The zwitterion (23'E)-(23R,25S)-23-[1-(oxidoiminio)eth-yl]-5β-spiro-stan-3β-yl acetate.

The title steroidal compound, C(31)H(49)NO(5), resulted from the selective oximation of (23R)-23-acetyl-sarsasapogenin acetate. One- and two-dimensional (1)H and (13)C NMR spectra, as well as IR data, are in agreement with the presence of a ketoxime group at C-23. However, recrystallization in slightly acidic media affords the title compound in the rare zwitterionic oxime form, as a consequence of migration of the hydr-oxy H atom to the N atom in the oxime group. This H atom is clearly detected and its position was refined from X-ray data. The geometry for the C=N(+)(H)-O(-) group features long C=N and short N-O bond lengths compared to non-zwitterionic oximes. The ketoxime is stabilized with the E configuration, avoiding steric hindrance between the oxime O atom and H atom at C-23. The sum of the angles around the oxime N atom is 359.6°, giving a planar configuration for that atom, as expected for sp(2) hybridization.

Related literature

For the synthesis of (23R)-23-acetyl­sarsasapogenin acetate used as starting material, see: Meza-Reyes et al. (2005 ▶). For the full spectroscopic characterization of the tautomers of the title compound, see: Hernández-Linares (2005 ▶). For tautomerism between oximes and imine N-oxides, see: Fernández et al. (1994 ▶). For related zwitterionic oximes and hydro­chloride oximes characterized by X-ray diffraction, see: Witte et al. (1984 ▶); Fernández et al. (1994 ▶); Gurkova et al. (1988 ▶); Laus et al. (2008 ▶); Forgan et al. (2008 ▶).

Experimental

Crystal data

C31H49NO5

M = 515.71

Orthorhombic,

a = 8.385 (2) Å

b = 11.5627 (16) Å

c = 30.420 (5) Å

V = 2949.2 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 298 K

0.60 × 0.60 × 0.35 mm

Data collection

Bruker P4 diffractometer

Absorption correction: none

4182 measured reflections

2956 independent reflections

2512 reflections with I > 2σ(I)

R int = 0.041

3 standard reflections every 97 reflections intensity decay: 3%

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.129

S = 1.02

2956 reflections

344 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.25 e Å−3

Data collection: XSCANS (Siemens, 1994 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809044651/nk2010sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044651/nk2010Isup2.hkl

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

C31H49NO5	Dx = 1.161 Mg m−3
Mr = 515.71	Melting point: 516 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 44 reflections
a = 8.385 (2) Å	θ = 4.7–12.5°
b = 11.5627 (16) Å	µ = 0.08 mm−1
c = 30.420 (5) Å	T = 298 K
V = 2949.2 (10) Å3	Irregular, colourless
Z = 4	0.60 × 0.60 × 0.35 mm
F(000) = 1128

Bruker P4 diffractometer	Rint = 0.041
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.9°
graphite	h = −9→2
ω scans	k = −13→1
4182 measured reflections	l = −36→1
2956 independent reflections	3 standard reflections every 97 reflections
2512 reflections with I > 2σ(I)	intensity decay: 3%

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 atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.129	w = 1/[σ2(Fo2) + (0.0651P)2 + 1.0057P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2956 reflections	Δρmax = 0.46 e Å−3
344 parameters	Δρmin = −0.25 e Å−3
2 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0095 (18)

