16-(4-Cyano­benzyl­idene)-17-oxo­androst-5-en-3β-ol

In the title compound, 4-(3β-hydroxy-17-oxoandrost-5-en-16-ylidenemethyl)benzonitrile, C₂₇H₃₁NO₂, rings A and C of the steroid nucleus are in chair conformations. The central six-membered ring B is in an 8β,9α-half-chair conformation, while the five-membered ring D adopts a 13β,14α-half-chair conformation. The cyano­benzyl­idene moiety has an E configuration with respect to the carbonyl group at position C17. The dihedral angle between the planes of the steroid nucleus and the cyano­benzyl­idene moiety is 22.61 (15)°. Intermolecular O—H...N hydrogen bonds formed between the hydroxyl group of the steroid and the N atom of the cyano­benzyl­idene moiety of symmetry-related mol­ecules link the steroid mol­ecules into chains which run parallel to the b axis.

S1. Comment

The present study of the title compound, (I), is the 11t h in our series of X-ray crystal-structure analyses of androstene and its derivatives (Thamotharan et al., 2002, and references therein). The conformation of steroids having flexible unsaturated ring and/or substituents is of particular interest. We are particularly interested in studying the conformational flexibilities of the steroids resulting from various substitutions at the C3, C16 and C17 positions. The crystals of (I) are enantiomerically pure. However, due to the absence of significant anomalous scatterers in the compound, the absolute configuration of the molecule has not been determined by the X-ray diffraction experiment. The enantiomer used in the refinement was assigned to correspond to that of the known chiral centre in a precursor molecule, namely dehydroepiandrosterone (Weeks et al., 1971), which remained unchanged during the synthesis of (I).

Among the few conformational options, both methyl groups of the steroidal nucleus adopt the expected staggered arrangements. The geometry of the rings is trans at the B/C and C/D ring junctions (see Scheme and Fig. 1).

The C5—C6 distance of 1.318 (6) Å is comparable with that of the related structure (Bhacca et al., 1996) and confirms the localization of the double bond at this position. Rings A and C are slightly flattened, the mean values of their torsion angles being 52.5 (2) and 55.2 (2)°, respectively. Both ring conformations are close to that of a chair as shown by the values of Cremer & Pople (1975) puckering parameters [ring A: Q = 0.538 (5) Å, θ = 9.3 (5)°, ϕ = 81 (3)° for the atom sequence C1—C2—C3—C4—C5—C10; ring C: Q = 0.565 (5) Å, θ = 5.8 (5)°,ϕ = 266 (6)° for the atom sequence C8—C9—C11—C12—C13—C14]. Thus, the presence of the hydroxyl group bonded to C3 has not disturbed the usual chair conformation of ring A of the steroidal nucleus. The C3—O31 bond is oriented equatorially and (+)antiperiplanar to the C3—C4 bond. The dihedral angle between the planes of the cyanobenzylidene group and the steroidal nucleus is 22.61 (15)°.

Due to the C5═C6 double bond, the environment of atom C5 is planar, and hence ring B adopts the 8β,9α-half-chair conformation generally found in steroids with a C5═C6 double bond (Thamotharan et al., 2002, and references therein), with puckering parameters Q = 0.464 (2) Å, θ = 49.8 (6)° and ϕ =217.9 (7)° for the atom sequence C5—C6—C7—C8—C9—C10. The five-membered ring D exhibits a 13β,14α-half-chair conformation when compared to the unsubstituted dehydroxy steroid nucleus in which ring D is in a 14α-envelope conformation. It seems that a bulky sustitution of cyanobenzylidene moiety caused conformational change observed in ring D in (I) ϕ_m = 42.9 (3)° for the atoms sequence C13—C14—C15—C16—C17 (Altona et al., 1968).

