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Acta Cryst. (2009). E65, o1283    [ doi:10.1107/S1600536809017243 ]

Methyl 3[beta]-methoxycarbonyloxy-4,4-dimethyl-17-oxo-16[alpha]-(3-oxobutyl)-16[beta]-carboxylate

X. Yan, S. Xu, J. Wang, Y. Chen and P. Xia

Abstract top

The title steroid, C29H44O7, is a new androgen derivative and a key intermediate for synthesizing novel anti-HIV steroid agents. There are four trans-fused rings in the structure. The three six-membered rings exhibit chair conformations, while the five-membered ring adopts an envelope conformation.

Comment top

As part of an on-going study synthesizing potential anti-HIV steroid agents (Yan et al., 2009), the title compound (I) was prepared as a key intermediate by Michael addition of 3β-methoxycarbonyloxy-4,4-dimethyl-16β-methoxycarbonyl-androstane-17-one with methyl vinyl ketone in 73.8% yield. Full structural details of (I) are reported herein.

The molecular structure of (I), Fig.1, shows the A/B, B/C and C/D ring junctions to be all trans. The cyclohexane rings adopt chair conformations, and the cyclopentane ring adopts an envelope conformation. Based on the known configurations of the methyl groups at the C10 and C13 atoms, see Experimental, the C16-(3'-oxobutyl) group is assigned an α-configuration. The 3-methoxycarbonyloxy and 16-methoxycarbonyl groups are in β-configurations. The stereogenic sites of (I) exhibit the following chirality: C3 = S, C5 = R, C8 = R, C9 = S, C10 = R, C13 = S, C14 = S, and C16 = S.

Related literature top

For discussion of absolute configuration, see: Marker et al. (1940); Fieser & Fieser (1959); Castro-Méndez et al. (2002). For background to our on-going study synthesizing potential anti-HIV steroid agents, see: Yan et al. (2009).

Experimental top

Methyl vinyl ketone (0.10 ml, 1.24 mmol) was added dropwise to a well stirred mixture of 3β-methoxycarbonyloxy-4,4-dimethyl-16β-methoxycarbonyl-androstane-17-one (214.80 mg, 0.49 mmol) and sodium methoxide (c = 0.5 M, 0.50 ml) in methanol (2 ml) under N2. The reaction mixture was stirred for 2 h at 293 K and TLC showed the reaction had completed. After adding brine, the reaction mixture was extracted with ethyl acetate and dried over Na2SO4. The removal of solvent gave a residue which was purified by chromatography on a silica gel column with petroleum ether/ethyl acetate (7:1) as eluent to afford 182.36 mg (73.8%) of (I). Recrystallization from ether to give colorless crystals.

The starting material, 3β-methoxycarbonyloxy-4,4-dimethyl-16β-methoxycarbonyl-androstane-17-one, was derived initially from diosgenin, for which the absolute configurations of all chiral centers of the steroid skeleton have been determined (Fieser & Fieser, 1959; Marker et al., 1940). Recently, the absolute configurations of the chiral centres were confirmed by the X-ray crystal structure determination of a 3-Br substituted steroid substrate synthesized from diosgenin. (Castro-Méndez et al., 2002). Introduction of a side-chain at C16 by Michael addition did not cause inversion of the configurations at C8, C9, C10, C13 and C14. Thus, by comparing the orientation of 16-substitutes to that of methyl groups at C10 and C13, the absolute configuration of (I) could be determined.