	x	y	z	Uiso*/Ueq
C1	1.0856 (4)	0.6448 (3)	0.33730 (11)	0.0516 (9)
H1A	1.0915	0.5917	0.3619	0.062*
H1B	1.1393	0.6086	0.3126	0.062*
C2	1.1766 (4)	0.7539 (4)	0.34940 (12)	0.0560 (9)
H2D	1.1862	0.8030	0.3237	0.067*
H2E	1.2832	0.7333	0.3589	0.067*
C3	1.0929 (5)	0.8205 (3)	0.38583 (11)	0.0554 (9)
H3A	1.1486	0.8934	0.3917	0.066*
C4	0.9219 (5)	0.8431 (3)	0.37427 (11)	0.0531 (9)
H4A	0.9182	0.8964	0.3497	0.064*
H4B	0.8701	0.8802	0.3991	0.064*
C5	0.8285 (4)	0.7338 (3)	0.36217 (10)	0.0485 (8)
H5A	0.8271	0.6848	0.3885	0.058*
C6	0.6548 (4)	0.7627 (4)	0.35160 (11)	0.0599 (11)
H6A	0.6116	0.8113	0.3747	0.072*
H6B	0.5929	0.6919	0.3508	0.072*
C7	0.6396 (5)	0.8252 (4)	0.30744 (11)	0.0587 (10)
H7B	0.5277	0.8390	0.3012	0.070*
H7C	0.6925	0.8996	0.3093	0.070*
C8	0.7128 (4)	0.7551 (3)	0.27006 (10)	0.0447 (8)
H8B	0.6522	0.6831	0.2670	0.054*
C9	0.8885 (4)	0.7238 (3)	0.27973 (10)	0.0421 (7)
H9B	0.9461	0.7972	0.2821	0.051*
C10	0.9083 (4)	0.6615 (3)	0.32507 (10)	0.0441 (8)
C11	0.9635 (5)	0.6585 (3)	0.24098 (10)	0.0552 (9)
H11B	0.9145	0.5827	0.2389	0.066*
H11C	1.0761	0.6473	0.2469	0.066*
C12	0.9452 (4)	0.7207 (3)	0.19660 (11)	0.0519 (9)
H12A	1.0078	0.7913	0.1970	0.062*
H12B	0.9866	0.6716	0.1734	0.062*
C13	0.7726 (4)	0.7502 (3)	0.18680 (10)	0.0410 (7)
C14	0.7059 (4)	0.8196 (3)	0.22627 (10)	0.0434 (8)
H14B	0.7764	0.8867	0.2296	0.052*
C15	0.5478 (4)	0.8673 (4)	0.20928 (10)	0.0531 (9)
H15B	0.5123	0.9329	0.2266	0.064*
H15C	0.4655	0.8084	0.2093	0.064*
C16	0.5917 (4)	0.9040 (3)	0.16224 (10)	0.0448 (8)
H16B	0.6064	0.9880	0.1607	0.054*
C17	0.7482 (4)	0.8411 (3)	0.14966 (10)	0.0405 (7)
H17C	0.8361	0.8968	0.1508	0.049*
C18	0.6769 (5)	0.6401 (3)	0.17818 (12)	0.0576 (9)
H18C	0.6759	0.5932	0.2042	0.086*
H18D	0.7251	0.5976	0.1545	0.086*
H18E	0.5695	0.6602	0.1704	0.086*