The C17—C16—C20—C21 torsion angle of 171.1 (4)° indicates that the cyanobenzylidene moiety has an E configuration with respect to the carbonyl group at position C17 as has been observed in our previous compound (Thamotharan et al., 2002)·The C15—C16—C20 exocyclic angle of 133.0 (4)° is significantly larger than the normal value of 120° and this may be due to the steric repulsion between atoms H15B and H22 (2.41 Å). In (I), the skeletal bond angles are close to the expected values (Duax et al., 1976).

In the crystal, the steroid nucleus forms head to tail chains of O—H···N intermolecular hydrogen bonds involving the O—H group and the N atom of cyanobenzylidene moiety of a symmetry-related molecule. This interaction links the steroid molecules into chains which run parellel to the [110] direction. These hydrogen bonds form a C(18) graph-set motif (Bernstein et al., 1995).

S2. Experimental

A mixture of a dehydroepiandrosterone (0.5 g), sodium hydroxide (0.75 g) and 4-cyanobenzaldehyde (0.75 g) in methanol (10 ml) was stirred for 1.5 h at room temperature. The reaction mixture was added to ice cold water. The precipitate was filtered, washed thorougly with water and crystallized from methanol to afford crystals of (I); yield: 0.23 g (43%) and m.p. 565–571 K. Analysis: UV_max(MeOH): 296.2 nm (logε = 4.35); IR_max: 2980, 2210. 1720, 1640 and 900 cm^{−1. 1}H NMR: 0.99 (s, 3H, 18-CH₃), 1.08 (s, 3H, 19-CH₃), 3.50 (m, 1H, 3-H), 5.40 (d, 1H, 6-CH), 3.9 (s) and 7.4 (s) [0.29:1 area ratio, 1H, vinyl-H of 16-(4-cyanobenzylidene)], 7.60 (d, 2H, J_o = 8.4, 2-CH and 6-CH aromatic proton), 7.70 (d, 2H, J_o = 8.2, 3-CH and 5-CH aromatic proton); calculated for C₂₇H₃₁NO₂: C 80.8, H 7.8, N,3.5%; found: C 80.8, H 7.8, N 3.6%.

S3. Refinement

The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å), with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.95–1.00 Å) and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C), except for the hydroxyl H atom, which was located in a difference Fourier map and refined using the DFIX option in SHELXL97 (Sheldrick, 1997), with H31—O31 = 0.81 (2) Å. It was included in the structure-factor calculations with U_iso(H31) = 1.2U_eq(O31). The Friedel pairs were merged before the final refinement and the absolute configuration was assigned to correspond with that of the known chiral centres in a precursor molecule which remained unchanged during the synthesis of the title compound.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Version 1.64.02; Farrugia, 1999); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Figures

	Fig. 1. View of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a chain by O—H···N interactions. Atoms marked with a hash (#) and asterisk (*) are at the symmetry positions (1 + x, −1 + y, z) and (−1 + x, 1 + y, z), respectively.

16-(4-Cyanobenzylidene)-17-oxoandrost-5-en-3β-ol

Crystal data

C27H31NO2	F(000) = 432
Mr = 401.53	Dx = 1.220 Mg m^−3
Monoclinic, P21	Melting point = 565–571 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.005 (3) Å	Cell parameters from 25 reflections
b = 17.448 (4) Å	θ = 20–30°
c = 10.453 (5) Å	µ = 0.08 mm^−1
β = 93.846 (4)°	T = 293 K
V = 1092.8 (8) Å^3	Block, pale yellow
Z = 2	0.25 × 0.20 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1520 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
non–profiled ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→20
Tmin = 0.981, Tmax = 0.989	l = −12→12
2184 measured reflections	2 standard reflections every 60 min
1986 independent reflections	intensity decay: 4%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: geom & difmap
wR(F^2) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.082P)^2] where P = (Fo^2 + 2Fc^2)/3
1986 reflections	(Δ/σ)max < 0.001
276 parameters	Δρmax = 0.20 e Å^−3
2 restraints	Δρmin = −0.21 e Å^−3

