(20S,2''S)-20-[4'-(3''-Hydroxy-2''-methyl-prop-yl)-3'-methylisoxazol-5-yl]-5β-preg-nan-3β,16β-diol.

The title steroidal compound, C(29)H(47)NO(4), was prepared in a one-pot reaction starting from a sarsasapogenin derivative of known configuration. The isoxazole heterocycle is oriented towards the α face of the steroid nucleus and, although fully functionalized on C atoms, does not provoke steric hindrance with the adjacent D ring. The absolute configuration observed for chiral centers is as expected, and shows that no epimerization occurred in the precursors. In the crystal, the three OH groups serve as donors for hydrogen bonding with O and N atoms. The isoxazole N atom is involved in O-H⋯N hydrogen bonds, forming chains along [100]. These chains are further connected via O-H⋯O and weak C-H⋯O contacts, giving rise to a three-dimensional supra-molecular network.

Related literature

For a general introduction to steroids functionalized with heterocycles, see: Banday et al. (2008 ▶); Pathak & Jindal (1998 ▶); Litvinovskaya et al. (1998 ▶); Beam et al. (2000 ▶). For the biological activity of danazol, a steroid sharing structural features with the title compound, see: Gupta et al. (1999 ▶). For 23-acetylsarsasapogenin, used as starting material, see: Meza-Reyes et al. (2005 ▶).

Experimental

Crystal data

C29H47NO4

M = 473.68

Monoclinic,

a = 6.5540 (8) Å

b = 30.131 (4) Å

c = 7.1971 (10) Å

β = 98.500 (13)°

V = 1405.6 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 296 K

0.6 × 0.2 × 0.2 mm

Data collection

Bruker P4 diffractometer

8425 measured reflections

2534 independent reflections

2003 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.092

S = 1.07

2534 reflections

322 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.13 e Å−3

Δρmin = −0.12 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050478/jj2015sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050478/jj2015Isup2.hkl

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

C29H47NO4	F(000) = 520
Mr = 473.68	Dx = 1.119 Mg m−3
Monoclinic, P21	Melting point: 500 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.5540 (8) Å	Cell parameters from 64 reflections
b = 30.131 (4) Å	θ = 3.7–11.9°
c = 7.1971 (10) Å	µ = 0.07 mm−1
β = 98.500 (13)°	T = 296 K
V = 1405.6 (3) Å3	Needle, colorless
Z = 2	0.6 × 0.2 × 0.2 mm

Bruker P4 diffractometer	Rint = 0.030
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.7°
graphite	h = −7→7
ω scans	k = −35→35
8425 measured reflections	l = −8→8
2534 independent reflections	3 standard reflections every 97 reflections
2003 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.041P)2 + 0.1586P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2534 reflections	Δρmax = 0.13 e Å−3
322 parameters	Δρmin = −0.12 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.026 (2)
Primary atom site location: structure-invariant direct methods

Experimental. Colourless crystals, m.p. 227-228°C (acetone); [α]D -106.4° (c 1.0, EtOH); IR ν max (cm-1): 3386, 3355, 3321, 2933, 2821, 1629. 1H-NMR δ: 4.12 (1H, s, H-3), 3.97 (1H, m, H-16), 3.51 and 3.47 (2H, ABX system, J3'',2'' = 6 Hz, Jgem = 11 Hz, H-3''), 3.30 (1H, dc, J20,17 = 9 Hz and J20,21 = 7 Hz, H-20), 2.47 and 2.16 (2H, dd, J1 = J2 = 8 Hz, H-1''), 2.22 (3H, s, CH3-3'), 1.28 (3H, d, J21,20 = 7 Hz, CH3-21), 0.98 (3H, s, CH3-19), 0.95 (3H, d, J = 6 Hz, CH3-2''), 0.93 (3H, s, CH3-18). 13C-NMR, δ: 10.7 (CH3-3'), 13.2 (C-18), 17.0 (C-21), 19.4 (CH3-2''), 20.9 (C-11), 24.0 (C-19), 26.1 (C-1''), 26.2 (C-7), 26.6 (C-1), 27.8 (C-12), 29.0 (C-20), 29.9 (C-2), 33.5 (C-15), 35.2 (C-6), 35.2 (C-8), 36.1 (C-9), 36.4 (C-13), 36.5 (C-5), 39.8 (C-2''), 40.4 (C-4), 42.6 (C-10), 53.9 (C-14), 58.8 (C-17), 67.0 (C-3), 67.5 (C-3''), 72.5 (C-16), 109.9 (C-5'), 159.7 (C-3', C=N), 173.0 (C-4').

