17-Oxo-16-(2-pyridyl­methyl­ene)­androst-5-en-3[beta]-ol monohydrate

The title compound, C₂₅H₃₁NO₂·H₂O, has the outer two six-membered rings in chair conformations, while the central ring is in an 8[beta],9[alpha]-half-chair conformation. The five-membered ring adopts a 13,14-half-chair conformation. The pyridyl­methyl­ene moiety has an E configuration with respect to the carbonyl group at position 17. The structure is stabilized by intermolecular O-H...N and O-H...O hydrogen bonds.

S1. Comment

The structure determination of the title compound, (I), was undertaken to investigate the conformation of the fused-ring system and the configuration of the 16-(2-pyridylmethylene) functionaly with respect to the carbonyl group at position 17.

Compound (I), an epiandrostene derivative, is a steroid in which rings A, B and C are essentially rigid, whereas ring D has a flexible conformation with respect to the side chain. The absolute configuration of (I) is based on the known configuration of the starting material, namely epiandrosterone (Weeks et al., 1971). The torsion angles show that rings A and C adopt chair conformations. The short C2—C3 bond distance of 1.507 (4) Å in (I) is in agreement with other related steroids (Paixao et al., 1998). Ring B has an 8β,9α-half-chair conformation. The C5—C6 distance of 1.338 (4) Å confirms the localization of a double bond at this position. Atoms C8 and C9 are displaced to opposite sides by 0.359 (5) and 0.389 (5) Å, respectively, from the mean C10/C5/C6/C7 plane (Cox et al., 1981). Ring D has a 13,14-half-chair conformation. The five torsion angles of ring D [C13–C14–C15–C16 - 32.4 (3), C14–C15–C16–C17 12.0 (3), C15–C16–C17–C13 12.8 (3), C16–C17–C13–C14 - 32.3 (3) and C17–C13–C14–C15 40.1 (3)°] are comparable with the reported values of -37.6 (2), 16.3 (2), 11.3 (2), -33.7 (2) and 43.7 (2)°, respectively (Paixao et al., 1998). The C17–C16–C20–C21 torsion angle of 173.2 (3)° indicates that the 2-pyridyl ring has an E configuration with respect to the carbonyl group at position 17; the C20 H atom is Z with respect to this carbonyl group. The O17 atom is equatorially substituted at C17, and O3 is equatorially substituted at C3. The dihedral angle between the pyridine ring and the androstene moiety is 8.71 (12)°. The geometry of the rings is trans at the B/C and C/D ring junctions.

The structure of (I) is stabilized by a network of hydrogen bonds involving the hydroxyl O, carbonyl O and pyridyl N atoms of the steroid moiety, and the O atom of the water molecule (Table 2). The hydroxyl O3 atom at C3 takes part in two intermolecular hydrogen bonds, one as a donor towards the pyridyl nitrogen (N26) and the other as an acceptor from the water molecule (O27). In addition to this, the water molecule also has another intermolecular hydrogen bond involving the carbonyl oxygen (O17). In this way an infinite one-dimensional chain of molecules is assembled (Fig. 2).

S2. Experimental

The title compound was prepared by condensing dehydroepiandrosterone (1 g, 3.47 mM) with 2-pyridine carboxaldehyde (1.75 g, 16.34 mM) in the presence of sodium hydroxide (1.75 g, 43.75 mM) in methanol (20 ml). The absolute configuration of the epiandrosterone is already known (Weeks et al., 1971). The reaction mixture was shaken at room temperature for 1 h, and then poured into ice-cold water and allowed to stand overnight. The precipitate was filtered, washed with distilled water and dried under vacuum. The solid residue was crystallized from methanol to afford crystals of (I)·H₂O (1.0 g, 72.9%, m.p.: 478–483 K).

S3. Refinement

All H atoms of the steroid were located from difference Fourier maps and were then included in the structure-factor calculations as riding atoms with C—H distances in the range 0.93–0.98 Å. The H atoms of the water molecule were also obtained from a difference map and were initially refined subject to a free-variable DFIX O—H restraint with a common U_iso free variable. In the final cycles, the water H atoms were then not adjusted (AFIX 1) from the O—H distance (1.01 Å) so obtained. The analysis does not allow the absolute configuration of (I) to be determined, but this was known from the synthesis.