Special details

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
C1	0.6176 (7)	0.9445 (3)	0.7316 (4)	0.0427 (11)
H1A	0.5235	0.9472	0.6526	0.051*
H1B	0.5279	0.9241	0.7975	0.051*
C2	0.6909 (8)	1.0249 (3)	0.7695 (5)	0.0469 (12)
H2A	0.7709	1.0476	0.7013	0.056*
H2B	0.5608	1.0563	0.7818	0.056*
C3	0.8401 (9)	1.0232 (3)	0.8918 (4)	0.0472 (12)
H3	0.7568	1.0011	0.9604	0.057*
C4	1.0418 (8)	0.9741 (3)	0.8734 (5)	0.0473 (12)
H4A	1.1311	0.9707	0.9540	0.057*
H4B	1.1320	0.9984	0.8114	0.057*
C5	0.9813 (7)	0.8942 (2)	0.8277 (4)	0.0345 (10)
C6	1.0714 (7)	0.8333 (3)	0.8848 (4)	0.0398 (10)
H6	1.1724	0.8420	0.9547	0.048*
C7	1.0280 (8)	0.7515 (3)	0.8486 (4)	0.0400 (11)
H7A	0.9454	0.7272	0.9142	0.048*
H7B	1.1694	0.7249	0.8455	0.048*
C8	0.8955 (7)	0.7432 (2)	0.7183 (4)	0.0330 (10)
H8	0.9982	0.7485	0.6498	0.040*
C9	0.7158 (7)	0.8060 (2)	0.7022 (4)	0.0351 (10)
H9	0.6218	0.8002	0.7747	0.042*
C10	0.8128 (7)	0.8882 (2)	0.7122 (4)	0.0360 (10)
C11	0.5602 (9)	0.7932 (3)	0.5797 (5)	0.0507 (13)
H11A	0.4386	0.8298	0.5790	0.061*
H11B	0.6436	0.8032	0.5052	0.061*
C12	0.4629 (8)	0.7125 (3)	0.5688 (5)	0.0501 (13)
H12A	0.3615	0.7046	0.6361	0.060*
H12B	0.3786	0.7069	0.4869	0.060*
C13	0.6458 (7)	0.6528 (3)	0.5802 (4)	0.0367 (10)
C14	0.7854 (7)	0.6651 (3)	0.7075 (4)	0.0353 (9)
H14	0.6784	0.6640	0.7743	0.042*
C15	0.9239 (8)	0.5911 (3)	0.7263 (4)	0.0392 (10)
H15A	1.0581	0.5933	0.6797	0.047*
H15B	0.9649	0.5819	0.8163	0.047*
C16	0.7642 (7)	0.5302 (3)	0.6715 (4)	0.0368 (10)
C17	0.5756 (8)	0.5710 (3)	0.5976 (4)	0.0397 (11)
C18	0.7890 (9)	0.6528 (3)	0.4628 (4)	0.0525 (13)
H18A	0.6977	0.6388	0.3875	0.079*
H18B	0.9084	0.6164	0.4763	0.079*
H18C	0.8500	0.7030	0.4517	0.079*
C19	0.9302 (8)	0.9100 (3)	0.5920 (4)	0.0465 (12)
H19A	1.0271	0.8691	0.5698	0.070*
H19B	1.0164	0.9558	0.6083	0.070*
H19C	0.8207	0.9190	0.5224	0.070*
C20	0.7660 (8)	0.4545 (3)	0.6765 (4)	0.0434 (11)
H20	0.6416	0.4312	0.6354	0.052*
C21	0.9304 (7)	0.4011 (3)	0.7358 (4)	0.0394 (11)
C22	1.1426 (8)	0.4235 (3)	0.7832 (5)	0.0493 (12)
H22	1.1849	0.4747	0.7778	0.059*
C23	1.2905 (8)	0.3708 (3)	0.8380 (5)	0.0496 (12)
H23	1.4298	0.3869	0.8719	0.060*
C24	1.2336 (8)	0.2939 (3)	0.8431 (4)	0.0449 (11)
C25	1.0228 (9)	0.2704 (3)	0.7919 (4)	0.0499 (13)
H25	0.9824	0.2190	0.7939	0.060*
C26	0.8769 (9)	0.3237 (3)	0.7392 (4)	0.0456 (12)
H26	0.7380	0.3077	0.7045	0.055*