	x	y	z	Uiso*/Ueq
C1	0.6068 (5)	0.66437 (9)	0.3655 (4)	0.0550 (8)
H1B	0.7108	0.6874	0.3689	0.066*
H1C	0.5438	0.6608	0.2357	0.066*
C2	0.4435 (5)	0.67967 (10)	0.4788 (5)	0.0647 (9)
H2A	0.3322	0.6581	0.4669	0.078*
H2B	0.3868	0.7077	0.4293	0.078*
C3	0.5310 (6)	0.68522 (11)	0.6842 (5)	0.0726 (9)
H3A	0.4185	0.6922	0.7551	0.087*
C4	0.6348 (6)	0.64271 (11)	0.7600 (5)	0.0747 (10)
H4A	0.5305	0.6199	0.7616	0.090*
H4B	0.6991	0.6476	0.8887	0.090*
C5	0.7976 (5)	0.62606 (10)	0.6460 (4)	0.0622 (8)
H5A	0.9072	0.6484	0.6565	0.075*
C6	0.8957 (7)	0.58263 (12)	0.7296 (5)	0.0806 (11)
H6B	1.0192	0.5765	0.6745	0.097*
H6C	0.9364	0.5864	0.8638	0.097*
C7	0.7507 (7)	0.54323 (11)	0.6954 (5)	0.0737 (10)
H7A	0.6348	0.5477	0.7629	0.088*
H7B	0.8227	0.5166	0.7443	0.088*
C8	0.6706 (5)	0.53673 (9)	0.4874 (4)	0.0524 (7)
H8A	0.7884	0.5303	0.4221	0.063*
C9	0.5657 (5)	0.57996 (9)	0.4041 (4)	0.0467 (6)
H9D	0.4531	0.5861	0.4760	0.056*
C10	0.7136 (4)	0.62065 (9)	0.4332 (4)	0.0504 (7)
C11	0.4650 (5)	0.57340 (9)	0.1993 (4)	0.0531 (7)
H11B	0.3837	0.5995	0.1593	0.064*
H11C	0.5729	0.5711	0.1210	0.064*
C12	0.3259 (5)	0.53243 (9)	0.1663 (4)	0.0534 (7)
H12A	0.2800	0.5290	0.0327	0.064*
H12B	0.2049	0.5368	0.2272	0.064*
C13	0.4376 (4)	0.48992 (8)	0.2428 (4)	0.0448 (6)
C14	0.5181 (5)	0.49856 (9)	0.4517 (4)	0.0519 (7)
H14C	0.3978	0.5071	0.5098	0.062*
C15	0.5816 (6)	0.45203 (10)	0.5279 (4)	0.0640 (9)
H15C	0.7132	0.4433	0.4931	0.077*
H15D	0.5907	0.4510	0.6635	0.077*
C16	0.4078 (5)	0.42238 (9)	0.4337 (4)	0.0531 (7)
H16B	0.3074	0.4196	0.5213	0.064*
C17	0.2987 (4)	0.44850 (9)	0.2579 (4)	0.0476 (7)
H17C	0.1690	0.4597	0.2923	0.057*
C18	0.6125 (5)	0.47874 (10)	0.1303 (4)	0.0528 (7)
