D-Secoestrone derivatives. VI. 17[beta]-Benzyl-17[alpha]-hydroxy-3-methoxyestra-1,3,5(10)-trien-16-one

The title mol­ecule, C₂₆H₃₀O₃, shows a novel chemical rearrangement of the substituents at position 17, i.e. an [alpha]-­orientation of the hydroxy group and a [beta]-orientation of the bulky benzyl moiety. The packing arrangement consists of coils formed by O2...O3 hydrogen bonds along the c axis. The compound shows complete loss of oestrogenic activity, and neither does it exhibit an antagonistic effect.

S1. Comment

In our earlier reports (Miljković et al., 1973, 1978; Miljković & Petrović, 1977; Miljković & Gaši, 1981), we established that D-ring fragmentation occurs in selected 16-oximino-17β-hydroxy steroid derivatives, under the conditions of the Beckmann reaction, affording the corresponding 16,17-seco-16-cyano-17-oxo-derivatives in reasonable yields. While continuing the study of the Beckmann fragmentation reaction, we have now unexpectedly discovered a novel rearrangement reaction.

By the action of acidic aqueous TiCl₃ (a reagent which caused fragmentation in all earlier cases) upon 16-oximino-17α-benzyl-17β-hydroxy derivatives in the androstane and estrane series, 16-oxo-17β-benzyl-17α-hydroxy derivatives with the inverse configuration at C17 were obtained (Miljković et al., 1997). Thus, acidic aqueous TiCl₃ mainly caused the hydrolysis of the 16-oximino group to the corresponding 16-keto group, with simultaneous rearrangement of the benzyl substituent from the 17α to the 17β position. The same rearrangement reaction was observed in the case of α-oxyimino alcohol, (I) (Stanković et al., 1996), which afforded compound (II) as the main reaction product under analogous reaction conditions. The intended and expected fragmentation product, (III), was isolated only as a minor product in 10% yield. \sch

The crude structure of (II) was deduced on the basis of spectroscopic evidence. Subsequently, X-ray diffraction analysis revealed the detailed structure, indicating a novel chemical rearrangement, described recently by Miljković et al. (1997), i.e. the migration of the benzyl substituent from the 17α-position in (I) to the 17β-position in (II).

Fig. 1 shows a perspective view of the molecule of (II). Since the starting materials were synthesized from the natural oestrone, the absolute stereochemistry of which is known (Fieser & Fieser, 1967), the X-ray structure of (II) is described for the appropriate enantiomer. The puckering (Cremer & Pople, 1975) and asymmetry parameters (Duax et al., 1976) reveal the usual ring conformations: ring B is a 7α,8β half-chair, ring C has a chair conformation, and ring D exhibits a transitional form between a 13β envelope and a 13β,14α half-chair conformation.

The C1—C10···C13—C18 non-bonded torsion angle of 88.1 (3)° shows that there is no significant twist along the principal axis of the molecule. The conformation of the steroidal skeleton of (II) compared with its precursor, (I), shows no significant difference (Fig. 2). Even so, the orientations of the two substituents at C17 are reversed. Biological screening demonstrated that (II) showed a complete loss of oestrogenic activity, which was considerable in (I) (a dose of 25 mg kg^-1 in experimental animals showed 74.98% of agonistic activity), as well as an absence of antagonistic effect. The unexpected α-orientation of the bulky substituent is thought to be the main reason for this significant change of biological activity (Duax et al., 1976).

In the crystal packing of (II), molecules related by the screw axis are linked by O2···O3 hydrogen bonds (Table 2), forming coils along the c axis.

S2. Experimental

The action of acidic aqueous TiCl₃ upon 16-oximino-17α-benzyl-17β-hydroxy-16-hydroxyimino-3-methoxyestra-1,3,5(10)- triene, (I), at room temperature afforded the title compound, (II), as the main reaction product (78% yield; m.p. 385–387 K from methanol). The expected fragmentation product, (III), was isolated only as a minor product in 10% yield.

S3. Refinement

H atoms were generated and refined as riding groups, with C—H = 0.93–0.98 Å and U_iso(H) = 1.2U_eq(carrier atom) or 1.5U_eq(methyl C).