C27	1.3894 (9)	0.2387 (3)	0.8989 (5)	0.0571 (13)
O17	0.3977 (6)	0.5425 (2)	0.5616 (3)	0.0577 (9)
O31	0.9180 (6)	1.0977 (2)	0.9305 (4)	0.0648 (11)
H31	0.802 (6)	1.121 (3)	0.929 (5)	0.077*
N28	1.5144 (9)	0.1959 (3)	0.9447 (5)	0.0798 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.032 (3)	0.042 (3)	0.053 (3)	0.011 (2)	−0.003 (2)	0.001 (2)
C2	0.044 (3)	0.036 (3)	0.060 (3)	0.009 (2)	0.002 (2)	−0.001 (2)
C3	0.056 (3)	0.037 (3)	0.049 (3)	0.005 (2)	0.002 (2)	−0.001 (2)
C4	0.038 (3)	0.043 (3)	0.060 (3)	−0.002 (2)	−0.007 (2)	−0.002 (2)
C5	0.032 (2)	0.031 (2)	0.040 (2)	0.0017 (18)	−0.0019 (18)	0.0002 (18)
C6	0.033 (2)	0.039 (3)	0.047 (2)	0.000 (2)	−0.0077 (19)	−0.001 (2)
C7	0.037 (3)	0.039 (3)	0.043 (2)	0.003 (2)	−0.0057 (19)	0.002 (2)
C8	0.034 (3)	0.028 (2)	0.037 (2)	0.0058 (19)	−0.0002 (17)	0.0018 (17)
C9	0.029 (2)	0.033 (2)	0.042 (2)	0.0037 (19)	−0.0010 (18)	0.0014 (18)
C10	0.035 (2)	0.031 (2)	0.042 (2)	0.0045 (19)	0.0009 (18)	0.0034 (18)
C11	0.045 (3)	0.040 (3)	0.064 (3)	0.010 (2)	−0.014 (2)	0.000 (2)
C12	0.040 (3)	0.043 (3)	0.065 (3)	0.005 (2)	−0.016 (2)	−0.005 (2)
C13	0.037 (2)	0.033 (3)	0.039 (2)	−0.001 (2)	−0.0048 (18)	−0.0008 (18)
C14	0.035 (2)	0.033 (2)	0.038 (2)	0.003 (2)	0.0003 (18)	0.0018 (18)
C15	0.041 (3)	0.031 (2)	0.046 (2)	0.002 (2)	−0.0028 (19)	−0.0013 (19)
C16	0.036 (3)	0.036 (3)	0.039 (2)	−0.001 (2)	0.0053 (19)	−0.0030 (18)
C17	0.041 (3)	0.036 (3)	0.042 (2)	0.001 (2)	0.000 (2)	−0.0025 (19)
C18	0.057 (3)	0.052 (3)	0.048 (3)	−0.004 (3)	0.002 (2)	0.000 (2)
C19	0.052 (3)	0.041 (3)	0.046 (3)	0.002 (2)	0.004 (2)	0.004 (2)
C20	0.042 (3)	0.041 (3)	0.046 (3)	−0.005 (2)	−0.003 (2)	−0.005 (2)
C21	0.042 (3)	0.036 (3)	0.041 (2)	0.003 (2)	0.008 (2)	0.0016 (19)
C22	0.050 (3)	0.032 (3)	0.066 (3)	−0.002 (2)	0.004 (2)	−0.002 (2)
C23	0.042 (3)	0.044 (3)	0.062 (3)	0.000 (2)	−0.002 (2)	−0.002 (2)
C24	0.050 (3)	0.037 (3)	0.048 (3)	0.011 (2)	0.009 (2)	0.004 (2)
C25	0.063 (4)	0.034 (3)	0.053 (3)	0.002 (2)	0.007 (2)	0.000 (2)
C26	0.052 (3)	0.035 (3)	0.049 (3)	0.000 (2)	0.001 (2)	−0.004 (2)
C27	0.056 (4)	0.050 (3)	0.066 (3)	0.003 (3)	0.010 (3)	−0.001 (3)
O17	0.046 (2)	0.050 (2)	0.074 (2)	−0.0096 (18)	−0.0136 (17)	−0.0042 (18)
O31	0.066 (3)	0.035 (2)	0.090 (3)	0.0081 (18)	−0.018 (2)	−0.0153 (19)
N28	0.071 (3)	0.055 (3)	0.111 (4)	0.018 (3)	−0.017 (3)	−0.001 (3)