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: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. A view showing part of the infinite molecular hydrogen-bonded chain in (I). All H atoms except those involved in hydrogen bonding have been discarded. The hash (#) and asterisk (*) labels denote equivalent positions (1 + x, y, 1 + z) and (-1 + x, y, -1 + z), respectively.

17-Oxo-16-(2-pyridylmethylene)-androst-5-en-3β-ol monohydrate

Crystal data

C25H31NO2·H2O	F(000) = 428
Mr = 395.52	Dx = 1.251 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.5418 Å
a = 6.5376 (3) Å	Cell parameters from 25 reflections
b = 11.8766 (10) Å	θ = 20–30°
c = 13.5312 (15) Å	µ = 0.64 mm^−1
β = 91.197 (12)°	T = 293 K
V = 1050.39 (15) Å^3	Rectangular, colourless
Z = 2	0.3 × 0.2 × 0.1 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	1888 reflections with I > 2s(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 67.9°, θmin = 3.3°
ω–2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
Tmin = 0.800, Tmax = 0.988	l = −16→16
2187 measured reflections	2 standard reflections every 120 min
2003 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0724P)^2 + 0.1862P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
2003 reflections	Δρmax = 0.27 e Å^−3
267 parameters	Δρmin = −0.22 e Å^−3
3 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (10)

