A derivative of diosgenin: (25R)-23-acetyl-3β-bromo-16β-acetoxy-22,26-epoxy-5α-cholest-22-en-6-one

The crystal structure of the title compound, C₃₁H₄₅BrO₅, has been determined at 0.80 Å resolution. This study demonstrates that the Marker transformation applied to a diosgenin derivative does not affect the A–D ring structure of the steroid. The configurations of the stereogenic centres C20 and C25 also remain unchanged during the reaction.

Key indicators

• Single-crystal X-ray study
• T = 300 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.056
• wR factor = 0.139
• Data-to-parameter ratio = 17.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_031  Alert C Refined Extinction parameter within range ....       2.80 Sigma

PLAT_213  Alert C Atom O30     has ADP max/min Ratio ...........       3.50 prolate

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.25
         From the CIF: _reflns_number_total               5918
         Count of symmetry unique reflns         3412
         Completeness (_total/calc)            173.45%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2506
         Fraction of Friedel pairs measured     0.734
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

Computing details

Data collection: XSCANS (Fait, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: RASTEP-3D (Merritt & Bacon, 1997); software used to prepare material for publication: SHELXL97.

(25R)-23-acetyl-3-β-bromo-16-β-acetoxy-22,26-epoxy-5-α-cholest-22-en-6-one

Crystal data

C31H45BrO5	Dx = 1.290 Mg m^−3
Mr = 577.58	Melting point: 491 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2ab	Cell parameters from 67 reflections
a = 8.5963 (11) Å	θ = 4.7–13.2°
b = 12.4609 (8) Å	µ = 1.42 mm^−1
c = 27.7642 (15) Å	T = 300 K
V = 2974.0 (5) Å^3	Irregular block, colourless
Z = 4	0.70 × 0.44 × 0.40 mm
F(000) = 1224

Data collection

Bruker P4 diffractometer	3490 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 26.3°, θmin = 2.2°
2θ/ω scans	h = −10→9
Absorption correction: ψ scan (XSCANS; Fait, 1996)	k = −15→1
Tmin = 0.528, Tmax = 0.567	l = −1→34
7094 measured reflections	3 standard reflections every 97 reflections
5918 independent reflections	intensity decay: 0.5%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.0489P)^2 + 2.0696P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.139	(Δ/σ)max = 0.002
S = 1.01	Δρmax = 0.62 e Å^−3
5918 reflections	Δρmin = −0.52 e Å^−3
345 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0014 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983); 2511 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.008 (12)

Special details

Experimental. The title compound was fully characterized by spectroscopic techniques:

Elemental analysis: Calc. for C₃₁H₄₅BrO₅: C 64.5%, H 7.8%, Br 13.8%, O 13.8%; found: C 64.2%, H 7.8%, Br 13.7%, O 13.8%.

IR (KBr, cm_-1): 2972 to 2865 (C—H sat.), 1737 (C═O of ester), 1709 (C═O of ketone), 1663 (C═O of α,β-insat.).

¹H-NMR (CDCl₃, 400 MHz, relative to TMS, p.p.m.): δ 0.75 (s, Me-19); 0.84 (s, Me-18); 0.92 (d, J_27,25=6.24 Hz, Me-27); 1.12 (d, J_21,20=6.88 Hz, Me-21); 1.8 (s, H31); 3.4 (t, J_{26a,25 e}=9.88 Hz, H26); 3.8 (m, H3), 4.0 (m, H26e); 5.1 (m, H16).

¹³H-NMR (CDCl₃, 100 MHz, relative to TMS, p.p.m.): δ C1, 33.38; C2, 32.34; C3, 50.51; C4, 31.66; C5, 58.99; C6, 209.08; C7, 46.34; C8, 37.18; C9, 53.85; C10, 40.62; C11, 21.20; C12, 39.07; C13, 42.94; C14, 54.34; C15, 34.51; C16, 74.51; C17, 55.94; C18, 13.14; C19, 18.18; C20, 32.78; C21, 19.45; C22, 106.95; C23, 171.01; C24, 39.46; C25, 26.61; C26, 71.61; C27, 16.92; C28, 198.27; C29, 29.77; C30, 170.60; C31, 21.18.

For NMR data, chemical shifts, δ, were assigned using COSY, ATP and HETCOR techniques. Coupling constants, J, were obtained by first order analysis of the expanded ¹H-NMR spectrum.