Geometric parameters (Å, º)

C1—C2	1.515 (6)	C13—C17	1.501 (7)
C1—C10	1.553 (6)	C13—C14	1.540 (5)
C1—H1A	0.9700	C13—C18	1.545 (6)
C1—H1B	0.9700	C14—C15	1.540 (6)
C2—C3	1.512 (7)	C14—H14	0.9800
C2—H2A	0.9700	C15—C16	1.518 (6)
C2—H2B	0.9700	C15—H15A	0.9700
C3—O31	1.430 (6)	C15—H15B	0.9700
C3—C4	1.507 (7)	C16—C20	1.322 (6)
C3—H3	0.9800	C16—C17	1.506 (6)
C4—C5	1.509 (6)	C17—O17	1.216 (5)
C4—H4A	0.9700	C18—H18A	0.9600
C4—H4B	0.9700	C18—H18B	0.9600
C5—C6	1.318 (6)	C18—H18C	0.9600
C5—C10	1.526 (6)	C19—H19A	0.9600
C6—C7	1.495 (6)	C19—H19B	0.9600
C6—H6	0.9300	C19—H19C	0.9600
C7—C8	1.538 (6)	C20—C21	1.465 (6)
C7—H7A	0.9700	C20—H20	0.9300
C7—H7B	0.9700	C21—C26	1.388 (7)
C8—C14	1.516 (6)	C21—C22	1.392 (7)
C8—C9	1.540 (5)	C22—C23	1.377 (7)
C8—H8	0.9800	C22—H22	0.9300
C9—C10	1.549 (6)	C23—C24	1.385 (7)
C9—C11	1.550 (6)	C23—H23	0.9300
C9—H9	0.9800	C24—C25	1.403 (7)
C10—C19	1.530 (6)	C24—C27	1.439 (7)
C11—C12	1.525 (7)	C25—C26	1.369 (7)
C11—H11A	0.9700	C25—H25	0.9300
C11—H11B	0.9700	C26—H26	0.9300
C12—C13	1.513 (6)	C27—N28	1.141 (7)
C12—H12A	0.9700	O31—H31	0.81 (2)
C12—H12B	0.9700
C2—C1—C10	114.3 (4)	C13—C12—H12B	109.5
C2—C1—H1A	108.7	C11—C12—H12B	109.5
C10—C1—H1A	108.7	H12A—C12—H12B	108.0
C2—C1—H1B	108.7	C17—C13—C12	117.1 (4)
C10—C1—H1B	108.7	C17—C13—C14	99.7 (3)
H1A—C1—H1B	107.6	C12—C13—C14	108.8 (4)
C3—C2—C1	110.4 (4)	C17—C13—C18	105.8 (4)
C3—C2—H2A	109.6	C12—C13—C18	112.2 (4)
C1—C2—H2A	109.6	C14—C13—C18	112.8 (4)
C3—C2—H2B	109.6	C8—C14—C13	113.5 (3)
C1—C2—H2B	109.6	C8—C14—C15	121.0 (3)
H2A—C2—H2B	108.1	C13—C14—C15	104.6 (3)
O31—C3—C4	107.6 (4)	C8—C14—H14	105.5
O31—C3—C2	112.7 (4)	C13—C14—H14	105.5
C4—C3—C2	109.8 (4)	C15—C14—H14	105.5
O31—C3—H3	108.9	C16—C15—C14	102.5 (4)
C4—C3—H3	108.9	C16—C15—H15A	111.3
C2—C3—H3	108.9	C14—C15—H15A	111.3
C3—C4—C5	112.8 (4)	C16—C15—H15B	111.3
C3—C4—H4A	109.0	C14—C15—H15B	111.3
