
C14A—C27A—H27C109.5C14B—C27B—H27F109.5
H27A—C27A—H27C109.5H27D—C27B—H27F109.5
H27B—C27A—H27C109.5H27E—C27B—H27F109.5
C16A—C15A—C14A113.7 (2)C16B—C15B—C14B113.2 (2)
C16A—C15A—H15A108.8C16B—C15B—H15C108.9
C14A—C15A—H15A108.8C14B—C15B—H15C108.9
C16A—C15A—H15B108.8C16B—C15B—H15D108.9
C14A—C15A—H15B108.8C14B—C15B—H15D108.9
H15A—C15A—H15B107.7H15C—C15B—H15D107.7
C15A—C16A—C17A113.9 (2)C15B—C16B—C17B113.8 (2)
C15A—C16A—H16A108.8C15B—C16B—H16C108.8
C17A—C16A—H16A108.8C17B—C16B—H16C108.8
C15A—C16A—H16B108.8C15B—C16B—H16D108.8
C17A—C16A—H16B108.8C17B—C16B—H16D108.8
H16A—C16A—H16B107.7H16C—C16B—H16D107.7
C16A—C17A—C28A112.5 (2)C28B—C17B—C16B114.9 (3)
C16A—C17A—C22A111.7 (2)C28B—C17B—C18B100.2 (2)
C28A—C17A—C22A109.6 (2)C16B—C17B—C18B113.0 (2)
C16A—C17A—C18A113.90 (18)C28B—C17B—C22B109.1 (3)
C28A—C17A—C18A100.9 (2)C16B—C17B—C22B110.9 (2)
C22A—C17A—C18A107.5 (2)C18B—C17B—C22B108.2 (3)
C13A—C18A—C19A113.9 (2)C19B—C18B—C17B98.7 (2)
C13A—C18A—C17A114.4 (2)C19B—C18B—C13B114.1 (2)
C19A—C18A—C17A98.75 (18)C17B—C18B—C13B114.0 (2)
C13A—C18A—H18A109.8C19B—C18B—H18B109.9
C19A—C18A—H18A109.8C17B—C18B—H18B109.9
C17A—C18A—H18A109.8C13B—C18B—H18B109.9
O19A—C19A—C18A103.5 (2)O19B—C19B—C18B103.1 (3)
O19A—C19A—C20A109.8 (2)O19B—C19B—C20B110.3 (3)
C18A—C19A—C20A112.0 (2)C18B—C19B—C20B112.6 (3)
O19A—C19A—H19A110.5O19B—C19B—H19B110.2
C18A—C19A—H19A110.5C18B—C19B—H19B110.2
C20A—C19A—H19A110.5C20B—C19B—H19B110.2
C30A—C20A—C21A112.1 (3)C30B—C20B—C29B108.7 (4)
C30A—C20A—C29A107.6 (3)C30B—C20B—C19B110.5 (3)
C21A—C20A—C29A109.9 (2)C29B—C20B—C19B108.2 (3)
C30A—C20A—C19A109.6 (2)C30B—C20B—C21B112.2 (4)
C21A—C20A—C19A108.1 (2)C29B—C20B—C21B109.6 (3)
C29A—C20A—C19A109.6 (2)C19B—C20B—C21B107.5 (3)
C20A—C29A—H29A109.5C20B—C29B—H29D109.5
C20A—C29A—H29B109.5C20B—C29B—H29E109.5
H29A—C29A—H29B109.5H29D—C29B—H29E109.5
C20A—C29A—H29C109.5C20B—C29B—H29F109.5
H29A—C29A—H29C109.5H29D—C29B—H29F109.5
H29B—C29A—H29C109.5H29E—C29B—H29F109.5
C20A—C30A—H30A109.5C20B—C30B—H30D109.5
C20A—C30A—H30B109.5C20B—C30B—H30E109.5
H30A—C30A—H30B109.5H30D—C30B—H30E109.5
C20A—C30A—H30C109.5C20B—C30B—H30F109.5
H30A—C30A—H30C109.5H30D—C30B—H30F109.5
H30B—C30A—H30C109.5H30E—C30B—H30F109.5
C22A—C21A—C20A114.5 (2)C22B—C21B—C20B112.8 (3)
C22A—C21A—H21A108.6C22B—C21B—H21C109.0
C20A—C21A—H21A108.6C20B—C21B—H21C109.0