C19	0.8329 (5)	0.5408 (3)	0.32368 (13)	0.0615 (10)
H19A	0.8376	0.5066	0.3524	0.092*
H19B	0.8903	0.4932	0.3032	0.092*
H19C	0.7237	0.5471	0.3145	0.092*
C20	0.7218 (4)	0.8046 (3)	0.10144 (10)	0.0435 (8)
H20A	0.7122	0.7202	0.1007	0.052*
C21	0.8573 (4)	0.8390 (4)	0.07093 (12)	0.0606 (10)
H21B	0.8276	0.8230	0.0411	0.091*
H21C	0.9512	0.7956	0.0783	0.091*
H21D	0.8787	0.9201	0.0741	0.091*
C22	0.5588 (4)	0.8561 (3)	0.08961 (10)	0.0391 (7)
O22	0.4759 (2)	0.86704 (19)	0.13038 (6)	0.0415 (5)
C23	0.4554 (4)	0.7843 (3)	0.05791 (10)	0.0430 (8)
H23C	0.5201	0.7697	0.0317	0.052*
C24	0.3086 (4)	0.8530 (3)	0.04293 (11)	0.0511 (8)
H24C	0.2537	0.8100	0.0201	0.061*
H24D	0.2359	0.8616	0.0675	0.061*
C25	0.3526 (5)	0.9721 (3)	0.02546 (11)	0.0541 (9)
H25C	0.2538	1.0157	0.0209	0.065*
C26	0.4476 (5)	1.0321 (3)	0.06089 (12)	0.0552 (9)
H26D	0.4773	1.1088	0.0509	0.066*
H26E	0.3821	1.0405	0.0870	0.066*
O26	0.5890 (3)	0.96787 (19)	0.07171 (7)	0.0473 (6)
C27	0.4413 (6)	0.9665 (4)	−0.01843 (12)	0.0700 (11)
H27C	0.4699	1.0432	−0.0275	0.105*
H27D	0.3735	0.9319	−0.0402	0.105*
H27E	0.5360	0.9207	−0.0151	0.105*
O28	1.0885 (3)	0.7483 (2)	0.42577 (7)	0.0540 (6)
C29	1.2125 (5)	0.7503 (3)	0.45297 (11)	0.0539 (9)
O30	1.3306 (4)	0.8083 (3)	0.44684 (10)	0.0741 (8)
C31	1.1864 (5)	0.6731 (4)	0.49129 (12)	0.0710 (12)
H31B	1.2539	0.6970	0.5151	0.106*
H31C	1.2117	0.5950	0.4833	0.106*
H31D	1.0769	0.6775	0.5003	0.106*
C32	0.4111 (4)	0.6680 (3)	0.07679 (11)	0.0483 (8)
C33	0.2777 (5)	0.6538 (4)	0.10802 (13)	0.0660 (11)
H33A	0.3050	0.5962	0.1295	0.099*
H33B	0.1839	0.6299	0.0924	0.099*
H33C	0.2574	0.7260	0.1225	0.099*
N34	0.5075 (6)	0.5826 (3)	0.06127 (13)	0.0854 (13)
H34	0.605 (5)	0.585 (2)	0.0434 (17)	0.128*
O35	0.4610 (5)	0.4795 (3)	0.07914 (14)	0.1043 (12)

