Westphalen's diol diacetate: 19(10→5)-abeo-5β-cholest-9-ene-3β,6β-diyl diacetate.

THE STRUCTURE OF THE TITLE STEROID [ALTERNATIVE NAME: 3β,6β-diacet-oxy-5β-methyl-19-norcholest-9(10)-ene], C31H50O4, confirms the generally accepted mechanism for the rearrangement of a cholestan-5α-ol derivative reported a century ago by Westphalen. The methyl group at position 10 of the starting material migrates to position 5 in the steroidal nucleus, while a Δ(9) bond is formed, as indicated by the C=C bond length of 1.347 (4) Å. The methyl transposition leaves the 5R configuration unchanged, with the methyl oriented towards the β face. During the rearrangement, the steroidal B ring experiences a conformational distortion from chair to envelope with the C atom at position 6 as the flap. In the title structure, the isopropyl group of the side chain is disordered over two positions, with occupancies of 0.733 (10) and 0.267 (10). The carbonyl O atom in the acetyl group at C3 is also disordered with an occupancy ratio of 0.62 (4):0.38 (4).

Related literature

For the initial report on the Westphalen rearrangement, see: Westphalen (1915 ▶). For applications in steroid synthesis, see: Rodig et al. (1961 ▶); Knights & Hanson (2004 ▶); Pinto et al. (2008 ▶, 2009 ▶). For mechanistic aspects of this rearrangement, see: Kočovský & Černý (1977 ▶); Kočovský et al. (1979 ▶); Kamernitskii et al. (1987 ▶).

Experimental

Crystal data

C31H50O4

M = 486.71

Orthorhombic,

a = 9.2846 (15) Å

b = 10.7203 (18) Å

c = 29.982 (4) Å

V = 2984.2 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.07 mm−1

T = 298 K

0.6 × 0.5 × 0.5 mm

Data collection

Siemens P4 diffractometer

4350 measured reflections

3393 independent reflections

2827 reflections with I > 2σ(I)

R int = 0.043

3 standard reflections every 97 reflections intensity decay: 0.5%

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.136

S = 1.05

3393 reflections

364 parameters

57 restraints

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.13 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; 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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812045278/ff2087sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045278/ff2087Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C31H50O4	Dx = 1.083 Mg m−3
Mr = 486.71	Melting point: 393 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 70 reflections
a = 9.2846 (15) Å	θ = 4.4–12.6°
b = 10.7203 (18) Å	µ = 0.07 mm−1
c = 29.982 (4) Å	T = 298 K
V = 2984.2 (8) Å3	Prism, colourless
Z = 4	0.6 × 0.5 × 0.5 mm
F(000) = 1072