MS (EI, 70 Ev), m/z (%): 577 (M^.+, 1.5%); 517 (M⁺-60, C₃H₅O₂, 8.5%); 502 (M⁺-15, Me, 18.6%); 474 (M⁺-28, CO, 4.1%); 436 (M⁺-38, C₃H₂, 2.7%); 420 (M⁺-16, O, 4.7%); 392 (M⁺-28, C₂H₄, 1.6%); 350 (M⁺-42, C₃H₆, 3.0%); 268 (M⁺-82, Br, 1.4%); 204, (M⁺-64, C₅H₄, 100%).

Optical purity: [α]_D²⁵ +10° C (c 0.0003 g/ml, CHCl₃).

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	1.21011 (9)	0.36295 (5)	0.88001 (2)	0.0995 (3)
O16	0.2747 (4)	0.5873 (2)	0.57822 (11)	0.0640 (8)
O28	−0.1372 (4)	0.4481 (4)	0.58459 (16)	0.0980 (14)
C1	0.7721 (6)	0.3175 (4)	0.81051 (18)	0.0659 (14)
H1A	0.6765	0.2916	0.8250	0.079*
H1B	0.8014	0.2674	0.7854	0.079*
C2	0.8999 (7)	0.3185 (4)	0.8490 (2)	0.0781 (17)
H2A	0.8646	0.3598	0.8766	0.094*
H2B	0.9195	0.2457	0.8597	0.094*
C3	1.0479 (6)	0.3663 (4)	0.83010 (18)	0.0674 (14)
H3A	1.0832	0.3224	0.8029	0.081*
C4	1.0216 (6)	0.4797 (4)	0.81196 (18)	0.0599 (13)
H4A	1.1180	0.5092	0.7996	0.072*
H4B	0.9856	0.5251	0.8380	0.072*
C5	0.8994 (6)	0.4750 (4)	0.77200 (16)	0.0530 (12)
H5A	0.9407	0.4250	0.7480	0.064*
C6	0.8779 (5)	0.5795 (4)	0.74596 (17)	0.0545 (12)
O6	0.9378 (4)	0.6625 (3)	0.75948 (13)	0.0702 (10)
C7	0.7751 (6)	0.5737 (4)	0.70281 (17)	0.0605 (13)
H7A	0.8299	0.5361	0.6774	0.073*
H7B	0.7546	0.6460	0.6916	0.073*
C8	0.6196 (6)	0.5173 (3)	0.71179 (16)	0.0500 (11)
H8A	0.5514	0.5657	0.7299	0.060*
C9	0.6427 (5)	0.4124 (3)	0.74147 (16)	0.0507 (11)
H9A	0.7025	0.3637	0.7208	0.061*
C10	0.7407 (5)	0.4284 (3)	0.78740 (15)	0.0505 (12)
C11	0.4833 (5)	0.3589 (4)	0.74896 (18)	0.0590 (12)
H11A	0.4183	0.4061	0.7681	0.071*
H11B	0.4975	0.2928	0.7669	0.071*
C12	0.3989 (6)	0.3334 (4)	0.70135 (16)	0.0568 (12)
H12A	0.4581	0.2801	0.6837	0.068*
H12B	0.2976	0.3031	0.7085	0.068*
C13	0.3782 (5)	0.4329 (4)	0.66995 (16)	0.0517 (11)
C14	0.5409 (5)	0.4878 (4)	0.66505 (17)	0.0503 (11)
H14A	0.6084	0.4340	0.6500	0.060*
C15	0.5139 (5)	0.5727 (4)	0.62664 (16)	0.0569 (12)
H15A	0.4659	0.6362	0.6403	0.068*
H15B	0.6108	0.5929	0.6112	0.068*
C16	0.4053 (5)	0.5178 (4)	0.59121 (17)	0.0554 (12)
H16A	0.4633	0.4983	0.5621	0.066*
C17	0.3427 (5)	0.4145 (3)	0.61575 (16)	0.0493 (11)
H17A	0.4113	0.3561	0.6054	0.059*