Refinement top

All H atoms were placed in the idealized positions with methine C—H = 0.98 Å, methylene C—H = 0.97 Å and methyl C—H = 0.96 Å), and treated as riding with Uiso(H) = 1.2 Ueq(CH2 and CH) and 1.5 Ueq(CH3). In the absence of significant anomalous scattering effects, 584 Friedel pairs were averaged in the final refinement.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing atom labels and 30% probability displacement ellipsoids for non-H atoms.
Methyl 3β-methoxycarbonyloxy-4,4-dimethyl-17-oxo- 16α-(3-oxobutyl)androstane-16β-carboxylate top
Crystal data top
C29H44O7F000 = 1096
Mr = 504.64Dx = 1.215 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 700 reflections
a = 8.464 (3) Åθ = 2.4–24.2º
b = 9.901 (3) ŵ = 0.09 mm−1
c = 32.917 (10) ÅT = 295 K
V = 2758.4 (14) Å3Block, colourless
Z = 40.15 × 0.06 × 0.05 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2846 independent reflections
Radiation source: sealed tube1785 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.070
T = 295 Kθmax = 25.2º
phi and ω scansθmin = 1.2º
Absorption correction: multi-scan
(Blessing, 1995)		h = −10→10
Tmin = 0.987, Tmax = 0.996k = −11→10
11219 measured reflectionsl = −39→31
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.089  w = 1/[σ2(Fo2) + (0.042P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.86(Δ/σ)max = 0.001
2846 reflectionsΔρmax = 0.15 e Å−3
332 parametersΔρmin = −0.16 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C29H44O7V = 2758.4 (14) Å3
Mr = 504.64Z = 4
Orthorhombic, P212121Mo Kα
a = 8.464 (3) ŵ = 0.09 mm−1
b = 9.901 (3) ÅT = 295 K
c = 32.917 (10) Å0.15 × 0.06 × 0.05 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2846 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		1785 reflections with I > 2σ(I)
Tmin = 0.987, Tmax = 0.996Rint = 0.070
11219 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042Δρmax = 0.15 e Å−3
wR(F2) = 0.089Δρmin = −0.16 e Å−3
S = 0.86Absolute structure: ?
2846 reflectionsFlack parameter: ?
332 parametersRogers parameter: ?
H-atom parameters constrained
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
O10.5861 (3)0.3685 (3)1.23879 (6)0.0805 (9)
O20.1349 (4)0.0393 (3)1.19374 (10)0.1119 (11)
O30.2929 (4)0.5217 (4)1.26075 (8)0.1202 (13)
O40.1781 (3)0.6056 (3)1.20619 (7)0.0641 (7)
O51.0487 (2)0.4975 (3)0.93458 (5)0.0621 (7)