H18A	0.7116	0.5024	0.1432	0.079*
H18B	0.5567	0.4751	0.0001	0.079*
H18C	0.6784	0.4517	0.1772	0.079*
C19	0.8950 (5)	0.61529 (13)	0.3227 (6)	0.0778 (10)
H19B	0.8434	0.6123	0.1913	0.117*
H19C	0.9725	0.5893	0.3655	0.117*
H19D	0.9827	0.6409	0.3420	0.117*
C20	0.2387 (5)	0.41917 (9)	0.0833 (4)	0.0504 (7)
H20B	0.3654	0.4067	0.0478	0.061*
C21	0.1250 (5)	0.44472 (10)	−0.0881 (5)	0.0631 (8)
H21C	0.0756	0.4241	−0.1861	0.095*
H21D	0.2184	0.4653	−0.1331	0.095*
H21E	0.0105	0.4606	−0.0515	0.095*
C22	0.1037 (4)	0.38157 (9)	0.1246 (4)	0.0499 (7)
O23	−0.0587 (3)	0.39290 (7)	0.2120 (4)	0.0703 (7)
N24	−0.1752 (4)	0.35417 (10)	0.2322 (4)	0.0703 (8)
C25	−0.0791 (5)	0.32195 (10)	0.1605 (4)	0.0538 (7)
C26	0.1011 (4)	0.33757 (9)	0.0881 (4)	0.0445 (6)
C27	−0.1567 (5)	0.27556 (11)	0.1658 (5)	0.0661 (9)
H27D	−0.2718	0.2748	0.2340	0.099*
H27E	−0.0487	0.2568	0.2268	0.099*
H27F	−0.1994	0.2652	0.0399	0.099*
C28	0.2554 (4)	0.31208 (9)	−0.0033 (4)	0.0474 (6)
H28C	0.2499	0.2812	0.0334	0.057*
H28D	0.3922	0.3231	0.0446	0.057*
C29	0.2250 (5)	0.31457 (10)	−0.2173 (4)	0.0554 (7)
H29C	0.2155	0.3459	−0.2545	0.067*
C30	0.0285 (6)	0.2913 (2)	−0.3036 (6)	0.123 (2)
H30B	0.0167	0.2925	−0.4381	0.185*
H30C	−0.0882	0.3059	−0.2641	0.185*
H30D	0.0325	0.2609	−0.2633	0.185*
C31	0.4103 (5)	0.29436 (10)	−0.2882 (4)	0.0624 (8)
H31C	0.5325	0.3107	−0.2351	0.075*
H31D	0.4266	0.2641	−0.2429	0.075*
O32	0.3985 (5)	0.29406 (8)	−0.4864 (3)	0.0788 (8)
H32	0.411 (8)	0.3187 (17)	−0.533 (7)	0.118*
O33	0.4750 (3)	0.37840 (6)	0.3970 (3)	0.0570 (6)
H33	0.584 (6)	0.3790 (14)	0.345 (5)	0.086*
O34	0.6814 (5)	0.71965 (8)	0.7127 (4)	0.0898 (9)
H34	0.633 (9)	0.743 (2)	0.640 (8)	0.135*