	U11	U22	U33	U12	U13	U23
C1	0.051 (2)	0.058 (2)	0.0460 (17)	0.0135 (19)	0.0002 (16)	0.0069 (16)
C2	0.0428 (18)	0.069 (2)	0.056 (2)	−0.003 (2)	−0.0010 (16)	0.013 (2)
C3	0.060 (2)	0.054 (2)	0.0515 (18)	−0.009 (2)	−0.0074 (18)	0.0068 (16)
C4	0.060 (2)	0.0538 (19)	0.0458 (17)	0.0118 (19)	−0.0014 (17)	−0.0013 (16)
C5	0.0440 (18)	0.059 (2)	0.0422 (17)	0.0067 (18)	0.0023 (15)	0.0068 (16)
C6	0.0442 (18)	0.094 (3)	0.0415 (17)	0.019 (2)	0.0072 (16)	0.003 (2)
C7	0.048 (2)	0.083 (3)	0.0454 (17)	0.027 (2)	0.0009 (16)	−0.0018 (18)
C8	0.0405 (17)	0.0530 (18)	0.0405 (16)	0.0062 (18)	0.0007 (14)	0.0011 (15)
C9	0.0392 (16)	0.0439 (17)	0.0433 (16)	0.0060 (15)	−0.0002 (14)	0.0001 (14)
C10	0.0425 (17)	0.0450 (17)	0.0449 (16)	0.0041 (16)	−0.0018 (15)	0.0045 (14)
C11	0.052 (2)	0.066 (2)	0.0474 (18)	0.019 (2)	0.0044 (16)	0.0054 (17)
C12	0.0462 (19)	0.064 (2)	0.0458 (17)	0.0113 (18)	0.0065 (16)	0.0026 (16)
C13	0.0413 (17)	0.0433 (16)	0.0385 (15)	0.0079 (16)	0.0020 (14)	−0.0003 (14)
C14	0.0425 (17)	0.0485 (18)	0.0392 (15)	0.0102 (17)	−0.0026 (14)	−0.0036 (15)
C15	0.052 (2)	0.069 (2)	0.0375 (15)	0.022 (2)	0.0008 (15)	−0.0045 (16)
C16	0.0460 (18)	0.0464 (17)	0.0421 (16)	0.0087 (17)	−0.0037 (15)	−0.0033 (14)
C17	0.0370 (16)	0.0425 (16)	0.0420 (16)	0.0005 (15)	−0.0003 (14)	−0.0008 (14)
C18	0.068 (2)	0.0508 (19)	0.0541 (19)	−0.007 (2)	0.0033 (19)	−0.0030 (17)
C19	0.069 (3)	0.053 (2)	0.063 (2)	−0.005 (2)	−0.002 (2)	0.0078 (18)
C20	0.0406 (17)	0.0491 (18)	0.0408 (16)	0.0034 (16)	0.0011 (14)	−0.0040 (15)
C21	0.0439 (19)	0.089 (3)	0.0490 (18)	0.005 (2)	0.0077 (17)	0.000 (2)
C22	0.0366 (16)	0.0435 (16)	0.0373 (14)	0.0037 (15)	0.0031 (14)	−0.0023 (13)
O22	0.0375 (11)	0.0500 (12)	0.0369 (10)	0.0064 (11)	0.0016 (9)	−0.0021 (10)
C23	0.0383 (17)	0.0507 (18)	0.0399 (16)	0.0009 (15)	0.0032 (15)	−0.0040 (14)
C24	0.0439 (18)	0.061 (2)	0.0485 (17)	0.0003 (18)	−0.0036 (16)	−0.0034 (17)
C25	0.050 (2)	0.059 (2)	0.0530 (19)	0.0090 (19)	−0.0032 (18)	0.0042 (17)
C26	0.061 (2)	0.0443 (18)	0.060 (2)	0.0087 (18)	0.001 (2)	0.0056 (16)
O26	0.0466 (13)	0.0468 (12)	0.0486 (12)	−0.0029 (12)	0.0005 (11)	0.0054 (10)
C27	0.079 (3)	0.079 (3)	0.052 (2)	0.004 (3)	−0.002 (2)	0.015 (2)
O28	0.0521 (13)	0.0620 (14)	0.0480 (12)	−0.0073 (14)	−0.0077 (12)	0.0084 (12)
C29	0.054 (2)	0.059 (2)	0.0481 (18)	0.009 (2)	−0.0064 (17)	−0.0047 (18)
O30	0.0616 (17)	0.0797 (19)	0.0810 (19)	−0.0100 (17)	−0.0189 (16)	0.0064 (17)
C31	0.065 (3)	0.092 (3)	0.056 (2)	0.015 (3)	−0.002 (2)	0.010 (2)
C32	0.0515 (19)	0.0424 (17)	0.0511 (18)	−0.0031 (17)	−0.0078 (17)	−0.0053 (15)
C33	0.064 (2)	0.061 (2)	0.073 (2)	−0.018 (2)	0.000 (2)	0.010 (2)
N34	0.118 (3)	0.0420 (17)	0.096 (3)	−0.013 (2)	−0.039 (3)	0.0033 (18)
O35	0.110 (3)	0.079 (2)	0.123 (3)	−0.018 (2)	0.028 (3)	0.001 (2)