O61.2733 (3)0.3782 (3)0.94059 (8)0.0770 (8)
O71.2090 (3)0.4978 (3)0.88526 (6)0.0845 (9)
C11.0195 (3)0.4992 (3)1.04937 (8)0.0476 (8)
H1A1.02880.40281.05390.057*
H1B1.08270.54481.06980.057*
C21.0844 (4)0.5335 (4)1.00704 (8)0.0526 (9)
H2A1.07760.63011.00250.063*
H2B1.19460.50731.00530.063*
C30.9909 (3)0.4604 (3)0.97519 (8)0.0473 (8)
H31.00420.36290.97900.057*
C40.8136 (3)0.4937 (3)0.97479 (8)0.0463 (8)
C50.7499 (3)0.4752 (3)1.01902 (7)0.0394 (7)
H50.75620.37791.02410.047*
C60.5740 (3)0.5094 (4)1.02278 (8)0.0503 (9)
H6A0.55990.60621.02030.060*
H6B0.51640.46641.00080.060*
C70.5068 (3)0.4624 (3)1.06332 (7)0.0507 (9)
H7A0.50520.36441.06380.061*
H7B0.39870.49391.06580.061*
C80.6018 (3)0.5136 (3)1.09946 (7)0.0405 (7)
H80.59020.61191.10120.049*
C90.7770 (3)0.4795 (3)1.09437 (8)0.0415 (7)
H90.78160.38131.09080.050*
C100.8464 (3)0.5411 (3)1.05431 (8)0.0393 (7)
C110.8755 (3)0.5099 (4)1.13285 (8)0.0563 (9)
H11A0.98160.47481.12910.068*
H11B0.88340.60701.13630.068*
C120.8048 (4)0.4484 (4)1.17139 (8)0.0560 (9)
H12A0.80890.35071.16970.067*
H12B0.86600.47651.19480.067*
C130.6353 (4)0.4937 (3)1.17633 (8)0.0480 (8)
C140.5419 (3)0.4510 (3)1.13849 (7)0.0440 (8)
H140.55710.35341.13570.053*
C150.3684 (4)0.4715 (4)1.15094 (8)0.0511 (9)
H15A0.29880.41631.13440.061*
H15B0.33770.56541.14810.061*
C160.3623 (4)0.4270 (4)1.19609 (9)0.0511 (9)
C170.5380 (4)0.4230 (4)1.20881 (9)0.0534 (9)
C180.6250 (5)0.6466 (3)1.18571 (10)0.0689 (11)
H18A0.66990.69681.16360.103*
H18B0.68240.66581.21020.103*
H18C0.51640.67191.18920.103*
C190.8356 (4)0.6959 (3)1.05608 (10)0.0581 (9)
H19A0.88890.73401.03300.087*
H19B0.88460.72771.08060.087*
H19C0.72670.72281.05570.087*
C200.7842 (4)0.6354 (3)0.95734 (9)0.0631 (10)
H20A0.67390.65680.95930.095*
H20B0.81600.63750.92940.095*
H20C0.84440.70050.97240.095*
C210.7327 (4)0.3888 (4)0.94739 (9)0.0664 (11)
H21A0.78460.38660.92150.100*
H21B0.62380.41300.94370.100*
H21C0.73920.30140.95990.100*
C220.2843 (4)0.2896 (4)1.20214 (10)0.0631 (10)
H22A0.28350.26931.23100.076*
H22B0.17520.29591.19330.076*
C230.3614 (4)0.1732 (4)1.18004 (10)0.0636 (10)
H23A0.37790.19911.15190.076*
H23B0.46430.15681.19200.076*
C240.2683 (5)0.0443 (4)1.18101 (10)0.0699 (11)
C250.3495 (5)−0.0768 (4)1.16541 (10)0.0794 (12)
H25A0.2729−0.14521.15920.119*
H25B0.4214−0.11011.18560.119*
H25C0.4072−0.05391.14130.119*