	U11	U22	U33	U12	U13	U23
C1	0.0655 (19)	0.0375 (15)	0.0597 (18)	−0.0086 (14)	0.0013 (15)	0.0075 (13)
C2	0.0618 (19)	0.0362 (16)	0.093 (3)	0.0006 (14)	0.0010 (18)	0.0017 (16)
C3	0.095 (3)	0.0424 (17)	0.083 (2)	0.0033 (18)	0.023 (2)	−0.0076 (16)
C4	0.121 (3)	0.0451 (18)	0.058 (2)	0.007 (2)	0.011 (2)	−0.0015 (15)
C5	0.079 (2)	0.0448 (17)	0.0573 (19)	0.0017 (15)	−0.0073 (16)	0.0000 (14)
C6	0.103 (3)	0.059 (2)	0.069 (2)	0.020 (2)	−0.025 (2)	−0.0043 (16)
C7	0.113 (3)	0.0437 (17)	0.0565 (19)	0.0123 (18)	−0.0130 (19)	0.0027 (15)
C8	0.0696 (18)	0.0367 (14)	0.0490 (15)	0.0109 (14)	0.0029 (14)	0.0027 (12)
C9	0.0567 (16)	0.0361 (14)	0.0479 (15)	0.0046 (12)	0.0099 (13)	0.0014 (11)
C10	0.0530 (16)	0.0428 (16)	0.0547 (17)	0.0034 (13)	0.0049 (13)	0.0003 (13)
C11	0.0653 (18)	0.0342 (14)	0.0564 (17)	0.0034 (13)	−0.0019 (14)	0.0071 (12)
C12	0.0599 (17)	0.0362 (14)	0.0618 (18)	0.0071 (14)	0.0009 (14)	0.0048 (13)
C13	0.0552 (16)	0.0327 (14)	0.0479 (15)	0.0084 (12)	0.0124 (13)	0.0024 (11)
C14	0.0733 (19)	0.0364 (14)	0.0471 (16)	0.0132 (13)	0.0124 (14)	0.0045 (12)
C15	0.103 (3)	0.0400 (16)	0.0488 (16)	0.0108 (17)	0.0088 (17)	0.0070 (13)
C16	0.075 (2)	0.0361 (15)	0.0540 (16)	0.0108 (14)	0.0284 (15)	0.0070 (13)
C17	0.0568 (16)	0.0341 (14)	0.0555 (16)	0.0111 (12)	0.0205 (13)	0.0027 (12)
C18	0.0611 (17)	0.0425 (15)	0.0582 (17)	0.0037 (14)	0.0198 (14)	0.0022 (13)
C19	0.064 (2)	0.083 (3)	0.090 (3)	−0.009 (2)	0.0209 (19)	−0.003 (2)
C20	0.0600 (17)	0.0341 (14)	0.0601 (17)	0.0051 (13)	0.0185 (14)	0.0018 (13)
C21	0.079 (2)	0.0459 (17)	0.0633 (19)	0.0029 (16)	0.0076 (16)	0.0018 (14)
C22	0.0503 (16)	0.0408 (15)	0.0615 (17)	0.0074 (13)	0.0175 (13)	0.0019 (13)
O23	0.0679 (14)	0.0463 (12)	0.1057 (18)	0.0066 (11)	0.0431 (13)	−0.0007 (11)
N24	0.0619 (16)	0.0570 (16)	0.099 (2)	0.0012 (14)	0.0343 (15)	0.0019 (15)
C25	0.0506 (16)	0.0491 (17)	0.0618 (18)	−0.0001 (13)	0.0082 (13)	0.0058 (14)
C26	0.0462 (15)	0.0391 (14)	0.0484 (15)	0.0026 (12)	0.0076 (12)	0.0026 (12)
C27	0.0631 (19)	0.0566 (19)	0.077 (2)	−0.0153 (16)	0.0056 (16)	0.0095 (16)
C28	0.0504 (15)	0.0388 (14)	0.0523 (16)	0.0052 (12)	0.0055 (12)	−0.0025 (12)
C29	0.0638 (18)	0.0488 (16)	0.0545 (17)	0.0065 (14)	0.0117 (14)	0.0048 (13)
C30	0.077 (2)	0.224 (7)	0.065 (2)	−0.029 (3)	0.000 (2)	−0.032 (3)
C31	0.087 (2)	0.0444 (17)	0.0610 (19)	0.0047 (16)	0.0275 (16)	0.0000 (15)
O32	0.139 (2)	0.0432 (12)	0.0641 (14)	−0.0046 (14)	0.0467 (14)	0.0002 (11)
O33	0.0660 (13)	0.0314 (10)	0.0785 (14)	0.0066 (9)	0.0266 (11)	0.0099 (10)
O34	0.128 (2)	0.0423 (13)	0.0880 (19)	−0.0053 (14)	−0.0196 (17)	−0.0085 (12)