C22A—C21A—H21B108.6C22B—C21B—H21D109.0
C20A—C21A—H21B108.6C20B—C21B—H21D109.0
H21A—C21A—H21B107.6H21C—C21B—H21D107.8
C21A—C22A—C17A112.9 (2)C21B—C22B—C17B113.4 (3)
C21A—C22A—H22A109.0C21B—C22B—H22C108.9
C17A—C22A—H22A109.0C17B—C22B—H22C108.9
C21A—C22A—H22B109.0C21B—C22B—H22D108.9
C17A—C22A—H22B109.0C17B—C22B—H22D108.9
H22A—C22A—H22B107.8H22C—C22B—H22D107.7
O19A—C28A—C17A106.4 (2)O19B—C28B—C17B107.0 (3)
O19A—C28A—H28A110.5O19B—C28B—H28C110.3
C17A—C28A—H28A110.5C17B—C28B—H28C110.3
O19A—C28A—H28B110.5O19B—C28B—H28D110.3
C17A—C28A—H28B110.5C17B—C28B—H28D110.3
H28A—C28A—H28B108.6H28C—C28B—H28D108.6
C3A—O3A—H3A1109.5C3B—O3B—H3B1109.5
C28A—O19A—C19A108.55 (19)C28B—O19B—C19B108.1 (2)
C10A—C1A—C2A—C3A−58.3 (3)C10B—C1B—C2B—C3B−58.4 (5)
C1A—C2A—C3A—O3A−174.8 (2)C1B—C2B—C3B—O3B−179.8 (3)
C1A—C2A—C3A—C4A59.4 (3)C1B—C2B—C3B—C4B58.4 (4)
O3A—C3A—C4A—C23A−52.3 (3)O3B—C3B—C4B—C23B−49.9 (4)
C2A—C3A—C4A—C23A70.9 (3)C2B—C3B—C4B—C23B73.2 (4)
O3A—C3A—C4A—C24A65.4 (3)O3B—C3B—C4B—C24B67.1 (3)
C2A—C3A—C4A—C24A−171.4 (2)C2B—C3B—C4B—C24B−169.8 (3)
O3A—C3A—C4A—C5A−178.45 (19)O3B—C3B—C4B—C5B−175.8 (3)
C2A—C3A—C4A—C5A−55.3 (3)C2B—C3B—C4B—C5B−52.7 (3)
C23A—C4A—C5A—C6A62.6 (3)C23B—C4B—C5B—C6B59.1 (3)
C24A—C4A—C5A—C6A−58.1 (3)C3B—C4B—C5B—C6B−176.0 (3)
C3A—C4A—C5A—C6A−173.5 (2)C24B—C4B—C5B—C6B−61.0 (4)
C23A—C4A—C5A—C10A−69.9 (3)C23B—C4B—C5B—C10B−73.6 (3)
C24A—C4A—C5A—C10A169.3 (2)C3B—C4B—C5B—C10B51.3 (3)
C3A—C4A—C5A—C10A53.9 (2)C24B—C4B—C5B—C10B166.3 (3)
C10A—C5A—C6A—C7A−63.0 (3)C10B—C5B—C6B—C7B−61.3 (3)
C4A—C5A—C6A—C7A161.6 (2)C4B—C5B—C6B—C7B162.8 (3)
C5A—C6A—C7A—C8A59.0 (3)C5B—C6B—C7B—C8B57.5 (4)
C6A—C7A—C8A—C26A71.5 (3)C6B—C7B—C8B—C26B72.7 (3)
C6A—C7A—C8A—C9A−49.8 (3)C6B—C7B—C8B—C9B−49.6 (3)
C6A—C7A—C8A—C14A−168.72 (19)C6B—C7B—C8B—C14B−168.8 (3)
C7A—C8A—C9A—C11A−178.7 (2)C7B—C8B—C9B—C11B−178.6 (2)
C26A—C8A—C9A—C11A62.9 (3)C26B—C8B—C9B—C11B62.7 (3)
C14A—C8A—C9A—C11A−58.7 (2)C14B—C8B—C9B—C11B−58.4 (3)
C7A—C8A—C9A—C10A48.2 (3)C7B—C8B—C9B—C10B49.0 (3)
C26A—C8A—C9A—C10A−70.2 (2)C26B—C8B—C9B—C10B−69.7 (3)
C14A—C8A—C9A—C10A168.15 (18)C14B—C8B—C9B—C10B169.2 (2)
C2A—C1A—C10A—C25A−70.7 (3)C2B—C1B—C10B—C5B52.9 (4)
C2A—C1A—C10A—C5A53.1 (3)C2B—C1B—C10B—C9B169.0 (3)
C2A—C1A—C10A—C9A167.3 (2)C2B—C1B—C10B—C25B−68.8 (4)
C6A—C5A—C10A—C25A−67.7 (3)C6B—C5B—C10B—C1B174.8 (3)