C260.2757 (4)0.5230 (4)1.22479 (11)0.0627 (10)
C270.0879 (4)0.6956 (4)1.23203 (11)0.0793 (12)
H27A0.15850.75611.24580.119*
H27B0.03030.64361.25170.119*
H27C0.01530.74671.21570.119*
C281.3557 (5)0.4633 (5)0.86532 (11)0.0947 (15)
H28A1.38010.37010.87040.142*
H28B1.43910.51920.87570.142*
H28C1.34530.47750.83660.142*
C291.1861 (4)0.4489 (4)0.92210 (10)0.0558 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0667 (18)0.131 (2)0.0434 (14)0.0043 (17)−0.0064 (13)0.0247 (15)
O20.0654 (19)0.110 (3)0.161 (3)−0.0093 (19)0.022 (2)−0.013 (2)
O30.146 (3)0.171 (3)0.0430 (16)0.067 (3)0.0101 (16)−0.0036 (18)
O40.0503 (16)0.0825 (18)0.0596 (15)0.0093 (14)0.0075 (13)−0.0078 (14)
O50.0458 (13)0.0985 (19)0.0421 (12)0.0121 (14)0.0106 (10)0.0020 (12)
O60.0684 (18)0.0835 (19)0.0793 (18)0.0202 (16)0.0232 (15)0.0053 (15)
O70.0592 (16)0.147 (3)0.0471 (14)0.0110 (19)0.0188 (12)0.0035 (16)
C10.0357 (18)0.067 (2)0.0405 (16)−0.0029 (18)−0.0008 (13)−0.0029 (16)
C20.0371 (19)0.070 (2)0.0506 (18)−0.0008 (18)0.0066 (15)−0.0023 (18)
C30.0424 (19)0.063 (2)0.0362 (16)0.0042 (17)0.0069 (14)−0.0008 (15)
C40.0408 (18)0.063 (2)0.0346 (15)0.0048 (18)−0.0005 (13)−0.0026 (16)
C50.0377 (17)0.0461 (19)0.0346 (15)0.0012 (16)−0.0013 (13)−0.0008 (13)
C60.0361 (17)0.080 (3)0.0352 (16)0.0033 (18)−0.0014 (13)0.0039 (17)
C70.0367 (18)0.077 (2)0.0379 (16)−0.0011 (18)−0.0036 (14)−0.0009 (16)
C80.0356 (18)0.049 (2)0.0366 (15)0.0028 (16)0.0005 (13)−0.0008 (15)
C90.0342 (17)0.052 (2)0.0379 (16)0.0012 (16)−0.0013 (13)−0.0038 (14)
C100.0391 (18)0.0412 (19)0.0377 (16)−0.0014 (15)0.0035 (13)−0.0041 (14)
C110.0375 (18)0.092 (3)0.0398 (17)0.002 (2)−0.0044 (14)−0.0055 (18)
C120.047 (2)0.083 (3)0.0386 (17)0.0035 (19)−0.0093 (15)−0.0019 (17)
C130.0427 (18)0.068 (2)0.0333 (15)0.0025 (18)−0.0013 (13)−0.0083 (17)
C140.0363 (18)0.061 (2)0.0344 (16)0.0008 (16)0.0011 (13)0.0012 (15)
C150.0452 (19)0.071 (2)0.0373 (16)0.0047 (19)0.0028 (14)0.0039 (16)
C160.047 (2)0.070 (2)0.0366 (17)0.0039 (19)0.0033 (15)0.0040 (16)
C170.051 (2)0.074 (3)0.0350 (18)0.002 (2)−0.0005 (16)−0.0020 (17)
C180.071 (3)0.076 (3)0.059 (2)0.000 (2)0.0023 (19)−0.0143 (19)
C190.063 (2)0.053 (2)0.058 (2)−0.0038 (19)0.0065 (18)−0.0067 (17)
C200.062 (2)0.083 (3)0.045 (2)0.017 (2)0.0094 (17)0.0130 (18)
C210.055 (2)0.102 (3)0.0421 (19)−0.006 (2)0.0003 (17)−0.021 (2)
C220.056 (2)0.085 (3)0.049 (2)0.006 (2)0.0034 (18)0.0055 (19)