Computing details

Data collection: PW1100 Software (Philips, 19??); cell refinement: PW1100 Software; data reduction: PW1100 Software; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CSU (Vicković, 1988).

Figures

	Fig. 1. A perspective view of the molecule of (II) with the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitary radii.
	Fig. 2. The superimposed fit for the molecules of (I) (dashed lines) and (II) (solid lines).

3-Methoxy-17α-hydroxy-17β-benzylestra-1,3,5(10)-trien-16-one

Crystal data

C26H30O3	Dx = 1.240 Mg m^−3
Mr = 390.50	Melting point = 385–387 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 20 reflections
a = 36.426 (9) Å	θ = 6.6–12.8°
b = 9.141 (1) Å	µ = 0.63 mm^−1
c = 6.281 (2) Å	T = 293 K
V = 2091.4 (9) Å^3	Prism, colourless
Z = 4	0.47 × 0.07 × 0.03 mm
F(000) = 840

Data collection

Philips PW1100 diffractometer	Rint = 0.066
Radiation source: fine-focus sealed tube	θmax = 70.0°, θmin = 4.9°
Graphite monochromator	h = −43→44
ω/2θ scans	k = 0→11
3923 measured reflections	l = 0→7
2222 independent reflections	3 standard reflections every 120 min
1827 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 0.2999] where P = (Fo^2 + 2Fc^2)/3
2222 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.19 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
O1	0.58133 (7)	0.4418 (3)	0.5603 (5)	0.0639 (8)
O2	0.30069 (6)	0.5030 (3)	0.5287 (4)	0.0432 (6)
HO2	0.2782	0.5023	0.5308	0.065*
C1	0.48718 (9)	0.5473 (4)	0.7025 (6)	0.0498 (9)
H1	0.4746	0.6048	0.8006	0.060*
C2	0.52519 (9)	0.5416 (4)	0.7138 (6)	0.0509 (9)
H2	0.5379	0.5958	0.8153	0.061*
C3	0.54382 (9)	0.4539 (4)	0.5709 (6)	0.0474 (8)
C4	0.52460 (9)	0.3744 (4)	0.4213 (6)	0.0471 (8)
H4	0.5374	0.3153	0.3263	0.056*
C5	0.48654 (9)	0.3804 (4)	0.4091 (6)	0.0436 (8)
C6	0.46726 (9)	0.2895 (4)	0.2410 (6)	0.0546 (10)
H61	0.4772	0.1912	0.2436	0.066*
H62	0.4725	0.3310	0.1020	0.066*
C7	0.42590 (9)	0.2811 (4)	0.2702 (7)	0.0498 (9)
H71	0.4201	0.2143	0.3854	0.060*
H72	0.4146	0.2441	0.1411	0.060*
C8	0.41064 (8)	0.4326 (3)	0.3208 (5)	0.0376 (7)
H8	0.4197	0.5012	0.2131	0.045*
C9	0.42534 (9)	0.4814 (4)	0.5396 (5)	0.0380 (7)
H9	0.4155	0.4129	0.6453	0.046*
C10	0.46702 (9)	0.4704 (4)	0.5501 (5)	0.0401 (7)
C11	0.41115 (9)	0.6352 (4)	0.6001 (6)	0.0435 (8)
H111	0.4186	0.6573	0.7448	0.052*
H112	0.4224	0.7070	0.5070	0.052*
C12	0.36936 (9)	0.6487 (4)	0.5834 (5)	0.0404 (7)
H121	0.3580	0.5888	0.6927	0.048*
H122	0.3623	0.7495	0.6087	0.048*
C13	0.35526 (8)	0.6011 (3)	0.3661 (5)	0.0320 (6)
C14	0.36903 (8)	0.4423 (3)	0.3255 (5)	0.0349 (6)
H13	0.3608	0.3834	0.4469	0.042*
C15	0.34640 (9)	0.3926 (4)	0.1328 (5)	0.0436 (8)
H151	0.3583	0.4199	0.0007	0.052*
H152	0.3428	0.2875	0.1345	0.052*
C16	0.31025 (8)	0.4725 (4)	0.1589 (5)	0.0387 (7)
C17	0.31324 (8)	0.5835 (3)	0.3442 (5)	0.0333 (6)
C18	0.36850 (9)	0.7067 (4)	0.1916 (6)	0.0437 (8)
H181	0.3946	0.7188	0.2022	0.066*
H182	0.3567	0.7999	0.2095	0.066*
H183	0.3624	0.6675	0.0543	0.066*
C19	0.28993 (8)	0.7185 (3)	0.3048 (5)	0.0378 (7)