Siemens P4 diffractometer	Rint = 0.043
Radiation source: fine-focus sealed tube	θmax = 26.2°, θmin = 2.0°
Graphite monochromator	h = −11→1
ω scans	k = −13→1
4350 measured reflections	l = −37→1
3393 independent reflections	3 standard reflections every 97 reflections
2827 reflections with I > 2σ(I)	intensity decay: 0.5%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.136	w = 1/[σ2(Fo2) + (0.0701P)2 + 0.3625P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3393 reflections	Δρmax = 0.14 e Å−3
364 parameters	Δρmin = −0.13 e Å−3
57 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.0087 (15)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.2670 (3)	0.4760 (3)	0.61696 (10)	0.0641 (7)
H1A	0.2466	0.5401	0.5950	0.077*
H1B	0.1814	0.4648	0.6351	0.077*
C2	0.3009 (4)	0.3544 (3)	0.59299 (9)	0.0726 (8)
H2A	0.2187	0.3299	0.5751	0.087*
H2B	0.3821	0.3670	0.5731	0.087*
C3	0.3362 (3)	0.2514 (3)	0.62582 (9)	0.0650 (7)
H3A	0.3650	0.1761	0.6096	0.078*
C4	0.4562 (3)	0.2908 (3)	0.65690 (9)	0.0606 (7)
H4A	0.5454	0.2912	0.6401	0.073*
H4B	0.4656	0.2278	0.6799	0.073*
C5	0.4402 (3)	0.4198 (2)	0.68004 (8)	0.0527 (6)
C6	0.5907 (3)	0.4565 (2)	0.69696 (8)	0.0532 (6)
H6A	0.6594	0.4481	0.6723	0.064*
C7	0.5959 (3)	0.5892 (2)	0.71400 (7)	0.0574 (6)
H7A	0.6899	0.6063	0.7267	0.069*
H7B	0.5240	0.6007	0.7371	0.069*
C8	0.5666 (3)	0.6791 (2)	0.67539 (7)	0.0516 (6)
H8A	0.5361	0.7588	0.6883	0.062*
C9	0.4467 (3)	0.6345 (2)	0.64463 (7)	0.0507 (5)
C10	0.3898 (3)	0.5190 (2)	0.64651 (8)	0.0514 (6)
C11	0.4104 (3)	0.7329 (3)	0.61009 (8)	0.0585 (6)
H11A	0.3727	0.8063	0.6250	0.070*
H11B	0.3362	0.7012	0.5904	0.070*
C12	0.5432 (3)	0.7699 (3)	0.58233 (8)	0.0586 (6)
H12A	0.5173	0.8380	0.5626	0.070*
H12B	0.5715	0.6996	0.5639	0.070*
C13	0.6728 (3)	0.8100 (2)	0.61110 (8)	0.0517 (6)
C14	0.6972 (3)	0.7048 (2)	0.64575 (7)	0.0513 (6)
H14A	0.7129	0.6285	0.6285	0.062*
C15	0.8427 (3)	0.7366 (3)	0.66716 (8)	0.0632 (7)
H15A	0.8891	0.6625	0.6789	0.076*
H15B	0.8314	0.7970	0.6910	0.076*
C16	0.9295 (3)	0.7920 (3)	0.62790 (9)	0.0659 (7)
H16A	1.0063	0.7356	0.6193	0.079*
H16B	0.9718	0.8712	0.6365	0.079*
C17	0.8231 (3)	0.8106 (3)	0.58856 (8)	0.0551 (6)
H17A	0.8285	0.7350	0.5703	0.066*
C18	0.6419 (3)	0.9375 (3)	0.63309 (10)	0.0661 (7)
H18A	0.5566	0.9315	0.6511	0.099*
H18B	0.6279	0.9994	0.6104	0.099*
H18C	0.7220	0.9610	0.6515	0.099*
C19	0.3317 (3)	0.4091 (3)	0.71907 (8)	0.0590 (6)
H19A	0.3584	0.3405	0.7379	0.089*