C230.059 (2)0.073 (3)0.058 (2)−0.004 (2)0.0035 (19)0.0063 (19)
C240.070 (3)0.084 (3)0.056 (2)0.004 (3)0.001 (2)0.012 (2)
C250.101 (3)0.077 (3)0.060 (2)0.001 (3)0.011 (2)0.003 (2)
C260.061 (3)0.082 (3)0.046 (2)0.007 (2)0.0127 (18)0.002 (2)
C270.058 (3)0.092 (3)0.088 (3)0.003 (2)0.016 (2)−0.025 (2)
C280.071 (3)0.142 (4)0.071 (3)0.002 (3)0.032 (2)−0.015 (3)
C290.045 (2)0.075 (3)0.047 (2)−0.002 (2)0.0076 (18)−0.0082 (19)
Geometric parameters (Å, °) top
O1—C171.196 (3)C12—H12A0.9700
O2—C241.205 (4)C12—H12B0.9700
O3—C261.193 (4)C13—C171.520 (4)
O4—C261.314 (4)C13—C141.535 (4)
O4—C271.449 (4)C13—C181.547 (4)
O5—C291.324 (4)C14—C151.538 (4)
O5—C31.470 (3)C14—H140.9800
O6—C291.185 (4)C15—C161.551 (4)
O7—C291.320 (4)C15—H15A0.9700
O7—C281.446 (4)C15—H15B0.9700
C1—C101.531 (4)C16—C221.525 (5)
C1—C21.536 (4)C16—C261.528 (5)
C1—H1A0.9700C16—C171.545 (4)
C1—H1B0.9700C18—H18A0.9599
C2—C31.500 (4)C18—H18B0.9599
C2—H2A0.9700C18—H18C0.9599
C2—H2B0.9700C19—H19A0.9599
C3—C41.536 (4)C19—H19B0.9599
C3—H30.9800C19—H19C0.9599
C4—C201.536 (4)C20—H20A0.9599
C4—C211.537 (4)C20—H20B0.9599
C4—C51.563 (4)C20—H20C0.9599
C5—C61.532 (4)C21—H21A0.9599
C5—C101.563 (4)C21—H21B0.9599
C5—H50.9800C21—H21C0.9599
C6—C71.523 (4)C22—C231.511 (5)
C6—H6A0.9700C22—H22A0.9700
C6—H6B0.9700C22—H22B0.9700
C7—C81.523 (4)C23—C241.501 (5)
C7—H7A0.9700C23—H23A0.9700
C7—H7B0.9700C23—H23B0.9700
C8—C141.514 (4)C24—C251.474 (5)
C8—C91.530 (4)C25—H25A0.9599
C8—H80.9800C25—H25B0.9599
C9—C111.546 (4)C25—H25C0.9599
C9—C101.567 (4)C27—H27A0.9599
C9—H90.9800C27—H27B0.9599
C10—C191.536 (4)C27—H27C0.9599
C11—C121.529 (4)C28—H28A0.9599
C11—H11A0.9700C28—H28B0.9599
C11—H11B0.9700C28—H28C0.9599
C12—C131.511 (4)
C26—O4—C27116.1 (3)C13—C14—C15103.9 (2)
C29—O5—C3119.0 (3)C8—C14—H14106.3
C29—O7—C28117.1 (3)C13—C14—H14106.3
C10—C1—C2112.2 (2)C15—C14—H14106.3
C10—C1—H1A109.2C14—C15—C16104.5 (2)
C2—C1—H1A109.2C14—C15—H15A110.9
C10—C1—H1B109.2C16—C15—H15A110.9
C2—C1—H1B109.2C14—C15—H15B110.9
H1A—C1—H1B107.9C16—C15—H15B110.9
C3—C2—C1109.8 (2)H15A—C15—H15B108.9
C3—C2—H2A109.7C22—C16—C26105.5 (3)
C1—C2—H2A109.7C22—C16—C17111.0 (3)
C3—C2—H2B109.7C26—C16—C17108.1 (3)
C1—C2—H2B109.7C22—C16—C15113.1 (3)
H2A—C2—H2B108.2C26—C16—C15115.6 (3)
O5—C3—C2109.8 (2)C17—C16—C15103.6 (2)
O5—C3—C4105.3 (2)O1—C17—C13127.1 (3)
C2—C3—C4114.7 (3)O1—C17—C16124.2 (3)