C1—C2	1.519 (5)	C17—C20	1.542 (4)
C1—C10	1.544 (5)	C17—H17C	0.9800
C1—H1A	0.9700	C18—H18C	0.9600
C1—H1B	0.9700	C18—H18D	0.9600
C2—C3	1.520 (5)	C18—H18E	0.9600
C2—H2D	0.9700	C19—H19A	0.9600
C2—H2E	0.9700	C19—H19B	0.9600
C3—O28	1.474 (4)	C19—H19C	0.9600
C3—C4	1.500 (5)	C20—C21	1.520 (5)
C3—H3A	0.9800	C20—C22	1.534 (5)
C4—C5	1.531 (5)	C20—H20A	0.9800
C4—H4A	0.9700	C21—H21B	0.9600
C4—H4B	0.9700	C21—H21C	0.9600
C5—C6	1.529 (5)	C21—H21D	0.9600
C5—C10	1.556 (5)	C22—O26	1.426 (4)
C5—H5A	0.9800	C22—O22	1.427 (4)
C6—C7	1.531 (5)	C22—C23	1.539 (5)
C6—H6A	0.9700	C23—C32	1.509 (5)
C6—H6B	0.9700	C23—C24	1.534 (5)
C7—C8	1.526 (5)	C23—H23C	0.9800
C7—H7B	0.9700	C24—C25	1.522 (5)
C7—H7C	0.9700	C24—H24C	0.9700
C8—C14	1.528 (4)	C24—H24D	0.9700
C8—C9	1.545 (5)	C25—C26	1.509 (5)
C8—H8B	0.9800	C25—C27	1.530 (5)
C9—C11	1.534 (5)	C25—H25C	0.9800
C9—C10	1.565 (4)	C26—O26	1.437 (4)
C9—H9B	0.9800	C26—H26D	0.9700
C10—C19	1.532 (5)	C26—H26E	0.9700
C11—C12	1.537 (5)	C27—H27C	0.9600
C11—H11B	0.9700	C27—H27D	0.9600
C11—H11C	0.9700	C27—H27E	0.9600
C12—C13	1.517 (5)	O28—C29	1.328 (4)
C12—H12A	0.9700	C29—O30	1.210 (5)
C12—H12B	0.9700	C29—C31	1.484 (5)
C13—C18	1.528 (5)	C31—H31B	0.9600
C13—C14	1.549 (4)	C31—H31C	0.9600
C13—C17	1.556 (4)	C31—H31D	0.9600
C14—C15	1.526 (5)	C32—C33	1.477 (5)
C14—H14B	0.9800	C32—N34	1.361 (6)
C15—C16	1.537 (5)	C33—H33A	0.9600
C15—H15B	0.9700	C33—H33B	0.9600
C15—H15C	0.9700	C33—H33C	0.9600
C16—O22	1.437 (4)	N34—H34	0.980 (18)
C16—C17	1.548 (4)	N34—O35	1.367 (5)
C16—H16B	0.9800
C2—C1—C10	116.0 (3)	O22—C16—H16B	110.3
C2—C1—H1A	108.3	C15—C16—H16B	110.3
C10—C1—H1A	108.3	C17—C16—H16B	110.3
C2—C1—H1B	108.3	C20—C17—C16	104.0 (2)
C10—C1—H1B	108.3	C20—C17—C13	121.6 (3)
H1A—C1—H1B	107.4	C16—C17—C13	104.4 (2)
C1—C2—C3	111.4 (3)	C20—C17—H17C	108.7
C1—C2—H2D	109.3	C16—C17—H17C	108.7
C3—C2—H2D	109.3	C13—C17—H17C	108.7
C1—C2—H2E	109.3	C13—C18—H18C	109.5
C3—C2—H2E	109.3	C13—C18—H18D	109.5
H2D—C2—H2E	108.0	H18C—C18—H18D	109.5
O28—C3—C4	105.5 (3)	C13—C18—H18E	109.5