H19B	0.2367	0.3953	0.7074	0.089*
H19C	0.3326	0.4849	0.7361	0.089*
C20	0.8656 (3)	0.9204 (3)	0.55802 (9)	0.0666 (7)
H20Z	0.8580	0.9974	0.5755	0.080*
C21	0.7641 (4)	0.9322 (5)	0.51798 (12)	0.1005 (13)
H21A	0.6682	0.9494	0.5283	0.151*
H21B	0.7643	0.8555	0.5014	0.151*
H21C	0.7960	0.9990	0.4991	0.151*
C22	1.0228 (4)	0.9080 (3)	0.54214 (11)	0.0741 (8)
H22A	1.0846	0.9012	0.5681	0.089*
H22B	1.0321	0.8311	0.5253	0.089*
C23	1.0756 (4)	1.0143 (4)	0.51364 (15)	0.0984 (12)
H23A	1.0590	1.0918	0.5295	0.118*
H23B	1.0186	1.0168	0.4866	0.118*
C24	1.2325 (4)	1.0079 (4)	0.50092 (13)	0.0883 (10)
H24A	1.2587	0.9211	0.4969	0.106*	0.733 (10)
H24B	1.2893	1.0402	0.5255	0.106*	0.733 (10)
H24C	1.2431	0.9432	0.4786	0.106*	0.267 (10)
H24D	1.2862	0.9814	0.5270	0.106*	0.267 (10)
C251	1.2727 (7)	1.0799 (5)	0.4585 (3)	0.088 (2)	0.733 (10)
H25A	1.2127	1.0454	0.4346	0.105*	0.733 (10)
C261	1.2338 (10)	1.2166 (6)	0.4617 (3)	0.116 (3)	0.733 (10)
H26A	1.1314	1.2249	0.4651	0.175*	0.733 (10)
H26B	1.2640	1.2587	0.4351	0.175*	0.733 (10)
H26C	1.2812	1.2528	0.4870	0.175*	0.733 (10)
C271	1.4250 (7)	1.0578 (8)	0.4448 (3)	0.127 (3)	0.733 (10)
H27A	1.4479	0.9711	0.4483	0.190*	0.733 (10)
H27B	1.4881	1.1070	0.4631	0.190*	0.733 (10)
H27C	1.4372	1.0812	0.4141	0.190*	0.733 (10)
C252	1.3037 (13)	1.1263 (15)	0.4829 (5)	0.076 (4)	0.267 (10)
H25B	1.2828	1.1972	0.5025	0.092*	0.267 (10)
C262	1.233 (4)	1.145 (4)	0.4374 (8)	0.192 (14)	0.267 (10)
H26D	1.1358	1.1140	0.4383	0.288*	0.267 (10)
H26E	1.2863	1.1010	0.4151	0.288*	0.267 (10)
H26F	1.2312	1.2325	0.4303	0.288*	0.267 (10)
C272	1.4604 (18)	1.109 (3)	0.4784 (16)	0.204 (14)	0.267 (10)
H27D	1.5024	1.0978	0.5073	0.306*	0.267 (10)
H27E	1.5016	1.1820	0.4646	0.306*	0.267 (10)
H27F	1.4795	1.0375	0.4602	0.306*	0.267 (10)
O28	0.2039 (2)	0.22733 (18)	0.65042 (8)	0.0734 (6)
C29	0.1753 (4)	0.1143 (3)	0.66520 (13)	0.0832 (10)
O301	0.2663 (9)	0.0327 (8)	0.6663 (4)	0.095 (3)	0.62 (4)
O302	0.228 (4)	0.0265 (18)	0.6439 (17)	0.186 (12)	0.38 (4)
C31	0.0398 (4)	0.1098 (4)	0.69085 (16)	0.1018 (12)
H31A	0.0254	0.0269	0.7022	0.153*
H31B	−0.0392	0.1320	0.6718	0.153*
H31C	0.0451	0.1674	0.7153	0.153*
O32	0.63096 (19)	0.36908 (19)	0.73216 (5)	0.0608 (5)
C33	0.7731 (3)	0.3523 (3)	0.73874 (9)	0.0630 (7)
O34	0.8643 (2)	0.4020 (3)	0.71683 (8)	0.0900 (8)
C35	0.8011 (3)	0.2691 (3)	0.77742 (10)	0.0759 (8)
H35A	0.9028	0.2546	0.7800	0.114*
H35B	0.7524	0.1911	0.7730	0.114*
H35C	0.7662	0.3079	0.8042	0.114*