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
O3	−0.2397 (4)	0.7248 (3)	−0.28994 (15)	0.0603 (7)
H3	−0.1564	0.7538	−0.3265	0.090*
O17	0.3275 (3)	0.6155 (2)	0.46889 (15)	0.0523 (6)
N26	0.9804 (4)	0.8130 (2)	0.54939 (17)	0.0432 (6)
C1	−0.1706 (4)	0.6331 (3)	−0.02775 (19)	0.0351 (6)
H1A	−0.2176	0.5653	0.0047	0.042*
H1B	−0.2349	0.6968	0.0040	0.042*
C2	−0.2407 (4)	0.6297 (3)	−0.1358 (2)	0.0411 (7)
H2A	−0.1876	0.5624	−0.1668	0.049*
H2B	−0.3889	0.6265	−0.1397	0.049*
C3	−0.1671 (4)	0.7322 (3)	−0.19021 (19)	0.0387 (6)
H3A	−0.2273	0.7991	−0.1600	0.046*
C4	0.0656 (4)	0.7417 (3)	−0.18152 (19)	0.0380 (6)
H4A	0.1272	0.6805	−0.2178	0.046*
H4B	0.1086	0.8119	−0.2113	0.046*
C5	0.1415 (4)	0.7380 (2)	−0.07507 (18)	0.0299 (5)
C6	0.2728 (4)	0.8155 (2)	−0.04007 (19)	0.0331 (6)
H6	0.3135	0.8718	−0.0832	0.040*
C7	0.3592 (4)	0.8183 (2)	0.06345 (19)	0.0349 (6)
H7A	0.2949	0.8790	0.0993	0.042*
H7B	0.5045	0.8342	0.0612	0.042*
C8	0.3279 (4)	0.7087 (2)	0.11905 (18)	0.0276 (5)
H8	0.4249	0.6524	0.0953	0.033*
C9	0.1071 (4)	0.6658 (2)	0.09947 (18)	0.0279 (5)
H9	0.0165	0.7280	0.1173	0.033*
C10	0.0638 (4)	0.6425 (2)	−0.01221 (18)	0.0286 (5)
C11	0.0480 (4)	0.5661 (3)	0.16598 (19)	0.0357 (6)
H11A	−0.0978	0.5526	0.1580	0.043*
H11B	0.1184	0.4992	0.1434	0.043*
C12	0.0980 (4)	0.5828 (3)	0.27624 (19)	0.0367 (6)
H12A	0.0116	0.6413	0.3028	0.044*
H12B	0.0723	0.5136	0.3120	0.044*
C13	0.3226 (4)	0.6160 (2)	0.28874 (18)	0.0309 (6)
C14	0.3600 (4)	0.7239 (2)	0.23019 (18)	0.0289 (5)
H14	0.2547	0.7772	0.2508	0.035*
C15	0.5654 (4)	0.7707 (3)	0.27197 (18)	0.0346 (6)
H15A	0.6808	0.7380	0.2384	0.042*
H15B	0.5712	0.8521	0.2660	0.042*
C16	0.5625 (4)	0.7348 (3)	0.37945 (19)	0.0354 (6)
C17	0.3912 (4)	0.6510 (3)	0.39193 (19)	0.0363 (6)
C18	0.4657 (4)	0.5173 (3)	0.2622 (2)	0.0411 (7)
H18A	0.6052	0.5385	0.2758	0.062*
H18B	0.4489	0.4996	0.1933	0.062*
H18C	0.4320	0.4525	0.3010	0.062*
C19	0.1667 (5)	0.5319 (3)	−0.0459 (2)	0.0409 (7)
H19A	0.1563	0.5259	−0.1166	0.061*
H19B	0.0994	0.4688	−0.0164	0.061*
H19C	0.3083	0.5323	−0.0256	0.061*
C20	0.6861 (4)	0.7582 (3)	0.4573 (2)	0.0370 (6)
H20	0.6468	0.7262	0.5167	0.044*
C21	0.8725 (4)	0.8259 (3)	0.46345 (19)	0.0361 (6)
C22	0.9409 (5)	0.8958 (3)	0.3895 (2)	0.0481 (8)
H22	0.8645	0.9042	0.3312	0.058*
C23	1.1231 (5)	0.9531 (3)	0.4025 (3)	0.0550 (9)
H23	1.1685	1.0024	0.3543	0.066*
C24	1.2368 (5)	0.9358 (3)	0.4881 (3)	0.0520 (8)
H24	1.3632	0.9704	0.4977	0.062*
C25	1.1584 (5)	0.8666 (3)	0.5585 (2)	0.0514 (9)