C4A—C5A—C10A—C25A66.6 (3)C4B—C5B—C10B—C1B−51.3 (3)
C6A—C5A—C10A—C1A172.5 (2)C6B—C5B—C10B—C9B58.0 (3)
C4A—C5A—C10A—C1A−53.2 (2)C4B—C5B—C10B—C9B−168.1 (2)
C6A—C5A—C10A—C9A57.8 (2)C6B—C5B—C10B—C25B−66.6 (3)
C4A—C5A—C10A—C9A−167.93 (18)C4B—C5B—C10B—C25B67.3 (3)
C11A—C9A—C10A—C25A−57.1 (3)C11B—C9B—C10B—C1B59.6 (3)
C8A—C9A—C10A—C25A74.4 (3)C8B—C9B—C10B—C1B−169.8 (3)
C11A—C9A—C10A—C1A62.0 (3)C11B—C9B—C10B—C5B175.8 (3)
C8A—C9A—C10A—C1A−166.42 (19)C8B—C9B—C10B—C5B−53.7 (3)
C11A—C9A—C10A—C5A176.2 (2)C11B—C9B—C10B—C25B−59.6 (4)
C8A—C9A—C10A—C5A−52.3 (2)C8B—C9B—C10B—C25B71.0 (3)
C8A—C9A—C11A—C12A55.8 (3)C8B—C9B—C11B—C12B58.7 (3)
C10A—C9A—C11A—C12A−169.6 (2)C10B—C9B—C11B—C12B−167.8 (3)
C9A—C11A—C12A—C13A−53.6 (3)C9B—C11B—C12B—C13B−56.3 (4)
C11A—C12A—C13A—C18A−178.5 (2)C11B—C12B—C13B—C18B−179.0 (2)
C11A—C12A—C13A—C14A55.1 (3)C11B—C12B—C13B—C14B54.0 (3)
C12A—C13A—C14A—C27A64.8 (3)C12B—C13B—C14B—C27B68.1 (3)
C18A—C13A—C14A—C27A−60.9 (2)C18B—C13B—C14B—C27B−59.1 (3)
C12A—C13A—C14A—C15A−178.8 (2)C12B—C13B—C14B—C15B−175.9 (2)
C18A—C13A—C14A—C15A55.5 (2)C18B—C13B—C14B—C15B56.9 (3)
C12A—C13A—C14A—C8A−57.9 (2)C12B—C13B—C14B—C8B−53.6 (3)
C18A—C13A—C14A—C8A176.36 (18)C18B—C13B—C14B—C8B179.1 (2)
C7A—C8A—C14A—C27A56.9 (3)C7B—C8B—C14B—C27B53.5 (3)
C26A—C8A—C14A—C27A175.0 (2)C26B—C8B—C14B—C27B170.9 (3)
C9A—C8A—C14A—C27A−62.1 (2)C9B—C8B—C14B—C27B−65.4 (3)
C7A—C8A—C14A—C15A−62.1 (2)C7B—C8B—C14B—C15B−65.2 (3)
C26A—C8A—C14A—C15A55.9 (3)C26B—C8B—C14B—C15B52.2 (3)
C9A—C8A—C14A—C15A178.82 (18)C9B—C8B—C14B—C15B175.9 (2)
C7A—C8A—C14A—C13A178.88 (18)C7B—C8B—C14B—C13B174.7 (2)
C26A—C8A—C14A—C13A−63.1 (2)C26B—C8B—C14B—C13B−67.8 (3)
C9A—C8A—C14A—C13A59.8 (2)C9B—C8B—C14B—C13B55.9 (3)
C27A—C14A—C15A—C16A61.8 (3)C27B—C14B—C15B—C16B60.5 (3)
C13A—C14A—C15A—C16A−57.0 (3)C13B—C14B—C15B—C16B−57.2 (3)
C8A—C14A—C15A—C16A−176.3 (2)C8B—C14B—C15B—C16B−178.7 (3)
C14A—C15A—C16A—C17A52.2 (3)C14B—C15B—C16B—C17B52.6 (4)
C15A—C16A—C17A—C28A70.5 (3)C15B—C16B—C17B—C28B68.9 (4)
C15A—C16A—C17A—C22A−165.6 (2)C15B—C16B—C17B—C18B−45.2 (4)
C15A—C16A—C17A—C18A−43.5 (3)C15B—C16B—C17B—C22B−166.8 (3)
C12A—C13A—C18A—C19A71.8 (3)C28B—C17B—C18B—C19B44.3 (3)
C14A—C13A—C18A—C19A−162.71 (19)C16B—C17B—C18B—C19B167.1 (3)
C12A—C13A—C18A—C17A−175.6 (2)C22B—C17B—C18B—C19B−69.8 (3)
C14A—C13A—C18A—C17A−50.1 (3)C28B—C17B—C18B—C13B−77.1 (3)