	U11	U22	U33	U12	U13	U23
C1	0.0599 (16)	0.0645 (16)	0.0680 (16)	−0.0031 (14)	−0.0182 (13)	0.0092 (13)
C2	0.0761 (18)	0.0797 (19)	0.0621 (14)	−0.0114 (17)	−0.0165 (15)	−0.0051 (15)
C3	0.0641 (16)	0.0630 (16)	0.0680 (15)	−0.0010 (14)	−0.0006 (13)	−0.0091 (13)
C4	0.0592 (15)	0.0591 (15)	0.0635 (14)	0.0069 (13)	0.0008 (13)	0.0015 (12)
C5	0.0540 (13)	0.0563 (13)	0.0478 (11)	0.0030 (12)	−0.0023 (11)	0.0047 (11)
C6	0.0536 (13)	0.0625 (14)	0.0436 (11)	0.0021 (12)	−0.0039 (11)	0.0126 (11)
C7	0.0614 (14)	0.0685 (15)	0.0423 (10)	−0.0083 (13)	−0.0085 (11)	0.0050 (11)
C8	0.0563 (14)	0.0524 (13)	0.0462 (11)	−0.0029 (12)	−0.0032 (11)	0.0014 (10)
C9	0.0485 (12)	0.0577 (13)	0.0460 (11)	0.0033 (12)	−0.0038 (10)	0.0042 (11)
C10	0.0481 (12)	0.0595 (13)	0.0466 (11)	0.0009 (12)	−0.0067 (10)	0.0054 (11)
C11	0.0557 (14)	0.0617 (14)	0.0580 (13)	0.0024 (13)	−0.0094 (12)	0.0116 (12)
C12	0.0628 (15)	0.0628 (15)	0.0503 (12)	0.0024 (13)	−0.0088 (11)	0.0135 (12)
C13	0.0532 (13)	0.0533 (13)	0.0487 (11)	0.0003 (11)	0.0001 (11)	0.0031 (11)
C14	0.0545 (13)	0.0561 (13)	0.0431 (11)	−0.0013 (12)	−0.0045 (10)	0.0027 (10)
C15	0.0590 (15)	0.0795 (18)	0.0512 (12)	−0.0108 (15)	−0.0083 (11)	0.0059 (13)
C16	0.0588 (15)	0.0781 (18)	0.0608 (14)	−0.0087 (15)	−0.0020 (12)	0.0067 (14)
C17	0.0582 (14)	0.0583 (14)	0.0487 (11)	−0.0006 (12)	0.0014 (11)	0.0027 (11)
C18	0.0716 (17)	0.0560 (14)	0.0709 (15)	0.0020 (14)	0.0103 (15)	−0.0015 (13)
C19	0.0593 (15)	0.0602 (15)	0.0576 (13)	0.0002 (12)	0.0054 (12)	0.0065 (13)
C20	0.0692 (17)	0.0693 (16)	0.0614 (14)	−0.0007 (15)	0.0067 (14)	0.0113 (13)
C21	0.086 (2)	0.133 (3)	0.083 (2)	−0.017 (2)	−0.0076 (19)	0.054 (2)
C22	0.0759 (19)	0.0755 (19)	0.0708 (16)	0.0012 (16)	0.0130 (15)	0.0091 (16)
C23	0.085 (2)	0.093 (3)	0.116 (3)	0.004 (2)	0.036 (2)	0.030 (2)
C24	0.077 (2)	0.093 (2)	0.095 (2)	−0.0035 (19)	0.0192 (18)	0.014 (2)
C251	0.081 (3)	0.089 (4)	0.094 (4)	−0.031 (3)	0.022 (3)	−0.009 (3)
C261	0.131 (6)	0.089 (4)	0.129 (6)	−0.019 (4)	0.030 (5)	0.025 (4)
C271	0.085 (4)	0.140 (6)	0.156 (7)	−0.028 (4)	0.051 (5)	−0.004 (5)
C252	0.073 (7)	0.076 (8)	0.080 (8)	−0.024 (7)	−0.001 (7)	−0.014 (7)
C262	0.21 (3)	0.23 (3)	0.14 (2)	−0.06 (3)	0.01 (2)	0.07 (2)
C272	0.094 (13)	0.19 (3)	0.32 (4)	−0.067 (16)	0.03 (2)	0.03 (3)
O28	0.0671 (12)	0.0578 (11)	0.0954 (14)	−0.0046 (10)	0.0088 (11)	−0.0056 (11)
C29	0.082 (2)	0.0616 (18)	0.107 (2)	−0.0112 (18)	0.0187 (19)	−0.0178 (18)
O301	0.096 (4)	0.056 (4)	0.132 (6)	0.021 (3)	0.031 (4)	0.009 (3)
O302	0.22 (2)	0.100 (8)	0.24 (3)	−0.058 (10)	0.132 (19)	−0.068 (12)
C31	0.091 (2)	0.079 (2)	0.135 (3)	−0.015 (2)	0.029 (2)	−0.012 (2)
O32	0.0512 (9)	0.0758 (12)	0.0553 (9)	0.0015 (9)	−0.0064 (8)	0.0217 (9)
C33	0.0545 (15)	0.0722 (17)	0.0622 (14)	0.0075 (14)	−0.0023 (13)	0.0093 (14)
O34	0.0587 (11)	0.1137 (19)	0.0976 (15)	0.0029 (12)	0.0072 (11)	0.0390 (15)
C35	0.0668 (17)	0.087 (2)	0.0740 (16)	0.0147 (17)	−0.0089 (15)	0.0185 (16)