O5—C3—H3109.0C13—C17—C16108.6 (3)
C2—C3—H3109.0C13—C18—H18A109.5
C4—C3—H3109.0C13—C18—H18B109.5
C3—C4—C20111.0 (3)H18A—C18—H18B109.5
C3—C4—C21107.1 (3)C13—C18—H18C109.5
C20—C4—C21109.0 (3)H18A—C18—H18C109.5
C3—C4—C5107.7 (2)H18B—C18—H18C109.5
C20—C4—C5113.6 (2)C10—C19—H19A109.5
C21—C4—C5108.3 (3)C10—C19—H19B109.5
C6—C5—C10110.8 (2)H19A—C19—H19B109.5
C6—C5—C4112.6 (2)C10—C19—H19C109.5
C10—C5—C4117.6 (2)H19A—C19—H19C109.5
C6—C5—H5104.8H19B—C19—H19C109.5
C10—C5—H5104.8C4—C20—H20A109.5
C4—C5—H5104.8C4—C20—H20B109.5
C7—C6—C5111.5 (2)H20A—C20—H20B109.5
C7—C6—H6A109.3C4—C20—H20C109.5
C5—C6—H6A109.3H20A—C20—H20C109.5
C7—C6—H6B109.3H20B—C20—H20C109.5
C5—C6—H6B109.3C4—C21—H21A109.5
H6A—C6—H6B108.0C4—C21—H21B109.5
C6—C7—C8112.7 (2)H21A—C21—H21B109.5
C6—C7—H7A109.1C4—C21—H21C109.5
C8—C7—H7A109.1H21A—C21—H21C109.5
C6—C7—H7B109.1H21B—C21—H21C109.5
C8—C7—H7B109.1C23—C22—C16115.5 (3)
H7A—C7—H7B107.8C23—C22—H22A108.4
C14—C8—C7110.5 (2)C16—C22—H22A108.4
C14—C8—C9109.1 (2)C23—C22—H22B108.4
C7—C8—C9110.7 (2)C16—C22—H22B108.4
C14—C8—H8108.8H22A—C22—H22B107.5
C7—C8—H8108.8C24—C23—C22114.3 (3)
C9—C8—H8108.8C24—C23—H23A108.7
C8—C9—C11112.9 (2)C22—C23—H23A108.7
C8—C9—C10111.7 (2)C24—C23—H23B108.7
C11—C9—C10114.3 (2)C22—C23—H23B108.7
C8—C9—H9105.7H23A—C23—H23B107.6
C11—C9—H9105.7O2—C24—C25121.7 (4)
C10—C9—H9105.7O2—C24—C23122.3 (4)
C1—C10—C19109.3 (3)C25—C24—C23116.1 (3)
C1—C10—C5107.9 (2)C24—C25—H25A109.5
C19—C10—C5114.4 (3)C24—C25—H25B109.5
C1—C10—C9110.0 (2)H25A—C25—H25B109.5
C19—C10—C9109.5 (2)C24—C25—H25C109.5
C5—C10—C9105.5 (2)H25A—C25—H25C109.5
C12—C11—C9113.0 (3)H25B—C25—H25C109.5
C12—C11—H11A109.0O3—C26—O4123.1 (4)
C9—C11—H11A109.0O3—C26—C16123.3 (4)
C12—C11—H11B109.0O4—C26—C16113.6 (3)
C9—C11—H11B109.0O4—C27—H27A109.5
H11A—C11—H11B107.8O4—C27—H27B109.5
C13—C12—C11110.0 (3)H27A—C27—H27B109.5
C13—C12—H12A109.7O4—C27—H27C109.5
C11—C12—H12A109.7H27A—C27—H27C109.5
C13—C12—H12B109.7H27B—C27—H27C109.5
C11—C12—H12B109.7O7—C28—H28A109.5
H12A—C12—H12B108.2O7—C28—H28B109.5
C12—C13—C17117.0 (3)H28A—C28—H28B109.5
C12—C13—C14108.7 (2)O7—C28—H28C109.5
C17—C13—C1499.5 (2)H28A—C28—H28C109.5
C12—C13—C18111.4 (3)H28B—C28—H28C109.5
C17—C13—C18106.2 (3)O6—C29—O7126.7 (3)
C14—C13—C18113.7 (3)O6—C29—O5127.0 (3)
C8—C14—C13113.8 (2)O7—C29—O5106.3 (3)
C8—C14—C15119.5 (2)
C10—C1—C2—C3−60.6 (3)C11—C12—C13—C18−68.1 (3)