C5—C4—H4A	109.0	H15A—C15—H15B	109.2
C3—C4—H4B	109.0	C20—C16—C17	119.8 (4)
C5—C4—H4B	109.0	C20—C16—C15	133.0 (4)
H4A—C4—H4B	107.8	C17—C16—C15	107.3 (4)
C6—C5—C4	121.3 (4)	O17—C17—C13	126.9 (4)
C6—C5—C10	122.2 (4)	O17—C17—C16	125.4 (4)
C4—C5—C10	116.5 (4)	C13—C17—C16	107.7 (4)
C5—C6—C7	126.6 (4)	C13—C18—H18A	109.5
C5—C6—H6	116.7	C13—C18—H18B	109.5
C7—C6—H6	116.7	H18A—C18—H18B	109.5
C6—C7—C8	112.7 (4)	C13—C18—H18C	109.5
C6—C7—H7A	109.1	H18A—C18—H18C	109.5
C8—C7—H7A	109.1	H18B—C18—H18C	109.5
C6—C7—H7B	109.1	C10—C19—H19A	109.5
C8—C7—H7B	109.1	C10—C19—H19B	109.5
H7A—C7—H7B	107.8	H19A—C19—H19B	109.5
C14—C8—C7	110.3 (3)	C10—C19—H19C	109.5
C14—C8—C9	109.5 (3)	H19A—C19—H19C	109.5
C7—C8—C9	110.3 (3)	H19B—C19—H19C	109.5
C14—C8—H8	108.9	C16—C20—C21	131.0 (4)
C7—C8—H8	108.9	C16—C20—H20	114.5
C9—C8—H8	108.9	C21—C20—H20	114.5
C8—C9—C10	113.2 (3)	C26—C21—C22	118.2 (4)
C8—C9—C11	111.5 (3)	C26—C21—C20	118.6 (4)
C10—C9—C11	113.1 (3)	C22—C21—C20	123.1 (4)
C8—C9—H9	106.1	C23—C22—C21	120.6 (5)
C10—C9—H9	106.1	C23—C22—H22	119.7
C11—C9—H9	106.1	C21—C22—H22	119.7
C5—C10—C19	108.4 (4)	C22—C23—C24	120.6 (5)
C5—C10—C9	110.1 (3)	C22—C23—H23	119.7
C19—C10—C9	111.5 (3)	C24—C23—H23	119.7
C5—C10—C1	108.6 (3)	C23—C24—C25	119.2 (4)
C19—C10—C1	110.1 (4)	C23—C24—C27	120.6 (5)
C9—C10—C1	108.1 (3)	C25—C24—C27	120.3 (5)
C12—C11—C9	113.7 (4)	C26—C25—C24	119.4 (5)
C12—C11—H11A	108.8	C26—C25—H25	120.3
C9—C11—H11A	108.8	C24—C25—H25	120.3
C12—C11—H11B	108.8	C25—C26—C21	121.9 (5)
C9—C11—H11B	108.8	C25—C26—H26	119.0
H11A—C11—H11B	107.7	C21—C26—H26	119.0
C13—C12—C11	110.9 (4)	N28—C27—C24	178.7 (6)
C13—C12—H12A	109.5	C3—O31—H31	101 (5)
C11—C12—H12A	109.5
C10—C1—C2—C3	−57.9 (5)	C7—C8—C14—C15	−55.5 (5)
C1—C2—C3—O31	178.8 (4)	C9—C8—C14—C15	−177.0 (4)
C1—C2—C3—C4	58.8 (5)	C17—C13—C14—C8	176.7 (4)
O31—C3—C4—C5	−178.0 (4)	C12—C13—C14—C8	−60.2 (5)