C1—C10	1.516 (4)	C19—H19C	0.9600
C1—C2	1.521 (4)	C20—C21	1.532 (5)
C1—H1A	0.9700	C20—C22	1.541 (4)
C1—H1B	0.9700	C20—H20Z	0.9800
C2—C3	1.516 (4)	C21—H21A	0.9600
C2—H2A	0.9700	C21—H21B	0.9600
C2—H2B	0.9700	C21—H21C	0.9600
C3—O28	1.456 (3)	C22—C23	1.507 (4)
C3—C4	1.513 (4)	C22—H22A	0.9700
C3—H3A	0.9800	C22—H22B	0.9700
C4—C5	1.554 (4)	C23—C24	1.507 (5)
C4—H4A	0.9700	C23—H23A	0.9700
C4—H4B	0.9700	C23—H23B	0.9700
C5—C10	1.537 (3)	C24—C251	1.534 (7)
C5—C6	1.538 (4)	C24—C252	1.530 (14)
C5—C19	1.548 (3)	C24—H24A	0.9700
C6—O32	1.460 (3)	C24—H24B	0.9700
C6—C7	1.513 (4)	C24—H24C	0.9700
C6—H6A	0.9800	C24—H24D	0.9699
C7—C8	1.530 (3)	C251—C261	1.512 (8)
C7—H7A	0.9700	C251—C271	1.492 (8)
C7—H7B	0.9700	C251—H25A	0.9800
C8—C9	1.523 (3)	C261—H26A	0.9600
C8—C14	1.528 (3)	C261—H26B	0.9600
C8—H8A	0.9800	C261—H26C	0.9600
C9—C10	1.347 (4)	C271—H27A	0.9600
C9—C11	1.516 (3)	C271—H27B	0.9600
C11—C12	1.539 (4)	C271—H27C	0.9600
C11—H11A	0.9700	C252—C262	1.529 (17)
C11—H11B	0.9700	C252—C272	1.473 (17)
C12—C13	1.542 (4)	C252—H25B	0.9800
C12—H12A	0.9700	C262—H26D	0.9600
C12—H12B	0.9700	C262—H26E	0.9600
C13—C18	1.545 (4)	C262—H26F	0.9600
C13—C14	1.550 (3)	C272—H27D	0.9600
C13—C17	1.550 (3)	C272—H27E	0.9600
C14—C15	1.535 (3)	C272—H27F	0.9600
C14—H14A	0.9800	O28—C29	1.317 (4)
C15—C16	1.545 (4)	C29—O301	1.216 (7)
C15—H15A	0.9700	C29—O302	1.238 (17)
C15—H15B	0.9700	C29—C31	1.475 (5)
C16—C17	1.551 (4)	C31—H31A	0.9600
C16—H16A	0.9700	C31—H31B	0.9600
C16—H16B	0.9700	C31—H31C	0.9600
C17—C20	1.543 (4)	O32—C33	1.346 (3)
C17—H17A	0.9800	C33—O34	1.197 (3)
C18—H18A	0.9600	C33—C35	1.486 (4)
C18—H18B	0.9600	C35—H35A	0.9600
C18—H18C	0.9600	C35—H35B	0.9600
C19—H19A	0.9600	C35—H35C	0.9600
C19—H19B	0.9600
C10—C1—C2	112.4 (2)	C16—C17—H17A	106.6
C10—C1—H1A	109.1	C13—C18—H18A	109.5
C2—C1—H1A	109.1	C13—C18—H18B	109.5
C10—C1—H1B	109.1	H18A—C18—H18B	109.5
C2—C1—H1B	109.1	C13—C18—H18C	109.5
H1A—C1—H1B	107.8	H18A—C18—H18C	109.5