C18	0.2577 (6)	0.5087 (4)	0.69233 (18)	0.0650 (14)
H18A	0.1595	0.4725	0.6948	0.097*
H18B	0.2464	0.5711	0.6724	0.097*
H18C	0.2918	0.5299	0.7239	0.097*
C19	0.6601 (6)	0.5034 (4)	0.82353 (18)	0.0667 (14)
H19A	0.6415	0.5717	0.8086	0.100*
H19B	0.7256	0.5128	0.8512	0.100*
H19C	0.5628	0.4724	0.8333	0.100*
C20	0.1786 (5)	0.3819 (4)	0.60046 (16)	0.0563 (12)
H20A	0.1054	0.4349	0.6134	0.068*
C21	0.1329 (7)	0.2706 (5)	0.6202 (2)	0.0829 (17)
H21A	0.0294	0.2531	0.6099	0.124*
H21B	0.1367	0.2718	0.6548	0.124*
H21C	0.2043	0.2176	0.6083	0.124*
C22	0.1597 (5)	0.3793 (4)	0.54623 (17)	0.0524 (11)
C23	0.0357 (5)	0.4089 (4)	0.51983 (18)	0.0556 (12)
C24	0.0366 (6)	0.3941 (4)	0.46574 (18)	0.0654 (14)
H24A	−0.0642	0.3673	0.4556	0.078*
H24B	0.0525	0.4632	0.4505	0.078*
C25	0.1611 (6)	0.3174 (4)	0.44875 (17)	0.0637 (14)
H25A	0.1301	0.2447	0.4581	0.076*
C26	0.3071 (6)	0.3441 (4)	0.47458 (16)	0.0619 (13)
H26A	0.3884	0.2954	0.4642	0.074*
H26B	0.3387	0.4164	0.4660	0.074*
O26	0.2913 (4)	0.3374 (3)	0.52617 (11)	0.0636 (9)
C27	0.1831 (7)	0.3190 (5)	0.39498 (18)	0.0790 (16)
H27A	0.2633	0.2690	0.3862	0.118*
H27B	0.2126	0.3898	0.3849	0.118*
H27C	0.0876	0.2991	0.3795	0.118*
C28	−0.1053 (6)	0.4548 (5)	0.5424 (2)	0.0744 (16)
C29	−0.2189 (8)	0.5098 (6)	0.5088 (3)	0.118 (3)
H29A	−0.3056	0.5365	0.5270	0.177*
H29B	−0.2553	0.4593	0.4852	0.177*
H29C	−0.1679	0.5684	0.4929	0.177*
C30	0.2852 (9)	0.6395 (6)	0.5374 (3)	0.0901 (18)
O30	0.411 (3)	0.662 (5)	0.521 (2)	0.204 (18)	0.54 (7)
O30'	0.380 (4)	0.610 (2)	0.5067 (5)	0.106 (9)	0.46 (7)
C31	0.1422 (9)	0.7008 (5)	0.5259 (2)	0.107 (2)
H31A	0.1553	0.7373	0.4957	0.160*
H31B	0.1231	0.7525	0.5509	0.160*
H31C	0.0555	0.6525	0.5238	0.160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.1147 (5)	0.0842 (4)	0.0996 (5)	−0.0047 (4)	−0.0418 (4)	0.0042 (4)
O16	0.072 (2)	0.0555 (18)	0.065 (2)	0.0037 (17)	0.0010 (18)	0.0169 (17)
O28	0.067 (3)	0.135 (4)	0.092 (3)	0.021 (2)	0.029 (2)	0.002 (3)
C1	0.073 (3)	0.052 (3)	0.073 (3)	−0.009 (3)	−0.007 (3)	0.008 (2)
C2	0.112 (5)	0.048 (3)	0.075 (4)	−0.004 (3)	−0.015 (4)	0.008 (3)
C3	0.082 (4)	0.054 (3)	0.067 (3)	−0.001 (3)	−0.016 (3)	0.003 (3)