H191	0.2644	0.6883	0.3022	0.045*
H192	0.2958	0.7554	0.1641	0.045*
C20	0.29345 (9)	0.8438 (3)	0.4608 (5)	0.0362 (7)
C21	0.30859 (9)	0.9771 (4)	0.3986 (6)	0.0433 (8)
H21	0.3179	0.9871	0.2615	0.052*
C22	0.31012 (10)	1.0955 (4)	0.5369 (7)	0.0537 (9)
H22	0.3204	1.1833	0.4920	0.064*
C23	0.29634 (9)	1.0831 (4)	0.7417 (7)	0.0514 (9)
H23	0.2971	1.1622	0.8346	0.062*
C24	0.28144 (9)	0.9514 (4)	0.8054 (6)	0.0458 (8)
H24	0.2722	0.9420	0.9428	0.055*
C25	0.28001 (9)	0.8331 (4)	0.6687 (6)	0.0403 (7)
H25	0.2700	0.7453	0.7156	0.048*
C26	0.60245 (10)	0.5170 (5)	0.7132 (8)	0.0676 (12)
H261	0.6280	0.4984	0.6886	0.101*
H262	0.5959	0.4838	0.8531	0.101*
H263	0.5978	0.6201	0.7022	0.101*
O3	0.28249 (6)	0.4515 (3)	0.0552 (5)	0.0579 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0421 (12)	0.0639 (16)	0.086 (2)	0.0100 (12)	−0.0096 (15)	−0.0129 (18)
O2	0.0432 (12)	0.0461 (13)	0.0403 (12)	−0.0033 (11)	0.0120 (11)	0.0142 (12)
C1	0.0457 (17)	0.061 (2)	0.0424 (17)	0.0036 (16)	−0.0030 (16)	−0.0186 (19)
C2	0.0495 (19)	0.054 (2)	0.0489 (19)	0.0033 (16)	−0.0065 (17)	−0.0102 (19)
C3	0.0414 (16)	0.0443 (17)	0.056 (2)	0.0067 (15)	−0.0051 (17)	0.0001 (19)
C4	0.0502 (19)	0.0439 (18)	0.0470 (19)	0.0124 (15)	0.0003 (16)	−0.0100 (18)
C5	0.0479 (17)	0.0367 (15)	0.0461 (18)	0.0050 (14)	−0.0008 (16)	−0.0051 (16)
C6	0.053 (2)	0.059 (2)	0.052 (2)	0.0113 (18)	−0.0046 (18)	−0.022 (2)
C7	0.0498 (19)	0.0421 (17)	0.058 (2)	0.0047 (15)	−0.0077 (18)	−0.0174 (19)
C8	0.0435 (16)	0.0355 (15)	0.0340 (15)	0.0030 (13)	−0.0011 (14)	−0.0088 (15)
C9	0.0447 (17)	0.0398 (16)	0.0295 (14)	0.0022 (13)	0.0025 (14)	−0.0052 (15)
C10	0.0401 (15)	0.0442 (16)	0.0358 (15)	0.0017 (14)	0.0005 (14)	−0.0025 (16)
C11	0.0438 (17)	0.0490 (19)	0.0378 (17)	0.0027 (14)	−0.0013 (15)	−0.0194 (17)
C12	0.0465 (17)	0.0456 (17)	0.0292 (15)	0.0003 (15)	−0.0005 (14)	−0.0079 (15)
C13	0.0388 (15)	0.0327 (14)	0.0246 (13)	−0.0064 (12)	0.0036 (13)	−0.0037 (13)
C14	0.0435 (15)	0.0333 (14)	0.0280 (14)	−0.0025 (13)	−0.0010 (14)	−0.0002 (14)
C15	0.0491 (17)	0.0423 (17)	0.0394 (17)	−0.0027 (15)	−0.0044 (16)	−0.0120 (16)
C16	0.0387 (16)	0.0388 (16)	0.0388 (16)	−0.0077 (14)	−0.0022 (14)	−0.0022 (16)
C17	0.0396 (15)	0.0322 (14)	0.0281 (14)	−0.0038 (12)	0.0035 (13)	0.0025 (14)
C18	0.0455 (17)	0.0406 (17)	0.0449 (18)	−0.0042 (15)	0.0144 (17)	0.0064 (17)
C19	0.0375 (15)	0.0395 (15)	0.0363 (16)	−0.0023 (13)	−0.0022 (14)	0.0003 (15)
C20	0.0387 (15)	0.0352 (14)	0.0346 (16)	0.0053 (13)	−0.0003 (14)	0.0035 (14)
C21	0.0428 (17)	0.0430 (17)	0.0441 (18)	−0.0053 (14)	0.0013 (15)	0.0063 (17)
C22	0.053 (2)	0.0410 (18)	0.067 (2)	−0.0052 (16)	−0.004 (2)	−0.002 (2)
C23	0.0448 (18)	0.0483 (19)	0.061 (2)	0.0093 (16)	−0.0105 (18)	−0.0138 (19)
C24	0.0434 (17)	0.0533 (19)	0.0406 (17)	0.0127 (16)	−0.0040 (16)	−0.0029 (18)
C25	0.0430 (16)	0.0382 (15)	0.0398 (17)	0.0047 (14)	0.0028 (15)	0.0027 (16)
C26	0.050 (2)	0.065 (2)	0.088 (3)	0.0043 (19)	−0.017 (2)	0.000 (3)
O3	0.0452 (13)	0.0674 (16)	0.0611 (16)	−0.0090 (12)	−0.0136 (13)	−0.0174 (16)