O28—C3—C2	109.0 (3)	H18C—C18—H18E	109.5
C4—C3—C2	111.0 (3)	H18D—C18—H18E	109.5
O28—C3—H3A	110.4	C10—C19—H19A	109.5
C4—C3—H3A	110.4	C10—C19—H19B	109.5
C2—C3—H3A	110.4	H19A—C19—H19B	109.5
C3—C4—C5	113.7 (3)	C10—C19—H19C	109.5
C3—C4—H4A	108.8	H19A—C19—H19C	109.5
C5—C4—H4A	108.8	H19B—C19—H19C	109.5
C3—C4—H4B	108.8	C21—C20—C22	114.9 (3)
C5—C4—H4B	108.8	C21—C20—C17	113.7 (3)
H4A—C4—H4B	107.7	C22—C20—C17	104.2 (3)
C6—C5—C4	110.9 (3)	C21—C20—H20A	107.9
C6—C5—C10	112.0 (3)	C22—C20—H20A	107.9
C4—C5—C10	113.4 (3)	C17—C20—H20A	107.9
C6—C5—H5A	106.7	C20—C21—H21B	109.5
C4—C5—H5A	106.7	C20—C21—H21C	109.5
C10—C5—H5A	106.7	H21B—C21—H21C	109.5
C5—C6—C7	111.6 (3)	C20—C21—H21D	109.5
C5—C6—H6A	109.3	H21B—C21—H21D	109.5
C7—C6—H6A	109.3	H21C—C21—H21D	109.5
C5—C6—H6B	109.3	O26—C22—O22	109.7 (2)
C7—C6—H6B	109.3	O26—C22—C20	106.4 (3)
H6A—C6—H6B	108.0	O22—C22—C20	105.3 (2)
C8—C7—C6	111.7 (3)	O26—C22—C23	110.5 (2)
C8—C7—H7B	109.3	O22—C22—C23	108.6 (2)
C6—C7—H7B	109.3	C20—C22—C23	116.1 (3)
C8—C7—H7C	109.3	C22—O22—C16	106.5 (2)
C6—C7—H7C	109.3	C32—C23—C24	112.1 (3)
H7B—C7—H7C	107.9	C32—C23—C22	112.4 (3)
C7—C8—C14	112.0 (3)	C24—C23—C22	111.1 (3)
C7—C8—C9	111.5 (3)	C32—C23—H23C	107.0
C14—C8—C9	108.4 (3)	C24—C23—H23C	107.0
C7—C8—H8B	108.3	C22—C23—H23C	107.0
C14—C8—H8B	108.3	C25—C24—C23	112.2 (3)
C9—C8—H8B	108.3	C25—C24—H24C	109.2
C11—C9—C8	111.1 (3)	C23—C24—H24C	109.2
C11—C9—C10	114.0 (3)	C25—C24—H24D	109.2
C8—C9—C10	112.2 (3)	C23—C24—H24D	109.2
C11—C9—H9B	106.3	H24C—C24—H24D	107.9
C8—C9—H9B	106.3	C26—C25—C24	107.1 (3)
C10—C9—H9B	106.3	C26—C25—C27	112.7 (3)
C19—C10—C1	106.9 (3)	C24—C25—C27	112.6 (3)
C19—C10—C5	109.4 (3)	C26—C25—H25C	108.1
C1—C10—C5	107.8 (3)	C24—C25—H25C	108.1
C19—C10—C9	110.5 (3)	C27—C25—H25C	108.1
C1—C10—C9	111.8 (3)	O26—C26—C25	111.2 (3)
C5—C10—C9	110.2 (3)	O26—C26—H26D	109.4
C9—C11—C12	113.8 (3)	C25—C26—H26D	109.4
C9—C11—H11B	108.8	O26—C26—H26E	109.4
C12—C11—H11B	108.8	C25—C26—H26E	109.4
C9—C11—H11C	108.8	H26D—C26—H26E	108.0