C4	0.064 (3)	0.055 (3)	0.060 (3)	−0.002 (2)	−0.002 (3)	−0.004 (2)
C5	0.065 (3)	0.042 (2)	0.052 (3)	0.000 (2)	0.007 (2)	−0.007 (2)
C6	0.056 (3)	0.044 (3)	0.064 (3)	−0.010 (2)	0.010 (3)	−0.003 (2)
O6	0.077 (2)	0.055 (2)	0.079 (2)	−0.0164 (18)	−0.0057 (19)	0.0028 (18)
C7	0.064 (3)	0.046 (3)	0.072 (3)	−0.015 (3)	0.004 (3)	0.008 (2)
C8	0.056 (3)	0.038 (2)	0.056 (3)	−0.002 (2)	0.010 (2)	0.000 (2)
C9	0.060 (3)	0.038 (2)	0.054 (3)	−0.002 (2)	0.004 (2)	0.003 (2)
C10	0.057 (3)	0.039 (2)	0.055 (3)	−0.007 (2)	0.010 (2)	0.001 (2)
C11	0.060 (3)	0.055 (3)	0.062 (3)	−0.015 (3)	0.000 (2)	0.010 (3)
C12	0.059 (3)	0.043 (3)	0.068 (3)	−0.011 (2)	0.004 (2)	0.006 (2)
C13	0.051 (3)	0.048 (3)	0.056 (3)	−0.002 (2)	0.014 (2)	0.003 (2)
C14	0.051 (3)	0.039 (2)	0.061 (3)	−0.004 (2)	0.012 (2)	0.001 (2)
C15	0.056 (3)	0.056 (3)	0.059 (3)	−0.007 (2)	0.007 (2)	0.006 (3)
C16	0.055 (3)	0.056 (3)	0.055 (3)	−0.003 (2)	0.011 (2)	0.004 (2)
C17	0.049 (3)	0.043 (2)	0.055 (3)	−0.0001 (19)	0.010 (2)	0.003 (2)
C18	0.057 (3)	0.064 (3)	0.074 (3)	0.002 (2)	0.018 (3)	−0.004 (3)
C19	0.075 (4)	0.059 (3)	0.066 (3)	−0.010 (3)	0.019 (3)	−0.013 (3)
C20	0.049 (3)	0.054 (3)	0.066 (3)	−0.002 (2)	0.005 (2)	0.004 (2)
C21	0.083 (4)	0.086 (4)	0.080 (4)	−0.035 (3)	−0.019 (3)	0.018 (3)
C22	0.047 (3)	0.043 (3)	0.068 (3)	−0.001 (2)	0.004 (2)	0.003 (2)
C23	0.048 (3)	0.048 (3)	0.070 (3)	−0.001 (2)	0.005 (2)	0.006 (2)
C24	0.051 (3)	0.073 (4)	0.072 (4)	−0.001 (3)	−0.004 (2)	0.011 (3)
C25	0.070 (4)	0.057 (3)	0.064 (3)	−0.004 (2)	−0.009 (3)	−0.008 (3)
C26	0.060 (3)	0.063 (3)	0.063 (3)	0.005 (3)	0.005 (2)	−0.007 (2)
O26	0.0556 (19)	0.071 (2)	0.064 (2)	0.0102 (19)	−0.0029 (17)	−0.0084 (16)
C27	0.078 (4)	0.085 (4)	0.074 (4)	−0.010 (3)	−0.003 (3)	−0.010 (3)
C28	0.048 (3)	0.083 (4)	0.092 (4)	0.010 (3)	0.011 (3)	0.008 (3)
C29	0.078 (4)	0.148 (6)	0.127 (6)	0.052 (5)	0.016 (5)	0.046 (5)
C30	0.099 (5)	0.082 (4)	0.089 (5)	−0.019 (5)	−0.008 (4)	0.032 (4)
O30	0.106 (11)	0.22 (3)	0.28 (3)	−0.018 (16)	0.022 (15)	0.20 (3)
O30'	0.147 (16)	0.103 (13)	0.066 (13)	−0.014 (9)	0.019 (8)	0.042 (9)
C31	0.150 (7)	0.065 (4)	0.105 (5)	0.009 (4)	−0.037 (5)	0.023 (4)