Geometric parameters (Å, º)

O1—C3	1.372 (4)	C13—C18	1.538 (4)
O1—C26	1.410 (5)	C13—C17	1.545 (4)
O2—C17	1.446 (4)	C13—C14	1.557 (4)
O2—HO2	0.8200	C14—C15	1.533 (4)
C1—C2	1.387 (5)	C14—H13	0.9800
C1—C10	1.396 (5)	C15—C16	1.515 (4)
C1—H1	0.9300	C15—H151	0.9700
C2—C3	1.382 (5)	C15—H152	0.9700
C2—H2	0.9300	C16—O3	1.218 (4)
C3—C4	1.379 (5)	C16—C17	1.548 (4)
C4—C5	1.390 (5)	C17—C19	1.518 (4)
C4—H4	0.9300	C18—H181	0.9600
C5—C10	1.403 (5)	C18—H182	0.9600
C5—C6	1.516 (5)	C18—H183	0.9600
C6—C7	1.520 (5)	C19—C20	1.513 (4)
C6—H61	0.9700	C19—H191	0.9700
C6—H62	0.9700	C19—H192	0.9700
C7—C8	1.526 (4)	C20—C21	1.394 (4)
C7—H71	0.9700	C20—C25	1.398 (5)
C7—H72	0.9700	C21—C22	1.388 (5)
C8—C14	1.519 (4)	C21—H21	0.9300
C8—C9	1.541 (4)	C22—C23	1.385 (6)
C8—H8	0.9800	C22—H22	0.9300
C9—C10	1.523 (4)	C23—C24	1.380 (5)
C9—C11	1.546 (4)	C23—H23	0.9300
C9—H9	0.9800	C24—C25	1.382 (5)
C11—C12	1.531 (4)	C24—H24	0.9300
C11—H111	0.9700	C25—H25	0.9300
C11—H112	0.9700	C26—H261	0.9600
C12—C13	1.522 (4)	C26—H262	0.9600
C12—H121	0.9700	C26—H263	0.9600
C12—H122	0.9700
C3—O1—C26	118.1 (3)	C18—C13—C14	111.6 (2)
C17—O2—HO2	109.5	C17—C13—C14	102.0 (2)
C2—C1—C10	122.7 (3)	C8—C14—C15	120.3 (3)
C2—C1—H1	118.6	C8—C14—C13	112.3 (2)
C10—C1—H1	118.6	C15—C14—C13	103.4 (2)
C3—C2—C1	118.6 (3)	C8—C14—H13	106.7
C3—C2—H2	120.7	C15—C14—H13	106.7
C1—C2—H2	120.7	C13—C14—H13	106.7
O1—C3—C4	115.5 (3)	C16—C15—C14	103.9 (3)
O1—C3—C2	124.6 (3)	C16—C15—H151	111.0
C4—C3—C2	119.9 (3)	C14—C15—H151	111.0
C3—C4—C5	121.5 (3)	C16—C15—H152	111.0
C3—C4—H4	119.2	C14—C15—H152	111.0
C5—C4—H4	119.2	H151—C15—H152	109.0
C4—C5—C10	119.6 (3)	O3—C16—C15	126.0 (3)
C4—C5—C6	118.6 (3)	O3—C16—C17	124.3 (3)
C10—C5—C6	121.8 (3)	C15—C16—C17	109.6 (3)
C5—C6—C7	113.8 (3)	O2—C17—C19	111.5 (3)
C5—C6—H61	108.8	O2—C17—C13	107.1 (2)