C12—C11—H11C	108.8	C22—O26—C26	114.2 (3)
H11B—C11—H11C	107.7	C25—C27—H27C	109.5
C13—C12—C11	111.9 (3)	C25—C27—H27D	109.5
C13—C12—H12A	109.2	H27C—C27—H27D	109.5
C11—C12—H12A	109.2	C25—C27—H27E	109.5
C13—C12—H12B	109.2	H27C—C27—H27E	109.5
C11—C12—H12B	109.2	H27D—C27—H27E	109.5
H12A—C12—H12B	107.9	C29—O28—C3	118.9 (3)
C12—C13—C18	110.3 (3)	O30—C29—O28	123.6 (3)
C12—C13—C14	108.0 (3)	O30—C29—C31	125.0 (4)
C18—C13—C14	112.1 (3)	O28—C29—C31	111.3 (4)
C12—C13—C17	114.8 (3)	C29—C31—H31B	109.5
C18—C13—C17	111.7 (3)	C29—C31—H31C	109.5
C14—C13—C17	99.5 (2)	H31B—C31—H31C	109.5
C15—C14—C8	120.3 (3)	C29—C31—H31D	109.5
C15—C14—C13	103.8 (2)	H31B—C31—H31D	109.5
C8—C14—C13	114.1 (3)	H31C—C31—H31D	109.5
C15—C14—H14B	105.8	C23—C32—C33	122.0 (3)
C8—C14—H14B	105.8	N34—C32—C23	111.6 (3)
C13—C14—H14B	105.8	N34—C32—C33	126.3 (3)
C14—C15—C16	101.9 (3)	C32—C33—H33A	109.5
C14—C15—H15B	111.4	C32—C33—H33B	109.5
C16—C15—H15B	111.4	H33A—C33—H33B	109.5
C14—C15—H15C	111.4	C32—C33—H33C	109.5
C16—C15—H15C	111.4	H33A—C33—H33C	109.5
H15B—C15—H15C	109.2	H33B—C33—H33C	109.5
O22—C16—C15	112.6 (3)	C32—N34—O35	109.0 (4)
O22—C16—C17	105.5 (2)	C32—N34—H34	132.0 (16)
C15—C16—C17	107.7 (3)	O35—N34—H34	118.6 (16)
C10—C1—C2—C3	54.0 (4)	O22—C16—C17—C20	19.0 (3)
C1—C2—C3—O28	62.8 (4)	C15—C16—C17—C20	139.4 (3)
C1—C2—C3—C4	−53.0 (4)	O22—C16—C17—C13	−109.5 (3)
O28—C3—C4—C5	−63.8 (4)	C15—C16—C17—C13	10.9 (3)
C2—C3—C4—C5	54.2 (4)	C12—C13—C17—C20	93.1 (4)
C3—C4—C5—C6	179.0 (3)	C18—C13—C17—C20	−33.5 (4)
C3—C4—C5—C10	−53.9 (4)	C14—C13—C17—C20	−151.9 (3)
C4—C5—C6—C7	72.1 (4)	C12—C13—C17—C16	−150.0 (3)
C10—C5—C6—C7	−55.8 (5)	C18—C13—C17—C16	83.4 (3)
C5—C6—C7—C8	56.3 (5)	C14—C13—C17—C16	−35.0 (3)
C6—C7—C8—C14	−177.0 (3)	C16—C17—C20—C21	129.4 (3)
C6—C7—C8—C9	−55.3 (4)	C13—C17—C20—C21	−113.5 (3)
C7—C8—C9—C11	−177.2 (3)	C16—C17—C20—C22	3.6 (3)
C14—C8—C9—C11	−53.4 (4)	C13—C17—C20—C22	120.6 (3)
C7—C8—C9—C10	53.9 (4)	C21—C20—C22—O26	−33.8 (4)
C14—C8—C9—C10	177.7 (3)	C17—C20—C22—O26	91.3 (3)