H25	1.2345	0.8562	0.6166	0.062*
O27	−0.5891 (4)	0.5797 (3)	−0.32162 (17)	0.0683 (8)
H27A	−0.5206	0.6560	−0.3215	0.097*
H27B	−0.6254	0.5933	−0.3937	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0610 (14)	0.0865 (18)	0.0325 (11)	−0.0300 (14)	−0.0179 (9)	0.0169 (12)
O17	0.0450 (12)	0.0773 (17)	0.0343 (11)	−0.0175 (11)	−0.0037 (8)	0.0114 (11)
N26	0.0373 (12)	0.0582 (16)	0.0338 (11)	−0.0091 (12)	−0.0068 (9)	−0.0016 (12)
C1	0.0306 (13)	0.0449 (16)	0.0295 (13)	−0.0093 (11)	−0.0031 (10)	0.0048 (12)
C2	0.0380 (15)	0.0509 (17)	0.0339 (14)	−0.0121 (13)	−0.0075 (11)	0.0051 (13)
C3	0.0421 (15)	0.0436 (15)	0.0301 (13)	−0.0036 (13)	−0.0094 (11)	0.0033 (12)
C4	0.0423 (14)	0.0438 (15)	0.0277 (12)	−0.0097 (13)	−0.0014 (10)	0.0040 (12)
C5	0.0288 (11)	0.0312 (13)	0.0296 (12)	0.0009 (10)	0.0003 (9)	0.0006 (11)
C6	0.0360 (13)	0.0306 (13)	0.0327 (13)	−0.0028 (11)	−0.0012 (10)	0.0054 (11)
C7	0.0347 (13)	0.0334 (13)	0.0365 (13)	−0.0046 (11)	−0.0048 (10)	0.0032 (12)
C8	0.0224 (11)	0.0298 (12)	0.0307 (12)	−0.0007 (10)	−0.0013 (9)	0.0007 (10)
C9	0.0262 (12)	0.0303 (13)	0.0270 (12)	−0.0017 (10)	−0.0023 (9)	0.0005 (10)
C10	0.0278 (13)	0.0311 (13)	0.0268 (12)	−0.0006 (10)	−0.0011 (9)	−0.0011 (10)
C11	0.0309 (13)	0.0430 (16)	0.0330 (13)	−0.0092 (11)	−0.0037 (10)	0.0058 (12)
C12	0.0303 (13)	0.0495 (16)	0.0303 (12)	−0.0083 (12)	−0.0024 (10)	0.0077 (12)
C13	0.0251 (13)	0.0373 (15)	0.0301 (12)	−0.0008 (10)	−0.0018 (9)	0.0040 (11)
C14	0.0238 (11)	0.0316 (13)	0.0311 (12)	0.0000 (10)	−0.0029 (9)	−0.0004 (11)
C15	0.0293 (13)	0.0413 (14)	0.0329 (13)	−0.0065 (11)	−0.0084 (10)	0.0037 (11)
C16	0.0294 (12)	0.0426 (15)	0.0339 (13)	−0.0015 (12)	−0.0048 (10)	0.0015 (12)
C17	0.0298 (13)	0.0454 (16)	0.0333 (14)	−0.0004 (12)	−0.0048 (10)	0.0041 (12)
C18	0.0385 (15)	0.0373 (15)	0.0474 (16)	0.0039 (12)	−0.0041 (12)	0.0063 (12)
C19	0.0481 (16)	0.0347 (15)	0.0400 (15)	0.0058 (13)	0.0011 (12)	−0.0051 (12)
C20	0.0324 (13)	0.0474 (16)	0.0311 (12)	−0.0031 (12)	−0.0034 (10)	0.0003 (12)
C21	0.0331 (13)	0.0438 (15)	0.0312 (13)	−0.0005 (12)	−0.0058 (10)	−0.0053 (12)
C22	0.0483 (17)	0.0561 (19)	0.0393 (15)	−0.0109 (15)	−0.0101 (13)	0.0037 (14)
C23	0.056 (2)	0.056 (2)	0.0530 (18)	−0.0196 (17)	−0.0007 (15)	0.0053 (16)
C24	0.0416 (17)	0.063 (2)	0.0511 (18)	−0.0140 (15)	−0.0045 (14)	−0.0101 (16)
C25	0.0421 (16)	0.071 (2)	0.0408 (16)	−0.0119 (16)	−0.0121 (12)	−0.0073 (17)
O27	0.0637 (16)	0.095 (2)	0.0463 (13)	−0.0181 (16)	−0.0069 (11)	0.0013 (14)