C29—O5—C3—C273.4 (4)C7—C8—C14—C13178.0 (3)
C29—O5—C3—C4−162.7 (3)C9—C8—C14—C1356.1 (3)
C1—C2—C3—O5177.7 (2)C7—C8—C14—C15−58.6 (4)
C1—C2—C3—C459.4 (4)C9—C8—C14—C15179.5 (3)
O5—C3—C4—C20−47.5 (3)C12—C13—C14—C8−61.2 (4)
C2—C3—C4—C2073.4 (3)C17—C13—C14—C8176.0 (3)
O5—C3—C4—C2171.4 (3)C18—C13—C14—C863.5 (4)
C2—C3—C4—C21−167.8 (3)C12—C13—C14—C15167.3 (3)
O5—C3—C4—C5−172.3 (2)C17—C13—C14—C1544.5 (3)
C2—C3—C4—C5−51.5 (4)C18—C13—C14—C15−68.1 (3)
C3—C4—C5—C6178.5 (3)C8—C14—C15—C16−166.0 (3)
C20—C4—C5—C655.3 (4)C13—C14—C15—C16−37.9 (3)
C21—C4—C5—C6−65.9 (3)C14—C15—C16—C22−105.2 (3)
C3—C4—C5—C1047.8 (4)C14—C15—C16—C26133.1 (3)
C20—C4—C5—C10−75.5 (3)C14—C15—C16—C1715.1 (4)
C21—C4—C5—C10163.3 (3)C12—C13—C17—O125.5 (5)
C10—C5—C6—C7−58.2 (4)C14—C13—C17—O1142.2 (4)
C4—C5—C6—C7167.8 (3)C18—C13—C17—O1−99.5 (4)
C5—C6—C7—C852.9 (4)C12—C13—C17—C16−152.2 (3)
C6—C7—C8—C14−173.4 (3)C14—C13—C17—C16−35.5 (3)
C6—C7—C8—C9−52.4 (3)C18—C13—C17—C1682.8 (3)
C14—C8—C9—C11−49.7 (3)C22—C16—C17—O1−43.0 (5)
C7—C8—C9—C11−171.5 (3)C26—C16—C17—O172.2 (5)
C14—C8—C9—C10179.8 (2)C15—C16—C17—O1−164.8 (3)
C7—C8—C9—C1058.0 (3)C22—C16—C17—C13134.7 (3)
C2—C1—C10—C19−70.6 (3)C26—C16—C17—C13−110.1 (3)
C2—C1—C10—C554.4 (3)C15—C16—C17—C1313.0 (4)
C2—C1—C10—C9169.1 (2)C26—C16—C22—C23−173.8 (3)
C6—C5—C10—C1178.3 (2)C17—C16—C22—C23−57.0 (4)
C4—C5—C10—C1−50.2 (3)C15—C16—C22—C2359.0 (4)
C6—C5—C10—C19−59.8 (3)C16—C22—C23—C24−170.7 (3)
C4—C5—C10—C1971.8 (3)C22—C23—C24—O29.1 (5)
C6—C5—C10—C960.7 (3)C22—C23—C24—C25−170.9 (3)
C4—C5—C10—C9−167.8 (3)C27—O4—C26—O3−1.1 (5)
C8—C9—C10—C1−177.4 (2)C27—O4—C26—C16177.7 (3)
C11—C9—C10—C152.9 (3)C22—C16—C26—O373.2 (5)
C8—C9—C10—C1962.4 (3)C17—C16—C26—O3−45.6 (5)
C11—C9—C10—C19−67.3 (3)C15—C16—C26—O3−161.0 (4)
C8—C9—C10—C5−61.2 (3)C22—C16—C26—O4−105.5 (3)
C11—C9—C10—C5169.0 (3)C17—C16—C26—O4135.7 (3)
C8—C9—C11—C1250.8 (4)C15—C16—C26—O420.2 (4)
C10—C9—C11—C12180.0 (3)C28—O7—C29—O6−0.7 (6)
C9—C11—C12—C13−54.7 (4)C28—O7—C29—O5177.7 (3)
C11—C12—C13—C17169.5 (3)C3—O5—C29—O6−1.4 (5)
C11—C12—C13—C1458.0 (4)C3—O5—C29—O7−179.9 (3)
Acknowledgements top

The authors acknowledge the Center of Analysis and Measurement, Fudan University, for providing necessary facilities.

references
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Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

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