C3—C2—C1	111.3 (2)	H18B—C18—H18C	109.5
C3—C2—H2A	109.4	C5—C19—H19A	109.5
C1—C2—H2A	109.4	C5—C19—H19B	109.5
C3—C2—H2B	109.4	H19A—C19—H19B	109.5
C1—C2—H2B	109.4	C5—C19—H19C	109.5
H2A—C2—H2B	108.0	H19A—C19—H19C	109.5
O28—C3—C4	111.0 (2)	H19B—C19—H19C	109.5
O28—C3—C2	106.0 (2)	C21—C20—C22	110.3 (3)
C4—C3—C2	110.8 (2)	C21—C20—C17	111.8 (3)
O28—C3—H3A	109.6	C22—C20—C17	111.1 (2)
C4—C3—H3A	109.6	C21—C20—H20Z	107.8
C2—C3—H3A	109.6	C22—C20—H20Z	107.8
C3—C4—C5	117.0 (2)	C17—C20—H20Z	107.8
C3—C4—H4A	108.1	C20—C21—H21A	109.5
C5—C4—H4A	108.1	C20—C21—H21B	109.5
C3—C4—H4B	108.1	H21A—C21—H21B	109.5
C5—C4—H4B	108.1	C20—C21—H21C	109.5
H4A—C4—H4B	107.3	H21A—C21—H21C	109.5
C10—C5—C6	108.4 (2)	H21B—C21—H21C	109.5
C10—C5—C19	110.4 (2)	C23—C22—C20	114.7 (3)
C6—C5—C19	111.16 (19)	C23—C22—H22A	108.6
C10—C5—C4	110.67 (19)	C20—C22—H22A	108.6
C6—C5—C4	106.7 (2)	C23—C22—H22B	108.6
C19—C5—C4	109.5 (2)	C20—C22—H22B	108.6
O32—C6—C7	110.59 (19)	H22A—C22—H22B	107.6
O32—C6—C5	107.9 (2)	C22—C23—C24	115.1 (3)
C7—C6—C5	112.4 (2)	C22—C23—H23A	108.5
O32—C6—H6A	108.6	C24—C23—H23A	108.5
C7—C6—H6A	108.6	C22—C23—H23B	108.5
C5—C6—H6A	108.6	C24—C23—H23B	108.5
C6—C7—C8	109.34 (18)	H23A—C23—H23B	107.5
C6—C7—H7A	109.8	C23—C24—C251	115.0 (4)
C8—C7—H7A	109.8	C23—C24—C252	118.0 (6)
C6—C7—H7B	109.8	C23—C24—H24A	108.5
C8—C7—H7B	109.8	C23—C24—H24B	108.5
H7A—C7—H7B	108.3	C23—C24—H24C	107.8
C9—C8—C14	106.51 (18)	C23—C24—H24D	107.8
C9—C8—C7	113.0 (2)	C251—C24—H24A	108.5
C14—C8—C7	114.4 (2)	C251—C24—H24B	108.5
C9—C8—H8A	107.6	C252—C24—H24C	107.8
C14—C8—H8A	107.6	C252—C24—H24D	107.8
C7—C8—H8A	107.6	H24A—C24—H24B	107.5
C10—C9—C11	125.5 (2)	H24C—C24—H24D	107.1
C10—C9—C8	123.4 (2)	C261—C251—C271	113.5 (6)
C11—C9—C8	111.0 (2)	C261—C251—C24	112.1 (6)
C9—C10—C1	123.4 (2)	C271—C251—C24	112.3 (6)
C9—C10—C5	123.0 (2)	C261—C251—H25A	106.1
C1—C10—C5	113.6 (2)	C271—C251—H25A	106.1
C9—C11—C12	111.7 (2)	C24—C251—H25A	106.1