C16A—C17A—C18A—C13A43.1 (3)C16B—C17B—C18B—C13B45.7 (3)
C28A—C17A—C18A—C13A−77.8 (2)C22B—C17B—C18B—C13B168.8 (2)
C22A—C17A—C18A—C13A167.4 (2)C12B—C13B—C18B—C19B67.9 (3)
C16A—C17A—C18A—C19A164.4 (2)C14B—C13B—C18B—C19B−165.3 (2)
C28A—C17A—C18A—C19A43.6 (2)C12B—C13B—C18B—C17B−179.8 (2)
C22A—C17A—C18A—C19A−71.2 (2)C14B—C13B—C18B—C17B−52.9 (3)
C13A—C18A—C19A—O19A78.2 (2)C17B—C18B—C19B—O19B−44.7 (3)
C17A—C18A—C19A—O19A−43.5 (2)C13B—C18B—C19B—O19B76.6 (3)
C13A—C18A—C19A—C20A−163.6 (2)C17B—C18B—C19B—C20B74.2 (3)
C17A—C18A—C19A—C20A74.6 (2)C13B—C18B—C19B—C20B−164.5 (3)
O19A—C19A—C20A—C30A176.4 (3)O19B—C19B—C20B—C30B175.2 (3)
C18A—C19A—C20A—C30A62.0 (3)C18B—C19B—C20B—C30B60.6 (4)
O19A—C19A—C20A—C21A54.0 (3)O19B—C19B—C20B—C29B−65.9 (4)
C18A—C19A—C20A—C21A−60.4 (3)C18B—C19B—C20B—C29B179.5 (4)
O19A—C19A—C20A—C29A−65.8 (3)O19B—C19B—C20B—C21B52.4 (3)
C18A—C19A—C20A—C29A179.8 (2)C18B—C19B—C20B—C21B−62.2 (4)
C30A—C20A—C21A—C22A−79.1 (3)C30B—C20B—C21B—C22B−77.8 (4)
C29A—C20A—C21A—C22A161.3 (3)C29B—C20B—C21B—C22B161.3 (4)
C19A—C20A—C21A—C22A41.8 (3)C19B—C20B—C21B—C22B43.9 (4)
C20A—C21A—C22A—C17A−44.1 (4)C20B—C21B—C22B—C17B−46.1 (5)
C16A—C17A—C22A—C21A−174.1 (2)C28B—C17B—C22B—C21B−47.1 (4)
C28A—C17A—C22A—C21A−48.6 (3)C16B—C17B—C22B—C21B−174.6 (3)
C18A—C17A—C22A—C21A60.3 (3)C18B—C17B—C22B—C21B61.0 (4)
C16A—C17A—C28A—O19A−151.2 (2)C16B—C17B—C28B—O19B−151.1 (3)
C22A—C17A—C28A—O19A83.8 (3)C18B—C17B—C28B—O19B−29.7 (3)
C18A—C17A—C28A—O19A−29.4 (3)C22B—C17B—C28B—O19B83.7 (3)
C17A—C28A—O19A—C19A2.1 (3)C17B—C28B—O19B—C19B1.7 (4)
C18A—C19A—O19A—C28A26.6 (3)C18B—C19B—O19B—C28B27.5 (3)
C20A—C19A—O19A—C28A−93.1 (2)C20B—C19B—O19B—C28B−93.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3A—H3A1···O19Ai0.822.042.853 (3)171
O3B—H3B1···O3Aii0.822.122.920 (3)164
Symmetry codes: (i) x+1, y, z; (ii) x−2, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3A—H3A1···O19Ai0.822.042.853 (3)171
O3B—H3B1···O3Aii0.822.122.920 (3)164
Symmetry codes: (i) x+1, y, z; (ii) x−2, y−1, z.
Acknowledgements top

This work was supported by Fundação para a Ciência e Tecnologia. RMAP and RCS thank FCT for grants (SFRH/BD/18013/2004; SFRH/BD/23700/2005). We gratefully acknowledge LCA-UC for the grant of computer time in the Milipeia cluster.

references
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