C2—C1—C10—C19	−168.4 (3)	C21—C20—C22—O22	−150.3 (3)
C2—C1—C10—C5	−50.8 (4)	C17—C20—C22—O22	−25.2 (3)
C2—C1—C10—C9	70.5 (4)	C21—C20—C22—C23	89.5 (4)
C6—C5—C10—C19	−68.2 (4)	C17—C20—C22—C23	−145.4 (3)
C4—C5—C10—C19	165.2 (3)	O26—C22—O22—C16	−75.4 (3)
C6—C5—C10—C1	175.9 (3)	C20—C22—O22—C16	38.8 (3)
C4—C5—C10—C1	49.3 (4)	C23—C22—O22—C16	163.8 (3)
C6—C5—C10—C9	53.5 (4)	C15—C16—O22—C22	−153.5 (3)
C4—C5—C10—C9	−73.0 (4)	C17—C16—O22—C22	−36.3 (3)
C11—C9—C10—C19	−58.8 (4)	O26—C22—C23—C32	−176.2 (3)
C8—C9—C10—C19	68.5 (4)	O22—C22—C23—C32	−55.8 (3)
C11—C9—C10—C1	60.1 (4)	C20—C22—C23—C32	62.6 (3)
C8—C9—C10—C1	−172.5 (3)	O26—C22—C23—C24	−49.7 (3)
C11—C9—C10—C5	−179.9 (3)	O22—C22—C23—C24	70.7 (3)
C8—C9—C10—C5	−52.5 (4)	C20—C22—C23—C24	−171.0 (3)
C8—C9—C11—C12	52.7 (4)	C32—C23—C24—C25	177.9 (3)
C10—C9—C11—C12	−179.3 (3)	C22—C23—C24—C25	51.2 (4)
C9—C11—C12—C13	−53.8 (4)	C23—C24—C25—C26	−54.9 (4)
C11—C12—C13—C18	−68.7 (4)	C23—C24—C25—C27	69.6 (4)
C11—C12—C13—C14	54.1 (4)	C24—C25—C26—O26	59.4 (4)
C11—C12—C13—C17	164.1 (3)	C27—C25—C26—O26	−65.0 (4)
C7—C8—C14—C15	−53.3 (4)	O22—C22—O26—C26	−63.2 (3)
C9—C8—C14—C15	−176.8 (3)	C20—C22—O26—C26	−176.7 (3)
C7—C8—C14—C13	−177.7 (3)	C23—C22—O26—C26	56.4 (3)
C9—C8—C14—C13	58.9 (4)	C25—C26—O26—C22	−63.0 (4)
C12—C13—C14—C15	167.9 (3)	C4—C3—O28—C29	−154.6 (3)
C18—C13—C14—C15	−70.4 (3)	C2—C3—O28—C29	86.1 (4)
C17—C13—C14—C15	47.8 (3)	C3—O28—C29—O30	−0.2 (5)
C12—C13—C14—C8	−59.3 (4)	C3—O28—C29—C31	179.7 (3)
C18—C13—C14—C8	62.4 (4)	C24—C23—C32—N34	135.1 (3)
C17—C13—C14—C8	−179.4 (3)	C22—C23—C32—N34	−99.0 (3)
C8—C14—C15—C16	−170.4 (3)	C24—C23—C32—C33	−44.6 (4)
C13—C14—C15—C16	−41.2 (3)	C22—C23—C32—C33	81.3 (4)
C14—C15—C16—O22	134.1 (3)	C33—C32—N34—O35	0.2 (6)
C14—C15—C16—C17	18.3 (4)	C23—C32—N34—O35	−179.5 (3)

C32—C33	1.477 (5)
C32—N34	1.361 (6)
N34—H34	0.980 (18)
N34—O35	1.367 (5)

C23—C32—C33	122.0 (3)
N34—C32—C23	111.6 (3)
N34—C32—C33	126.3 (3)
C32—N34—O35	109.0 (4)
C32—N34—H34	132.0 (16)
O35—N34—H34	118.6 (16)