C9—C11—H11A	109.3	C262—C252—C272	111.1 (19)
C12—C11—H11A	109.3	C262—C252—C24	103.8 (18)
C9—C11—H11B	109.3	C272—C252—C24	111.0 (15)
C12—C11—H11B	109.3	C262—C252—H25B	110.3
H11A—C11—H11B	107.9	C272—C252—H25B	110.3
C11—C12—C13	113.2 (2)	C24—C252—H25B	110.3
C11—C12—H12A	108.9	C252—C262—H26D	109.5
C13—C12—H12A	108.9	C252—C262—H26E	109.5
C11—C12—H12B	108.9	C252—C262—H26F	109.5
C13—C12—H12B	108.9	H26D—C262—H26E	109.5
H12A—C12—H12B	107.7	H26D—C262—H26F	109.5
C12—C13—C18	109.9 (2)	H26E—C262—H26F	109.5
C12—C13—C14	106.6 (2)	C252—C272—H27D	109.5
C18—C13—C14	112.64 (19)	C252—C272—H27E	109.5
C12—C13—C17	117.36 (19)	C252—C272—H27F	109.5
C18—C13—C17	110.5 (2)	H27D—C272—H27E	109.5
C14—C13—C17	99.4 (2)	H27D—C272—H27F	109.5
C8—C14—C15	119.70 (18)	H27E—C272—H27F	109.5
C8—C14—C13	113.9 (2)	C29—O28—C3	120.2 (3)
C15—C14—C13	104.3 (2)	O301—C29—O28	122.1 (5)
C8—C14—H14A	106.0	O302—C29—O28	116.5 (14)
C15—C14—H14A	106.0	O301—C29—C31	123.7 (5)
C13—C14—H14A	106.0	O302—C29—C31	125.5 (10)
C14—C15—C16	103.04 (19)	O28—C29—C31	112.2 (3)
C14—C15—H15A	111.2	C29—C31—H31A	109.5
C16—C15—H15A	111.2	C29—C31—H31B	109.5
C14—C15—H15B	111.2	H31A—C31—H31B	109.5
C16—C15—H15B	111.2	C29—C31—H31C	109.5
H15A—C15—H15B	109.1	H31A—C31—H31C	109.5
C15—C16—C17	107.3 (2)	H31B—C31—H31C	109.5
C15—C16—H16A	110.3	C33—O32—C6	116.3 (2)
C17—C16—H16A	110.3	O34—C33—O32	123.6 (3)
C15—C16—H16B	110.3	O34—C33—C35	124.9 (3)
C17—C16—H16B	110.3	O32—C33—C35	111.5 (2)
H16A—C16—H16B	108.5	C33—C35—H35A	109.5
C20—C17—C13	119.5 (2)	C33—C35—H35B	109.5
C20—C17—C16	112.7 (2)	H35A—C35—H35B	109.5
C13—C17—C16	103.94 (19)	C33—C35—H35C	109.5
C20—C17—H17A	106.6	H35A—C35—H35C	109.5
C13—C17—H17A	106.6	H35B—C35—H35C	109.5
C10—C1—C2—C3	57.8 (3)	C12—C13—C14—C8	−58.3 (3)
C1—C2—C3—O28	66.2 (3)	C18—C13—C14—C8	62.3 (3)
C1—C2—C3—C4	−54.4 (3)	C17—C13—C14—C8	179.29 (19)
O28—C3—C4—C5	−68.0 (3)	C12—C13—C14—C15	169.4 (2)
C2—C3—C4—C5	49.5 (3)	C18—C13—C14—C15	−70.0 (3)