C7—C6—H61	108.8	C19—C17—C13	119.0 (2)
C5—C6—H62	108.8	O2—C17—C16	104.3 (2)
C7—C6—H62	108.8	C19—C17—C16	111.7 (3)
H61—C6—H62	107.7	C13—C17—C16	101.8 (2)
C6—C7—C8	109.9 (3)	C13—C18—H181	109.5
C6—C7—H71	109.7	C13—C18—H182	109.5
C8—C7—H71	109.7	H181—C18—H182	109.5
C6—C7—H72	109.7	C13—C18—H183	109.5
C8—C7—H72	109.7	H181—C18—H183	109.5
H71—C7—H72	108.2	H182—C18—H183	109.5
C14—C8—C7	114.9 (3)	C17—C19—C20	117.5 (3)
C14—C8—C9	108.2 (3)	C17—C19—H191	107.9
C7—C8—C9	108.8 (3)	C20—C19—H191	107.9
C14—C8—H8	108.3	C17—C19—H192	107.9
C7—C8—H8	108.3	C20—C19—H192	107.9
C9—C8—H8	108.3	H191—C19—H192	107.2
C10—C9—C8	111.5 (3)	C21—C20—C25	117.5 (3)
C10—C9—C11	112.5 (3)	C21—C20—C19	121.0 (3)
C8—C9—C11	111.5 (3)	C25—C20—C19	121.5 (3)
C10—C9—H9	107.0	C20—C21—C22	121.5 (3)
C8—C9—H9	107.0	C20—C21—H21	119.3
C11—C9—H9	107.0	C22—C21—H21	119.3
C1—C10—C5	117.5 (3)	C21—C22—C23	120.2 (4)
C1—C10—C9	121.4 (3)	C21—C22—H22	119.9
C5—C10—C9	121.1 (3)	C23—C22—H22	119.9
C12—C11—C9	112.9 (3)	C24—C23—C22	118.9 (4)
C12—C11—H111	109.0	C24—C23—H23	120.6
C9—C11—H111	109.0	C22—C23—H23	120.6
C12—C11—H112	109.0	C23—C24—C25	121.1 (3)
C9—C11—H112	109.0	C23—C24—H24	119.4
H111—C11—H112	107.8	C25—C24—H24	119.4
C13—C12—C11	111.9 (3)	C24—C25—C20	120.9 (3)
C13—C12—H121	109.2	C24—C25—H25	119.6
C11—C12—H121	109.2	C20—C25—H25	119.6
C13—C12—H122	109.2	O1—C26—H261	109.5
C11—C12—H122	109.2	O1—C26—H262	109.5
H121—C12—H122	107.9	H261—C26—H262	109.5
C12—C13—C18	110.7 (2)	O1—C26—H263	109.5
C12—C13—C17	116.3 (3)	H261—C26—H263	109.5
C18—C13—C17	108.2 (3)	H262—C26—H263	109.5
C12—C13—C14	107.8 (3)
C10—C1—C2—C3	−1.3 (6)	C12—C13—C14—C8	−61.7 (3)
C26—O1—C3—C4	−178.1 (3)	C18—C13—C14—C8	60.1 (4)
C26—O1—C3—C2	4.0 (6)	C17—C13—C14—C8	175.4 (3)
C1—C2—C3—O1	177.9 (4)	C12—C13—C14—C15	167.2 (2)