C1—C2	1.511 (5)	C16—O33	1.433 (3)
C1—C10	1.537 (4)	C16—C17	1.569 (4)
C1—H1B	0.9700	C16—H16B	0.9800
C1—H1C	0.9700	C17—C20	1.539 (4)
C2—C3	1.514 (5)	C17—H17C	0.9800
C2—H2A	0.9700	C18—H18A	0.9600
C2—H2B	0.9700	C18—H18B	0.9600
C3—O34	1.425 (4)	C18—H18C	0.9600
C3—C4	1.514 (5)	C19—H19B	0.9600
C3—H3A	0.9800	C19—H19C	0.9600
C4—C5	1.524 (5)	C19—H19D	0.9600
C4—H4A	0.9700	C20—C22	1.494 (4)
C4—H4B	0.9700	C20—C21	1.549 (4)
C5—C6	1.540 (5)	C20—H20B	0.9800
C5—C10	1.558 (4)	C21—H21C	0.9600
C5—H5A	0.9800	C21—H21D	0.9600
C6—C7	1.518 (5)	C21—H21E	0.9600
C6—H6B	0.9700	C22—C26	1.351 (4)
C6—H6C	0.9700	C22—O23	1.358 (3)
C7—C8	1.524 (4)	O23—N24	1.414 (3)
C7—H7A	0.9700	N24—C25	1.304 (4)
C7—H7B	0.9700	C25—C26	1.438 (4)
C8—C14	1.521 (4)	C25—C27	1.490 (4)
C8—C9	1.551 (4)	C26—C28	1.497 (4)
C8—H8A	0.9800	C27—H27D	0.9600
C9—C11	1.536 (4)	C27—H27E	0.9600
C9—C10	1.558 (4)	C27—H27F	0.9600
C9—H9D	0.9800	C28—C29	1.525 (4)
C10—C19	1.534 (4)	C28—H28C	0.9700
C11—C12	1.532 (4)	C28—H28D	0.9700
C11—H11B	0.9700	C29—C31	1.513 (4)
C11—H11C	0.9700	C29—C30	1.517 (5)
C12—C13	1.536 (4)	C29—H29C	0.9800
C12—H12A	0.9700	C30—H30B	0.9600
C12—H12B	0.9700	C30—H30C	0.9600
C13—C18	1.535 (4)	C30—H30D	0.9600
C13—C14	1.540 (4)	C31—O32	1.417 (4)
C13—C17	1.558 (4)	C31—H31C	0.9700
C14—C15	1.540 (4)	C31—H31D	0.9700
C14—H14C	0.9800	O32—H32	0.82 (5)
C15—C16	1.525 (5)	O33—H33	0.85 (4)
C15—H15C	0.9700	O34—H34	0.90 (6)
C15—H15D	0.9700
C2—C1—C10	114.6 (3)	C16—C15—H15C	111.1
C2—C1—H1B	108.6	C14—C15—H15C	111.1
C10—C1—H1B	108.6	C16—C15—H15D	111.1
C2—C1—H1C	108.6	C14—C15—H15D	111.1
C10—C1—H1C	108.6	H15C—C15—H15D	109.1
H1B—C1—H1C	107.6	O33—C16—C15	113.2 (3)
C1—C2—C3	111.4 (3)	O33—C16—C17	115.5 (2)
C1—C2—H2A	109.4	C15—C16—C17	106.6 (2)
C3—C2—H2A	109.4	O33—C16—H16B	107.0
C1—C2—H2B	109.4	C15—C16—H16B	107.0
C3—C2—H2B	109.4	C17—C16—H16B	107.0
H2A—C2—H2B	108.0	C20—C17—C13	119.0 (2)
O34—C3—C2	112.0 (3)	C20—C17—C16	113.6 (2)
O34—C3—C4	107.5 (3)	C13—C17—C16	104.9 (2)
C2—C3—C4	110.1 (3)	C20—C17—H17C	106.2
O34—C3—H3A	109.1	C13—C17—H17C	106.2
C2—C3—H3A	109.1	C16—C17—H17C	106.2
C4—C3—H3A	109.1	C13—C18—H18A	109.5
C3—C4—C5	113.4 (3)	C13—C18—H18B	109.5
C3—C4—H4A	108.9	H18A—C18—H18B	109.5
C5—C4—H4A	108.9	C13—C18—H18C	109.5
C3—C4—H4B	108.9	H18A—C18—H18C	109.5
C5—C4—H4B	108.9	H18B—C18—H18C	109.5
H4A—C4—H4B	107.7	C10—C19—H19B	109.5
C4—C5—C6	110.8 (3)	C10—C19—H19C	109.5
C4—C5—C10	112.9 (3)	H19B—C19—H19C	109.5
C6—C5—C10	111.2 (3)	C10—C19—H19D	109.5
C4—C5—H5A	107.2	H19B—C19—H19D	109.5
C6—C5—H5A	107.2	H19C—C19—H19D	109.5
C10—C5—H5A	107.2	C22—C20—C17	111.1 (2)