Geometric parameters (Å, º)

Br1—C3	1.966 (5)	C13—C18	1.533 (6)
O16—C30	1.311 (7)	C13—C17	1.552 (6)
O16—C16	1.463 (6)	C13—C14	1.563 (6)
O28—C28	1.206 (6)	C14—C15	1.520 (6)
C1—C2	1.533 (7)	C15—C16	1.519 (7)
C1—C10	1.547 (6)	C16—C17	1.553 (6)
C2—C3	1.500 (8)	C17—C20	1.528 (6)
C3—C4	1.516 (7)	C20—C22	1.515 (6)
C4—C5	1.529 (7)	C20—C21	1.542 (7)
C5—C6	1.500 (6)	C22—C23	1.345 (6)
C5—C10	1.543 (7)	C22—O26	1.365 (5)
C6—O6	1.215 (5)	C23—C28	1.479 (7)
C6—C7	1.491 (7)	C23—C24	1.513 (7)
C7—C8	1.531 (7)	C24—C25	1.510 (7)
C8—C14	1.509 (6)	C25—C26	1.483 (7)
C8—C9	1.557 (6)	C25—C27	1.505 (7)
C9—C11	1.538 (7)	C26—O26	1.441 (5)
C9—C10	1.541 (6)	C28—C29	1.514 (8)
C10—C19	1.536 (6)	C30—O30	1.21 (2)
C11—C12	1.541 (6)	C30—O30'	1.24 (2)
C12—C13	1.526 (6)	C30—C31	1.482 (9)
C30—O16—C16	117.0 (5)	C8—C14—C15	120.2 (4)
C2—C1—C10	114.0 (4)	C8—C14—C13	115.6 (4)
C3—C2—C1	111.5 (4)	C15—C14—C13	103.2 (4)
C2—C3—C4	111.1 (4)	C16—C15—C14	103.6 (4)
C2—C3—Br1	110.3 (3)	O16—C16—C15	111.4 (4)
C4—C3—Br1	111.1 (3)	O16—C16—C17	109.4 (3)
C3—C4—C5	107.9 (4)	C15—C16—C17	107.6 (4)
C6—C5—C4	113.7 (4)	C20—C17—C16	114.7 (4)
C6—C5—C10	110.6 (4)	C20—C17—C13	119.3 (3)
C4—C5—C10	114.9 (4)	C16—C17—C13	103.5 (3)
O6—C6—C7	122.8 (4)	C22—C20—C17	112.4 (4)
O6—C6—C5	122.5 (4)	C22—C20—C21	107.9 (4)
C7—C6—C5	114.7 (4)	C17—C20—C21	112.0 (4)
C6—C7—C8	114.2 (4)	C23—C22—O26	122.6 (4)
C14—C8—C7	111.3 (4)	C23—C22—C20	128.4 (4)
C14—C8—C9	107.9 (3)	O26—C22—C20	109.0 (4)
C7—C8—C9	111.1 (4)	C22—C23—C28	121.6 (5)
C11—C9—C10	115.5 (4)	C22—C23—C24	120.2 (4)
C11—C9—C8	108.7 (4)	C28—C23—C24	118.1 (5)
C10—C9—C8	113.5 (4)	C25—C24—C23	113.0 (4)
C19—C10—C9	111.9 (4)	C26—C25—C27	111.7 (4)
C19—C10—C5	110.5 (4)	C26—C25—C24	107.9 (4)
C9—C10—C5	107.6 (3)	C27—C25—C24	113.0 (4)
C19—C10—C1	110.6 (4)	O26—C26—C25	112.8 (4)
C9—C10—C1	108.9 (3)	C22—O26—C26	117.4 (4)
C5—C10—C1	107.3 (4)	O28—C28—C23	124.8 (5)
C9—C11—C12	113.1 (4)	O28—C28—C29	118.9 (5)
C13—C12—C11	112.2 (4)	C23—C28—C29	116.3 (5)
C12—C13—C18	110.3 (4)	O30—C30—O16	120.7 (15)
C12—C13—C17	117.1 (4)	O30'—C30—O16	119.5 (11)
C18—C13—C17	110.6 (4)	O30—C30—C31	122.4 (13)
C12—C13—C14	107.5 (4)	O30'—C30—C31	123.8 (11)
C18—C13—C14	111.8 (4)	O16—C30—C31	112.6 (7)
C17—C13—C14	99.0 (3)
C10—C1—C2—C3	−53.9 (6)	C12—C13—C14—C15	170.3 (4)