C1—C2—C3—C4	0.0 (6)	C18—C13—C14—C15	−71.1 (3)
O1—C3—C4—C5	−177.8 (3)	C17—C13—C14—C15	44.2 (3)
C2—C3—C4—C5	0.3 (6)	C8—C14—C15—C16	−158.0 (3)
C3—C4—C5—C10	0.7 (6)	C13—C14—C15—C16	−31.7 (3)
C3—C4—C5—C6	−179.8 (3)	C14—C15—C16—O3	−170.5 (3)
C4—C5—C6—C7	168.6 (3)	C14—C15—C16—C17	7.8 (4)
C10—C5—C6—C7	−12.0 (5)	C12—C13—C17—O2	−45.8 (3)
C5—C6—C7—C8	44.8 (5)	C18—C13—C17—O2	−171.1 (2)
C6—C7—C8—C14	172.5 (3)	C14—C13—C17—O2	71.1 (3)
C6—C7—C8—C9	−66.1 (4)	C12—C13—C17—C19	81.8 (4)
C14—C8—C9—C10	178.3 (3)	C18—C13—C17—C19	−43.5 (4)
C7—C8—C9—C10	52.9 (4)	C14—C13—C17—C19	−161.3 (3)
C14—C8—C9—C11	−55.1 (3)	C12—C13—C17—C16	−155.0 (3)
C7—C8—C9—C11	179.5 (3)	C18—C13—C17—C16	79.7 (3)
C2—C1—C10—C5	2.3 (6)	C14—C13—C17—C16	−38.0 (3)
C2—C1—C10—C9	−178.8 (4)	O3—C16—C17—O2	86.2 (4)
C4—C5—C10—C1	−1.9 (5)	C15—C16—C17—O2	−92.1 (3)
C6—C5—C10—C1	178.6 (3)	O3—C16—C17—C19	−34.5 (4)
C4—C5—C10—C9	179.2 (3)	C15—C16—C17—C19	147.3 (3)
C6—C5—C10—C9	−0.3 (5)	O3—C16—C17—C13	−162.5 (3)
C8—C9—C10—C1	160.6 (3)	C15—C16—C17—C13	19.3 (3)
C11—C9—C10—C1	34.5 (5)	O2—C17—C19—C20	70.4 (3)
C8—C9—C10—C5	−20.6 (4)	C13—C17—C19—C20	−55.1 (4)
C11—C9—C10—C5	−146.6 (3)	C16—C17—C19—C20	−173.3 (3)
C10—C9—C11—C12	178.2 (3)	C17—C19—C20—C21	113.0 (3)
C8—C9—C11—C12	52.2 (4)	C17—C19—C20—C25	−70.3 (4)
C9—C11—C12—C13	−53.1 (4)	C25—C20—C21—C22	−0.4 (5)
C11—C12—C13—C18	−66.6 (4)	C19—C20—C21—C22	176.4 (3)
C11—C12—C13—C17	169.4 (3)	C20—C21—C22—C23	−0.2 (5)
C11—C12—C13—C14	55.7 (3)	C21—C22—C23—C24	0.5 (5)
C7—C8—C14—C15	−55.0 (4)	C22—C23—C24—C25	−0.2 (5)
C9—C8—C14—C15	−176.7 (3)	C23—C24—C25—C20	−0.4 (5)
C7—C8—C14—C13	−177.0 (3)	C21—C20—C25—C24	0.7 (5)
C9—C8—C14—C13	61.3 (3)	C19—C20—C25—C24	−176.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—HO2···O3^i	0.82	2.25	3.063 (4)	168

Symmetry code: (i) −x+1/2, −y+1, z+1/2.