C2—C3—C4—C5	−55.0 (5)	C18—C13—C14—C8	64.9 (5)
C3—C4—C5—C6	−130.3 (5)	C17—C13—C14—C15	42.8 (4)
C3—C4—C5—C10	50.1 (6)	C12—C13—C14—C15	165.9 (4)
C4—C5—C6—C7	−179.4 (4)	C18—C13—C14—C15	−68.9 (5)
C10—C5—C6—C7	0.1 (7)	C8—C14—C15—C16	−164.8 (3)
C5—C6—C7—C8	11.0 (7)	C13—C14—C15—C16	−35.2 (4)
C6—C7—C8—C14	−159.7 (4)	C14—C15—C16—C20	−167.4 (5)
C6—C7—C8—C9	−38.6 (5)	C14—C15—C16—C17	13.5 (4)
C14—C8—C9—C10	179.8 (3)	C12—C13—C17—O17	27.2 (6)
C7—C8—C9—C10	58.2 (4)	C14—C13—C17—O17	144.2 (5)
C14—C8—C9—C11	−51.3 (4)	C18—C13—C17—O17	−98.6 (5)
C7—C8—C9—C11	−172.8 (4)	C12—C13—C17—C16	−151.4 (4)
C6—C5—C10—C19	−104.9 (5)	C14—C13—C17—C16	−34.3 (4)
C4—C5—C10—C19	74.6 (5)	C18—C13—C17—C16	82.8 (4)
C6—C5—C10—C9	17.3 (6)	C20—C16—C17—O17	15.7 (7)
C4—C5—C10—C9	−163.1 (4)	C15—C16—C17—O17	−165.1 (4)
C6—C5—C10—C1	135.5 (4)	C20—C16—C17—C13	−165.7 (4)
C4—C5—C10—C1	−45.0 (5)	C15—C16—C17—C13	13.5 (5)
C8—C9—C10—C5	−46.4 (4)	C17—C16—C20—C21	177.1 (4)
C11—C9—C10—C5	−174.5 (4)	C15—C16—C20—C21	−1.8 (9)
C8—C9—C10—C19	74.0 (4)	C16—C20—C21—C26	172.6 (5)
C11—C9—C10—C19	−54.1 (5)	C16—C20—C21—C22	−10.9 (8)
C8—C9—C10—C1	−164.9 (3)	C26—C21—C22—C23	−3.4 (7)
C11—C9—C10—C1	67.0 (4)	C20—C21—C22—C23	−180.0 (4)
C2—C1—C10—C5	49.0 (5)	C21—C22—C23—C24	2.2 (7)
C2—C1—C10—C19	−69.6 (5)	C22—C23—C24—C25	−0.1 (7)
C2—C1—C10—C9	168.4 (4)	C22—C23—C24—C27	179.2 (5)
C8—C9—C11—C12	51.2 (5)	C23—C24—C25—C26	−0.6 (7)
C10—C9—C11—C12	−179.8 (4)	C27—C24—C25—C26	−179.9 (4)
C9—C11—C12—C13	−54.0 (6)	C24—C25—C26—C21	−0.7 (7)
C11—C12—C13—C17	168.2 (4)	C22—C21—C26—C25	2.7 (7)
C11—C12—C13—C14	56.2 (5)	C20—C21—C26—C25	179.4 (4)
C11—C12—C13—C18	−69.2 (5)	C19—C10—C13—C18	10.0 (4)
C7—C8—C14—C13	179.0 (4)	H31—O31—C3—C4	173 (4)
C9—C8—C14—C13	57.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···N28^i	0.81 (2)	2.18 (2)	2.980 (7)	172 (6)

Symmetry code: (i) x−1, y+1, z.