C3—C4—C5—C10	−44.6 (3)	C17—C13—C14—C15	47.0 (2)
C3—C4—C5—C6	−162.4 (2)	C8—C14—C15—C16	−164.2 (2)
C3—C4—C5—C19	77.2 (3)	C13—C14—C15—C16	−35.3 (3)
C10—C5—C6—O32	174.13 (19)	C14—C15—C16—C17	9.6 (3)
C19—C5—C6—O32	52.7 (3)	C12—C13—C17—C20	79.2 (3)
C4—C5—C6—O32	−66.6 (2)	C18—C13—C17—C20	−47.9 (3)
C10—C5—C6—C7	51.9 (2)	C14—C13—C17—C20	−166.5 (2)
C19—C5—C6—C7	−69.5 (3)	C12—C13—C17—C16	−154.1 (2)
C4—C5—C6—C7	171.17 (19)	C18—C13—C17—C16	78.8 (3)
O32—C6—C7—C8	174.9 (2)	C14—C13—C17—C16	−39.8 (2)
C5—C6—C7—C8	−64.5 (3)	C15—C16—C17—C20	150.2 (3)
C6—C7—C8—C9	41.3 (3)	C15—C16—C17—C13	19.4 (3)
C6—C7—C8—C14	−80.8 (3)	C13—C17—C20—C21	−60.8 (3)
C14—C8—C9—C10	115.5 (3)	C16—C17—C20—C21	176.7 (3)
C7—C8—C9—C10	−10.9 (3)	C13—C17—C20—C22	175.5 (2)
C14—C8—C9—C11	−60.0 (3)	C16—C17—C20—C22	53.0 (3)
C7—C8—C9—C11	173.6 (2)	C21—C20—C22—C23	58.0 (4)
C11—C9—C10—C1	−7.3 (4)	C17—C20—C22—C23	−177.5 (3)
C8—C9—C10—C1	177.8 (2)	C20—C22—C23—C24	175.5 (3)
C11—C9—C10—C5	174.8 (2)	C22—C23—C24—C252	−164.3 (8)
C8—C9—C10—C5	0.0 (4)	C22—C23—C24—C251	156.2 (4)
C2—C1—C10—C9	128.1 (3)	C23—C24—C251—C261	57.6 (8)
C2—C1—C10—C5	−53.8 (3)	C252—C24—C251—C261	−46.2 (10)
C6—C5—C10—C9	−19.8 (3)	C23—C24—C251—C271	−173.3 (5)
C19—C5—C10—C9	102.2 (3)	C252—C24—C251—C271	82.9 (11)
C4—C5—C10—C9	−136.5 (3)	C23—C24—C252—C272	172 (2)
C6—C5—C10—C1	162.2 (2)	C251—C24—C252—C272	−94 (2)
C19—C5—C10—C1	−75.9 (3)	C23—C24—C252—C262	−69 (2)
C4—C5—C10—C1	45.5 (3)	C251—C24—C252—C262	25.6 (19)
C10—C9—C11—C12	−118.3 (3)	C4—C3—O28—C29	−91.3 (3)
C8—C9—C11—C12	57.1 (3)	C2—C3—O28—C29	148.3 (3)
C9—C11—C12—C13	−53.6 (3)	C3—O28—C29—O301	13.5 (9)
C11—C12—C13—C18	−70.6 (3)	C3—O28—C29—O302	−28 (3)
C11—C12—C13—C14	51.7 (3)	C3—O28—C29—C31	177.6 (3)
C11—C12—C13—C17	162.0 (2)	C7—C6—O32—C33	−82.4 (3)
C9—C8—C14—C15	−172.7 (2)	C5—C6—O32—C33	154.3 (2)
C7—C8—C14—C15	−47.2 (3)	C6—O32—C33—O34	−2.0 (4)
C9—C8—C14—C13	62.9 (3)	C6—O32—C33—C35	175.8 (2)
C7—C8—C14—C13	−171.6 (2)