Geometric parameters (Å, º)

O3—C3	1.424 (3)	C11—H11B	0.97
O3—H3	0.82	C12—C13	1.526 (3)
O17—C17	1.206 (3)	C12—H12A	0.97
N26—C25	1.330 (4)	C12—H12B	0.97
N26—C21	1.356 (3)	C13—C17	1.516 (3)
C1—C2	1.523 (3)	C13—C14	1.529 (4)
C1—C10	1.546 (3)	C13—C18	1.547 (4)
C1—H1A	0.97	C14—C15	1.550 (3)
C1—H1B	0.97	C14—H14	0.98
C2—C3	1.507 (4)	C15—C16	1.516 (4)
C2—H2A	0.97	C15—H15A	0.97
C2—H2B	0.97	C15—H15B	0.97
C3—C4	1.528 (4)	C16—C20	1.343 (4)
C3—H3A	0.98	C16—C17	1.510 (4)
C4—C5	1.514 (3)	C18—H18A	0.96
C4—H4A	0.97	C18—H18B	0.96
C4—H4B	0.97	C18—H18C	0.96
C5—C6	1.338 (4)	C19—H19A	0.96
C5—C10	1.512 (4)	C19—H19B	0.96
C6—C7	1.500 (3)	C19—H19C	0.96
C6—H6	0.93	C20—C21	1.461 (4)
C7—C8	1.519 (4)	C20—H20	0.93
C7—H7A	0.97	C21—C22	1.382 (4)
C7—H7B	0.97	C22—C23	1.379 (5)
C8—C14	1.525 (3)	C22—H22	0.93
C8—C9	1.549 (3)	C23—C24	1.379 (5)
C8—H8	0.98	C23—H23	0.93
C9—C11	1.542 (4)	C24—C25	1.366 (5)
C9—C10	1.556 (3)	C24—H24	0.93
C9—H9	0.98	C25—H25	0.93
C10—C19	1.549 (4)	O27—H27A	1.01
C11—C12	1.534 (3)	O27—H27B	1.01
C11—H11A	0.97
C3—O3—H3	109.5	C13—C12—C11	109.0 (2)
C25—N26—C21	117.6 (3)	C13—C12—H12A	109.9
C2—C1—C10	114.2 (2)	C11—C12—H12A	109.9
C2—C1—H1A	108.7	C13—C12—H12B	109.9
C10—C1—H1A	108.7	C11—C12—H12B	109.9
C2—C1—H1B	108.7	H12A—C12—H12B	108.3
C10—C1—H1B	108.7	C17—C13—C12	116.0 (2)
H1A—C1—H1B	107.6	C17—C13—C14	101.5 (2)
C3—C2—C1	110.8 (2)	C12—C13—C14	108.9 (2)
C3—C2—H2A	109.5	C17—C13—C18	104.7 (2)
C1—C2—H2A	109.5	C12—C13—C18	111.3 (2)
C3—C2—H2B	109.5	C14—C13—C18	114.2 (2)
C1—C2—H2B	109.5	C8—C14—C13	113.1 (2)
H2A—C2—H2B	108.1	C8—C14—C15	120.2 (2)
O3—C3—C2	108.1 (2)	C13—C14—C15	105.0 (2)
O3—C3—C4	112.9 (2)	C8—C14—H14	105.9
C2—C3—C4	110.5 (2)	C13—C14—H14	105.9
O3—C3—H3A	108.4	C15—C14—H14	105.9
C2—C3—H3A	108.4	C16—C15—C14	102.7 (2)
C4—C3—H3A	108.4	C16—C15—H15A	111.2
C5—C4—C3	112.1 (2)	C14—C15—H15A	111.2
C5—C4—H4A	109.2	C16—C15—H15B	111.2
C3—C4—H4A	109.2	C14—C15—H15B	111.2
C5—C4—H4B	109.2	H15A—C15—H15B	109.1
C3—C4—H4B	109.2	C20—C16—C17	118.9 (2)
H4A—C4—H4B	107.9	C20—C16—C15	132.4 (3)
C6—C5—C10	122.5 (2)	C17—C16—C15	108.5 (2)
C6—C5—C4	120.8 (2)	O17—C17—C16	126.7 (2)
C10—C5—C4	116.7 (2)	O17—C17—C13	126.8 (3)
C5—C6—C7	124.9 (2)	C16—C17—C13	106.5 (2)
C5—C6—H6	117.6	C13—C18—H18A	109.5
C7—C6—H6	117.6	C13—C18—H18B	109.5
C6—C7—C8	113.1 (2)	H18A—C18—H18B	109.5
C6—C7—H7A	109.0	C13—C18—H18C	109.5
C8—C7—H7A	109.0	H18A—C18—H18C	109.5
C6—C7—H7B	109.0	H18B—C18—H18C	109.5
C8—C7—H7B	109.0	C10—C19—H19A	109.5
H7A—C7—H7B	107.8	C10—C19—H19B	109.5
C7—C8—C14	111.7 (2)	H19A—C19—H19B	109.5
C7—C8—C9	109.4 (2)	C10—C19—H19C	109.5
C14—C8—C9	108.44 (18)	H19A—C19—H19C	109.5
C7—C8—H8	109.1	H19B—C19—H19C	109.5
C14—C8—H8	109.1	C16—C20—C21	130.2 (3)
C9—C8—H8	109.1	C16—C20—H20	114.9