C7—C6—C5	112.7 (3)	C22—C20—C21	107.8 (2)
C7—C6—H6B	109.1	C17—C20—C21	113.6 (2)
C5—C6—H6B	109.1	C22—C20—H20B	108.1
C7—C6—H6C	109.1	C17—C20—H20B	108.1
C5—C6—H6C	109.1	C21—C20—H20B	108.1
H6B—C6—H6C	107.8	C20—C21—H21C	109.5
C6—C7—C8	112.1 (3)	C20—C21—H21D	109.5
C6—C7—H7A	109.2	H21C—C21—H21D	109.5
C8—C7—H7A	109.2	C20—C21—H21E	109.5
C6—C7—H7B	109.2	H21C—C21—H21E	109.5
C8—C7—H7B	109.2	H21D—C21—H21E	109.5
H7A—C7—H7B	107.9	C26—C22—O23	110.4 (3)
C14—C8—C7	112.7 (3)	C26—C22—C20	134.1 (3)
C14—C8—C9	109.1 (2)	O23—C22—C20	115.4 (2)
C7—C8—C9	109.9 (2)	C22—O23—N24	108.2 (2)
C14—C8—H8A	108.4	C25—N24—O23	105.9 (2)
C7—C8—H8A	108.4	N24—C25—C26	111.7 (3)
C9—C8—H8A	108.4	N24—C25—C27	120.1 (3)
C11—C9—C8	111.5 (2)	C26—C25—C27	128.1 (3)
C11—C9—C10	113.6 (2)	C22—C26—C25	103.8 (2)
C8—C9—C10	112.2 (2)	C22—C26—C28	126.8 (3)
C11—C9—H9D	106.3	C25—C26—C28	129.5 (3)
C8—C9—H9D	106.3	C25—C27—H27D	109.5
C10—C9—H9D	106.3	C25—C27—H27E	109.5
C19—C10—C1	106.1 (3)	H27D—C27—H27E	109.5
C19—C10—C5	109.4 (3)	C25—C27—H27F	109.5
C1—C10—C5	107.5 (2)	H27D—C27—H27F	109.5
C19—C10—C9	111.2 (2)	H27E—C27—H27F	109.5
C1—C10—C9	112.7 (2)	C26—C28—C29	115.0 (2)
C5—C10—C9	109.7 (2)	C26—C28—H28C	108.5
C12—C11—C9	114.4 (2)	C29—C28—H28C	108.5
C12—C11—H11B	108.7	C26—C28—H28D	108.5
C9—C11—H11B	108.7	C29—C28—H28D	108.5
C12—C11—H11C	108.7	H28C—C28—H28D	107.5
C9—C11—H11C	108.7	C31—C29—C30	110.6 (3)
H11B—C11—H11C	107.6	C31—C29—C28	109.2 (2)
C11—C12—C13	112.0 (2)	C30—C29—C28	111.5 (3)
C11—C12—H12A	109.2	C31—C29—H29C	108.5
C13—C12—H12A	109.2	C30—C29—H29C	108.5
C11—C12—H12B	109.2	C28—C29—H29C	108.5
C13—C12—H12B	109.2	C29—C30—H30B	109.5
H12A—C12—H12B	107.9	C29—C30—H30C	109.5
C18—C13—C12	110.3 (2)	H30B—C30—H30C	109.5
C18—C13—C14	112.2 (2)	C29—C30—H30D	109.5
C12—C13—C14	106.6 (2)	H30B—C30—H30D	109.5
C18—C13—C17	110.5 (2)	H30C—C30—H30D	109.5
C12—C13—C17	116.1 (2)	O32—C31—C29	114.5 (3)
C14—C13—C17	100.8 (2)	O32—C31—H31C	108.6
C8—C14—C13	114.5 (2)	C29—C31—H31C	108.6
C8—C14—C15	119.5 (3)	O32—C31—H31D	108.6
C13—C14—C15	103.3 (2)	C29—C31—H31D	108.6
C8—C14—H14C	106.2	H31C—C31—H31D	107.6
C13—C14—H14C	106.2	C31—O32—H32	114 (3)
C15—C14—H14C	106.2	C16—O33—H33	111 (3)
C16—C15—C14	103.3 (3)	C3—O34—H34	108 (4)
C10—C1—C2—C3	57.4 (3)	C18—C13—C14—C15	−71.8 (3)
C1—C2—C3—O34	64.8 (3)	C12—C13—C14—C15	167.4 (3)
C1—C2—C3—C4	−54.7 (4)	C17—C13—C14—C15	45.8 (3)
O34—C3—C4—C5	−68.1 (4)	C8—C14—C15—C16	−169.8 (2)
C2—C3—C4—C5	54.2 (4)	C13—C14—C15—C16	−41.3 (3)
C3—C4—C5—C6	−179.6 (3)	C14—C15—C16—O33	148.1 (2)
C3—C4—C5—C10	−54.1 (4)	C14—C15—C16—C17	20.0 (3)
C4—C5—C6—C7	72.2 (4)	C18—C13—C17—C20	−42.3 (3)