C1—C2—C3—C4	57.8 (6)	C18—C13—C14—C15	−68.4 (5)
C1—C2—C3—Br1	−178.6 (3)	C17—C13—C14—C15	48.0 (4)
C2—C3—C4—C5	−59.2 (6)	C8—C14—C15—C16	−168.7 (4)
Br1—C3—C4—C5	177.7 (3)	C13—C14—C15—C16	−38.1 (4)
C3—C4—C5—C6	−171.9 (4)	C30—O16—C16—C15	99.0 (6)
C3—C4—C5—C10	59.3 (5)	C30—O16—C16—C17	−142.2 (5)
C4—C5—C6—O6	−8.7 (7)	C14—C15—C16—O16	132.9 (4)
C10—C5—C6—O6	122.2 (5)	C14—C15—C16—C17	13.0 (5)
C4—C5—C6—C7	172.4 (4)	O16—C16—C17—C20	27.6 (5)
C10—C5—C6—C7	−56.7 (5)	C15—C16—C17—C20	148.8 (4)
O6—C6—C7—C8	−129.6 (5)	O16—C16—C17—C13	−104.2 (4)
C5—C6—C7—C8	49.3 (6)	C15—C16—C17—C13	17.0 (4)
C6—C7—C8—C14	−164.8 (4)	C12—C13—C17—C20	77.1 (5)
C6—C7—C8—C9	−44.5 (5)	C18—C13—C17—C20	−50.4 (5)
C14—C8—C9—C11	−57.2 (5)	C14—C13—C17—C20	−167.8 (4)
C7—C8—C9—C11	−179.5 (4)	C12—C13—C17—C16	−153.9 (4)
C14—C8—C9—C10	172.7 (4)	C18—C13—C17—C16	78.6 (4)
C7—C8—C9—C10	50.4 (5)	C14—C13—C17—C16	−38.8 (4)
C11—C9—C10—C19	−62.5 (5)	C16—C17—C20—C22	49.9 (5)
C8—C9—C10—C19	64.1 (5)	C13—C17—C20—C22	173.6 (4)
C11—C9—C10—C5	176.0 (4)	C16—C17—C20—C21	171.6 (4)
C8—C9—C10—C5	−57.4 (5)	C13—C17—C20—C21	−64.7 (5)
C11—C9—C10—C1	60.0 (5)	C17—C20—C22—C23	−142.3 (5)
C8—C9—C10—C1	−173.4 (4)	C21—C20—C22—C23	93.7 (6)
C6—C5—C10—C19	−63.5 (5)	C17—C20—C22—O26	39.6 (5)
C4—C5—C10—C19	66.8 (5)	C21—C20—C22—O26	−84.3 (5)
C6—C5—C10—C9	59.0 (5)	O26—C22—C23—C28	−179.6 (4)
C4—C5—C10—C9	−170.7 (4)	C20—C22—C23—C28	2.6 (8)
C6—C5—C10—C1	175.9 (4)	O26—C22—C23—C24	1.4 (7)
C4—C5—C10—C1	−53.8 (5)	C20—C22—C23—C24	−176.5 (4)
C2—C1—C10—C19	−70.9 (6)	C22—C23—C24—C25	16.8 (7)
C2—C1—C10—C9	165.9 (4)	C28—C23—C24—C25	−162.3 (4)
C2—C1—C10—C5	49.7 (5)	C23—C24—C25—C26	−44.7 (6)
C10—C9—C11—C12	−173.5 (4)	C23—C24—C25—C27	−168.7 (4)
C8—C9—C11—C12	57.6 (5)	C27—C25—C26—O26	−176.7 (4)
C9—C11—C12—C13	−56.2 (6)	C24—C25—C26—O26	58.5 (6)
C11—C12—C13—C18	−70.6 (5)	C23—C22—O26—C26	11.7 (6)
C11—C12—C13—C17	161.7 (4)	C20—C22—O26—C26	−170.1 (4)
C11—C12—C13—C14	51.5 (5)	C25—C26—O26—C22	−43.2 (6)
C7—C8—C14—C15	−53.1 (6)	C22—C23—C28—O28	−17.3 (9)
C9—C8—C14—C15	−175.3 (4)	C24—C23—C28—O28	161.7 (6)
C7—C8—C14—C13	−178.1 (4)	C22—C23—C28—C29	165.3 (5)
C9—C8—C14—C13	59.8 (5)	C24—C23—C28—C29	−15.6 (8)
C12—C13—C14—C8	−56.4 (5)	C16—O16—C30—O30	−27 (4)
C18—C13—C14—C8	64.8 (5)	C16—O16—C30—O30'	17.7 (18)
C17—C13—C14—C8	−178.7 (4)	C16—O16—C30—C31	175.7 (5)