C11—C9—C8	113.38 (19)	C21—C20—H20	114.9
C11—C9—C10	112.8 (2)	N26—C21—C22	121.3 (3)
C8—C9—C10	111.99 (19)	N26—C21—C20	113.9 (3)
C11—C9—H9	106.0	C22—C21—C20	124.9 (2)
C8—C9—H9	106.0	C23—C22—C21	119.7 (3)
C10—C9—H9	106.0	C23—C22—H22	120.1
C5—C10—C1	108.8 (2)	C21—C22—H22	120.1
C5—C10—C19	108.5 (2)	C24—C23—C22	118.8 (3)
C1—C10—C19	109.5 (2)	C24—C23—H23	120.6
C5—C10—C9	110.9 (2)	C22—C23—H23	120.6
C1—C10—C9	107.72 (18)	C25—C24—C23	118.1 (3)
C19—C10—C9	111.4 (2)	C25—C24—H24	120.9
C12—C11—C9	114.7 (2)	C23—C24—H24	120.9
C12—C11—H11A	108.6	N26—C25—C24	124.3 (3)
C9—C11—H11A	108.6	N26—C25—H25	117.8
C12—C11—H11B	108.6	C24—C25—H25	117.8
C9—C11—H11B	108.6	H27A—O27—H27B	87.3
H11A—C11—H11B	107.6
C10—C1—C2—C3	−57.1 (3)	C7—C8—C14—C13	178.1 (2)
C1—C2—C3—O3	−179.2 (2)	C9—C8—C14—C13	57.4 (3)
C1—C2—C3—C4	56.8 (3)	C7—C8—C14—C15	−57.0 (3)
O3—C3—C4—C5	−174.4 (3)	C9—C8—C14—C15	−177.6 (2)
C2—C3—C4—C5	−53.3 (3)	C17—C13—C14—C8	172.93 (19)
C3—C4—C5—C6	−130.4 (3)	C12—C13—C14—C8	−64.2 (3)
C3—C4—C5—C10	50.4 (3)	C18—C13—C14—C8	60.9 (3)
C10—C5—C6—C7	0.1 (4)	C17—C13—C14—C15	40.1 (3)
C4—C5—C6—C7	−179.1 (3)	C12—C13—C14—C15	163.0 (2)
C5—C6—C7—C8	14.8 (4)	C18—C13—C14—C15	−71.9 (3)
C6—C7—C8—C14	−163.7 (2)	C8—C14—C15—C16	−161.1 (2)
C6—C7—C8—C9	−43.6 (3)	C13—C14—C15—C16	−32.4 (3)
C7—C8—C9—C11	−170.3 (2)	C14—C15—C16—C20	−172.7 (3)
C14—C8—C9—C11	−48.3 (3)	C14—C15—C16—C17	12.0 (3)
C7—C8—C9—C10	60.6 (3)	C20—C16—C17—O17	13.9 (5)
C14—C8—C9—C10	−177.3 (2)	C15—C16—C17—O17	−170.0 (3)
C6—C5—C10—C1	133.7 (3)	C20—C16—C17—C13	−163.2 (3)
C4—C5—C10—C1	−47.1 (3)	C15—C16—C17—C13	12.8 (3)
C6—C5—C10—C19	−107.3 (3)	C12—C13—C17—O17	32.7 (4)
C4—C5—C10—C19	72.0 (3)	C14—C13—C17—O17	150.5 (3)
C6—C5—C10—C9	15.4 (3)	C18—C13—C17—O17	−90.4 (3)
C4—C5—C10—C9	−165.4 (2)	C12—C13—C17—C16	−150.1 (2)
C2—C1—C10—C5	50.1 (3)	C14—C13—C17—C16	−32.3 (3)
C2—C1—C10—C19	−68.3 (3)	C18—C13—C17—C16	86.8 (3)
C2—C1—C10—C9	170.4 (2)	C17—C16—C20—C21	173.2 (3)
C11—C9—C10—C5	−174.9 (2)	C15—C16—C20—C21	−1.7 (6)
C8—C9—C10—C5	−45.5 (3)	C25—N26—C21—C22	−2.5 (5)
C11—C9—C10—C1	66.2 (3)	C25—N26—C21—C20	176.1 (3)
C8—C9—C10—C1	−164.4 (2)	C16—C20—C21—N26	−167.4 (3)
C11—C9—C10—C19	−53.9 (3)	C16—C20—C21—C22	11.2 (5)
C8—C9—C10—C19	75.5 (3)	N26—C21—C22—C23	0.5 (5)
C8—C9—C11—C12	48.4 (3)	C20—C21—C22—C23	−177.9 (3)
C10—C9—C11—C12	177.0 (2)	C21—C22—C23—C24	2.3 (6)
C9—C11—C12—C13	−52.6 (3)	C22—C23—C24—C25	−3.0 (6)
C11—C12—C13—C17	172.1 (2)	C21—N26—C25—C24	1.7 (5)
C11—C12—C13—C14	58.5 (3)	C23—C24—C25—N26	1.0 (6)
C11—C12—C13—C18	−68.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N26^i	0.82	2.04	2.833 (3)	162
O27—H27A···O3	1.01	2.05	2.886 (3)	139
O27—H27B···O17^i	1.01	1.90	2.907 (3)	176

Symmetry code: (i) x−1, y, z−1.