C10—C5—C6—C7	−54.2 (4)	C12—C13—C17—C20	84.3 (3)
C5—C6—C7—C8	55.6 (4)	C14—C13—C17—C20	−161.1 (2)
C6—C7—C8—C14	−177.6 (3)	C18—C13—C17—C16	86.1 (3)
C6—C7—C8—C9	−55.7 (4)	C12—C13—C17—C16	−147.3 (2)
C14—C8—C9—C11	−50.7 (3)	C14—C13—C17—C16	−32.7 (2)
C7—C8—C9—C11	−174.7 (3)	O33—C16—C17—C20	12.9 (3)
C14—C8—C9—C10	−179.4 (2)	C15—C16—C17—C20	139.6 (3)
C7—C8—C9—C10	56.6 (3)	O33—C16—C17—C13	−118.7 (2)
C2—C1—C10—C19	−170.8 (3)	C15—C16—C17—C13	8.0 (3)
C2—C1—C10—C5	−53.8 (3)	C13—C17—C20—C22	−179.3 (2)
C2—C1—C10—C9	67.2 (3)	C16—C17—C20—C22	56.4 (3)
C4—C5—C10—C19	166.0 (3)	C13—C17—C20—C21	−57.6 (3)
C6—C5—C10—C19	−68.8 (4)	C16—C17—C20—C21	178.2 (3)
C4—C5—C10—C1	51.2 (3)	C17—C20—C22—C26	−134.1 (3)
C6—C5—C10—C1	176.4 (3)	C21—C20—C22—C26	100.9 (4)
C4—C5—C10—C9	−71.8 (3)	C17—C20—C22—O23	48.8 (3)
C6—C5—C10—C9	53.5 (4)	C21—C20—C22—O23	−76.2 (3)
C11—C9—C10—C19	−62.0 (3)	C26—C22—O23—N24	−0.6 (3)
C8—C9—C10—C19	65.5 (3)	C20—C22—O23—N24	177.2 (2)
C11—C9—C10—C1	57.0 (3)	C22—O23—N24—C25	0.9 (3)
C8—C9—C10—C1	−175.5 (2)	O23—N24—C25—C26	−0.8 (3)
C11—C9—C10—C5	176.8 (2)	O23—N24—C25—C27	177.5 (3)
C8—C9—C10—C5	−55.7 (3)	O23—C22—C26—C25	0.1 (3)
C8—C9—C11—C12	49.7 (3)	C20—C22—C26—C25	−177.1 (3)
C10—C9—C11—C12	177.6 (2)	O23—C22—C26—C28	−178.8 (2)
C9—C11—C12—C13	−53.1 (3)	C20—C22—C26—C28	4.0 (5)
C11—C12—C13—C18	−66.6 (3)	N24—C25—C26—C22	0.5 (4)
C11—C12—C13—C14	55.4 (3)	C27—C25—C26—C22	−177.7 (3)
C11—C12—C13—C17	166.7 (2)	N24—C25—C26—C28	179.3 (3)
C7—C8—C14—C13	−178.4 (3)	C27—C25—C26—C28	1.2 (5)
C9—C8—C14—C13	59.3 (3)	C22—C26—C28—C29	−81.4 (4)
C7—C8—C14—C15	−55.2 (4)	C25—C26—C28—C29	100.0 (3)
C9—C8—C14—C15	−177.6 (3)	C26—C28—C29—C31	170.2 (2)
C18—C13—C14—C8	59.7 (3)	C26—C28—C29—C30	−67.2 (4)
C12—C13—C14—C8	−61.1 (3)	C30—C29—C31—O32	55.9 (4)
C17—C13—C14—C8	177.3 (2)	C28—C29—C31—O32	179.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O32—H32···O33i	0.82 (5)	1.93 (5)	2.746 (3)	170 (5)
O33—H33···N24ii	0.85 (4)	2.03 (4)	2.828 (3)	157 (4)
O34—H34···O32iii	0.90 (6)	1.89 (6)	2.775 (4)	166 (5)
O33—H33···O23ii	0.85 (4)	2.69 (4)	3.536 (3)	171 (4)
C18—H18C···O23ii	0.96	2.46	3.362 (4)	157
C28—H28C···O34iv	0.97	2.60	3.471 (4)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O32—H32⋯O33i	0.82 (5)	1.93 (5)	2.746 (3)	170 (5)
O33—H33⋯N24ii	0.85 (4)	2.03 (4)	2.828 (3)	157 (4)
O34—H34⋯O32iii	0.90 (6)	1.89 (6)	2.775 (4)	166 (5)
O33—H33⋯O23ii	0.85 (4)	2.69 (4)	3.536 (3)	171 (4)
C18—H18C⋯O23ii	0.96	2.46	3.362 (4)	157
C28—H28C⋯O34iv	0.97	2.60	3.471 (4)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .