3,17-Dioxoandrost-4-en-4-yl acetate

The title compound, C₂₁H₂₈O₄, has a 4-acet­oxy substituent positioned on the steroid [alpha] face. The six-membered ring A assumes a conformation inter­mediate between 1[alpha],2[beta]-half chair and 1[alpha]-sofa. A long Csp³-Csp³ bond is observed in ring B and reproduced in quantum-mechanical ab initio calculations of the isolated mol­ecule using a mol­ecular-orbital Hartree-Fock method. Cohesion of the crystal can be attributed to van der Waals inter­actions and weak C-H...O hydrogen bonds.

S1. Comment

Following our interest in preparing steroidal enzymatic inhibitors aimed at breast cancer treatment, and in studying their structure–activity relationships (Cepa et al., 2005), the title compound, (I), which is the acetate derivative of formestane, was prepared as previously described in the literature (Marsh et al., 1985). We report here the molecular structure of (I) determined by single-crystal X-ray analysis, and compare it with that of the free molecule as given by quantum-mechanical ab initio calculations.

An ORTEPII (Johnson, 1976) plot of (I) is shown in Fig. 1. The 4-acetoxy substituent is positioned on the α face of the steroid nucleus. Average values for the atomic distances are in good agreement with reported ones (Allen et al., 1987), although for the Csp³—Csp³ bonds extreme values of 1.514 (3) (C12—C13) and 1.569 (3) Å (C9—C10) were found, deviating significantly from the average value of 1.535 (14) Å. The abnormally large value is probably due to the severe distortion of ring A (C1–C5/C10). A similar C9—C10 bond length was observed for one of the non-equivalent molecules in the asymmetric unit of formestane [1.571 (3) Å; Griffin et al., 1980].

As a consequence of the C4═C5 double bond present in ring A, this ring assumes a conformation intermediate between 1α,2β-half chair and 1α-sofa [asymmetry parameters (Duax & Norton, 1975) ΔC₂(1,2) = 12.5 (3)°, ΔC_s(1) = 13.7 (2)° and ΔC_s(3) = 45.1 (2)°]. Rings B (C5–C10) and C (C8/C9/C11–C14) have sightly distorted chair conformations with average torsion angles of 54.0 (18) and 55 (2)°, respectively. The five-membered ring D (C13–C17) has a 14α-conformation, most common for these 17-one steroids [puckering parameters (Cremer & Pople, 1975) q₂ = 0.417 (3) Å and ϕ₂ = 215.6 (4)°; pseudo-rotation (Altona et al., 1968) and asymmetry parameters (Duax & Norton, 1975): Δ = -34.4 (4)°, ϕ_m = 42.7 (1)°, ΔC_s(14) = 0.7 (2)°, ΔC₂(13,14) = 20.0 (2)°]. The distance between terminal atoms O3 and O17 is 10.564 (2) Å. The C19—C10···C13—C18 pseudo-torsion angle of -0.06 (19)° indicates that the molecule is not twisted. The dihedral angle between the least-squares plane of the four non-H atoms of the acetate group and that of ring A is 79.78 (10)°.

In order to check whether the observed large deviations from the mean of the C9—C10 and C12—C13 bond lengths were intrinsic to the free steroid molecule or rather due to an influence of crystal packing, we have performed a quantum chemical calculation of the equilibrium geometry of the free molecule. These calculations were performed with the computer program GAMESS (Schmidt et al., 1993). A molecular orbital Roothan Hartree–Fock method was used with an extended 6–31 G(d,p) basis set. Tight conditions for convergence of both the self-consistent field cycles and the maximum density and energy gradients were imposed (10^-5 atomic units). The programs were run on a Pentium IV PC (3.0 GHz) running Linux. Interestingly, the calculations reproduce the long C9—C10 bond [calculated value 1.570 Å]. For the shorter Csp³—Csp³ bond, the calculations give a slightly higher value than the observed one [calculated value 1.526 Å]. Overall, there is a very good agreement between the remaining calculated and observed bond lengths. However, the equilibrium geometry of the isolated molecule has a significantly more twisted steroid nucleus [calculated pseudo-torsion angle C19—C10···C13—C18 = 4.9°]. There is considerable freedom of rotation of the acetoxy group around the C4—O4 and O4—C41 bonds, as evidenced by the torsion angles C3—C4—O4—C41 [experimental 80.0 (2)°; calculated 77.0°] and C4—O4—C41—O41 [experimental 0.4 (4)°; calculated 15.4°].

Owing to the absence of a strong hydrogen-bond donor, cohesion of the structure of (I) is mainly achieved by van der Waals and weak C—H···O interactions. One intramolecular C—H···O short contact between the single-bonded O atom of the 4-acetoxy group and a neighbouring H atom of ring B is present, C6—H6A···O4 = 2.808 (5) Å. There are, in addition, two intermolecular C—H···O short distances of 3.357 (6) and 3.459 (6) Å between H atoms of rings B and C and O atoms.

Related literature

For related literature, see: Allen et al. (1987); Altona et al. (1968); Cepa et al. (2005); Cremer & Pople (1975); Duax & Norton (1975); Griffin et al. (1980); Johnson (1976); Marsh et al. (1985); Schmidt et al. (1993).

S2. Experimental

To an ice-cooled solution of formestane (0.3 g, 0.99 mmol) in pyridine (5.0 ml), acetyl chloride (0.11 ml, 1.48 mmol) was added, and the reaction was stirred for 3 h until completion. Dichloromethane (100 ml) was then added, and the organic layer was washed with aqueous 0.25 N HCl (2 × 100 ml), 10% NaHCO₃ (2 × 100 ml) and water (2 × 100 ml), dried over anhydrous MgSO₄ and evaporated to dryness giving the desired title compound as a yellow crystalline solid (yield 0.335 g, 98%). Crystals of (I) of good quality suitable for X-ray crystallographic analysis were grown from ethyl acetate [m.p. 457–458 K; literature value 457–457.5 K (Marsh et al., 1985)]. IR (Medium?, ν, cm^-1): 1758, 1735, 1681, 1625; ¹H NMR (CDCl₃, δ, p.p.m.): 0.91 (s, 3H, 18-H₃), 1.27 (s, 3H, 19-H₃), 2.24 [s, 3H, CH₃C(O)O], 2.73 (ddd, 1H, J_6α-6β = 15.0 Hz, J_6α-7α = 4.0 Hz, J_6α-7β = 2.5 Hz, 6α-H).

S3. Refinement

All H atoms were refined as riding on their parent atoms, with C—H = 0.96–0.98 Å and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for methyl H. [Please check added text] The absolute configuration was not determined from the X-ray data but was known from the synthesis route. Friedel pairs were merged before refinement.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: PLATON (Spek, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A plot of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

3,17-Dioxoandrost-4-en-4-yl acetate

Crystal data

C21H28O4	Dx = 1.213 Mg m^−3
Mr = 344.43	Melting point: 457.5(5) K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 11.5681 (3) Å	θ = 16.4–26.9°
b = 12.0702 (3) Å	µ = 0.66 mm^−1
c = 13.512 (2) Å	T = 294 K
V = 1886.6 (3) Å^3	Prism, colourless
Z = 4	0.36 × 0.17 × 0.17 mm
F(000) = 744

Data collection

Enraf–Nonius MACH-3 diffractometer	1795 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 73.8°, θmin = 4.9°
profile data from ω–2θ scans	h = −14→14
Absorption correction: ψ scan (North et al., 1968)	k = −6→15
Tmin = 0.851, Tmax = 0.890	l = −16→16
3577 measured reflections	3 standard reflections every 300 min
2135 independent reflections	intensity decay: 2.2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 0.3523P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.025
2128 reflections	Δρmax = 0.16 e Å^−3
230 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0095 (6)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O3	0.16071 (19)	0.83111 (14)	0.70155 (15)	0.0703 (6)
O4	0.01306 (13)	0.69137 (13)	0.60928 (11)	0.0478 (4)
O17	0.43619 (16)	0.00475 (15)	0.59791 (15)	0.0676 (5)
O41	0.14471 (17)	0.7197 (2)	0.49048 (14)	0.0755 (6)
C1	0.30303 (18)	0.57501 (18)	0.7628 (2)	0.0483 (6)
H1A	0.3546	0.5482	0.8141	0.058*
H1B	0.3476	0.5818	0.7022	0.058*
C2	0.2583 (2)	0.6892 (2)	0.7922 (2)	0.0572 (6)
H2A	0.2211	0.6846	0.8564	0.069*
H2B	0.3228	0.7402	0.7978	0.069*
C3	0.1739 (2)	0.73266 (18)	0.71761 (18)	0.0487 (5)
C4	0.10241 (18)	0.64852 (18)	0.66895 (16)	0.0417 (5)
C5	0.10965 (18)	0.53964 (17)	0.68459 (16)	0.0398 (5)
C6	0.02065 (19)	0.46203 (19)	0.6436 (2)	0.0506 (6)
H6A	−0.0273	0.5018	0.5967	0.061*
H6B	−0.0287	0.4368	0.6970	0.061*
C7	0.0733 (2)	0.3617 (2)	0.5922 (2)	0.0548 (6)
H7A	0.1094	0.3852	0.5309	0.066*
H7B	0.0124	0.3096	0.5759	0.066*
C8	0.16294 (18)	0.30427 (17)	0.65691 (17)	0.0419 (5)
H8	0.1251	0.2762	0.7167	0.050*
C9	0.25714 (17)	0.38909 (16)	0.68698 (15)	0.0379 (4)
H9	0.2870	0.4201	0.6250	0.046*
C10	0.20659 (17)	0.48954 (17)	0.74670 (16)	0.0383 (4)
C11	0.36155 (19)	0.33567 (18)	0.73938 (18)	0.0457 (5)
H11A	0.4223	0.3906	0.7457	0.055*
H11B	0.3385	0.3137	0.8056	0.055*
C12	0.41010 (18)	0.23401 (19)	0.68508 (19)	0.0473 (5)
H12A	0.4450	0.2571	0.6231	0.057*
H12B	0.4695	0.1995	0.7252	0.057*
C13	0.31464 (18)	0.15127 (18)	0.66461 (16)	0.0421 (5)
C14	0.22060 (18)	0.20822 (18)	0.60298 (17)	0.0440 (5)
H14	0.2603	0.2409	0.5459	0.053*
C15	0.1488 (2)	0.1118 (2)	0.5620 (2)	0.0603 (7)
H15A	0.1044	0.1344	0.5046	0.072*
H15B	0.0967	0.0826	0.6118	0.072*
C16	0.2418 (2)	0.0265 (2)	0.5341 (2)	0.0628 (7)
H16A	0.2147	−0.0482	0.5467	0.075*
H16B	0.2619	0.0328	0.4646	0.075*
C17	0.3454 (2)	0.05331 (19)	0.59882 (19)	0.0503 (5)
C18	0.2694 (3)	0.0988 (2)	0.76160 (19)	0.0583 (7)
H18A	0.3318	0.0623	0.7951	0.087*
H18B	0.2100	0.0459	0.7464	0.087*
H18C	0.2382	0.1557	0.8034	0.087*
C19	0.1564 (2)	0.4529 (2)	0.84711 (17)	0.0529 (6)
H19A	0.1259	0.5163	0.8812	0.079*
H19B	0.2162	0.4197	0.8863	0.079*
H19C	0.0956	0.4001	0.8364	0.079*
C41	0.0471 (2)	0.7260 (2)	0.51771 (18)	0.0501 (6)
C42	−0.0518 (3)	0.7691 (3)	0.4599 (2)	0.0684 (8)
H42A	−0.0444	0.8479	0.4525	0.103*
H42B	−0.1226	0.7524	0.4938	0.103*
H42C	−0.0526	0.7349	0.3957	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0844 (13)	0.0391 (8)	0.0872 (14)	0.0084 (9)	0.0022 (12)	−0.0050 (9)
O4	0.0459 (8)	0.0518 (8)	0.0457 (8)	0.0133 (7)	0.0034 (7)	0.0097 (7)
O17	0.0640 (11)	0.0637 (11)	0.0753 (12)	0.0153 (9)	0.0043 (10)	−0.0155 (10)
O41	0.0620 (11)	0.1170 (18)	0.0476 (10)	0.0101 (13)	0.0109 (9)	0.0080 (11)
C1	0.0406 (11)	0.0453 (12)	0.0590 (14)	−0.0004 (9)	−0.0086 (11)	−0.0013 (11)
C2	0.0543 (13)	0.0484 (12)	0.0688 (16)	−0.0013 (11)	−0.0109 (13)	−0.0129 (12)
C3	0.0485 (12)	0.0410 (11)	0.0567 (14)	0.0050 (10)	0.0101 (11)	−0.0031 (10)
C4	0.0382 (10)	0.0451 (11)	0.0418 (11)	0.0067 (9)	0.0021 (9)	0.0047 (10)
C5	0.0350 (9)	0.0446 (11)	0.0398 (11)	0.0012 (9)	0.0031 (9)	0.0041 (9)
C6	0.0376 (11)	0.0483 (12)	0.0660 (15)	0.0013 (10)	−0.0098 (11)	0.0055 (11)
C7	0.0446 (12)	0.0533 (13)	0.0666 (15)	−0.0013 (10)	−0.0186 (12)	−0.0031 (12)
C8	0.0360 (9)	0.0411 (10)	0.0485 (12)	−0.0033 (9)	−0.0032 (9)	0.0026 (9)
C9	0.0350 (9)	0.0393 (10)	0.0395 (11)	−0.0013 (8)	−0.0009 (9)	0.0057 (9)
C10	0.0369 (10)	0.0405 (10)	0.0377 (10)	0.0000 (8)	−0.0025 (9)	0.0036 (9)
C11	0.0401 (11)	0.0450 (11)	0.0522 (13)	0.0026 (9)	−0.0094 (10)	−0.0034 (10)
C12	0.0378 (10)	0.0495 (12)	0.0545 (13)	0.0034 (9)	−0.0045 (10)	0.0001 (11)
C13	0.0441 (11)	0.0413 (10)	0.0409 (11)	0.0016 (9)	0.0020 (9)	0.0027 (9)
C14	0.0426 (11)	0.0444 (11)	0.0449 (11)	−0.0035 (9)	−0.0028 (10)	0.0011 (10)
C15	0.0528 (14)	0.0559 (14)	0.0723 (17)	−0.0050 (12)	−0.0117 (13)	−0.0118 (13)
C16	0.0670 (15)	0.0524 (14)	0.0689 (17)	−0.0026 (14)	−0.0067 (15)	−0.0165 (13)
C17	0.0553 (13)	0.0454 (12)	0.0504 (13)	0.0008 (11)	0.0042 (12)	0.0011 (11)
C18	0.0737 (17)	0.0504 (13)	0.0508 (14)	0.0011 (13)	0.0101 (13)	0.0089 (11)
C19	0.0562 (13)	0.0580 (14)	0.0444 (12)	0.0072 (12)	0.0062 (11)	0.0088 (11)
C41	0.0591 (14)	0.0514 (13)	0.0396 (12)	0.0082 (12)	0.0021 (11)	−0.0007 (10)
C42	0.0817 (19)	0.0746 (18)	0.0490 (14)	0.0250 (16)	−0.0076 (14)	0.0031 (13)

Geometric parameters (Å, º)

O3—C3	1.218 (3)	C10—C19	1.541 (3)
O4—C41	1.364 (3)	C11—C12	1.536 (3)
O4—C4	1.409 (3)	C11—H11A	0.9700
O41—C41	1.190 (3)	C11—H11B	0.9700
O17—C17	1.203 (3)	C12—C13	1.514 (3)
C1—C2	1.525 (3)	C12—H12A	0.9700
C1—C10	1.535 (3)	C12—H12B	0.9700
C1—H1A	0.9700	C13—C17	1.521 (3)
C1—H1B	0.9700	C13—C14	1.533 (3)
C2—C3	1.498 (3)	C13—C18	1.547 (3)
C2—H2A	0.9700	C14—C15	1.533 (3)
C2—H2B	0.9700	C14—H14	0.9800
C3—C4	1.465 (3)	C15—C16	1.536 (4)
C4—C5	1.334 (3)	C15—H15A	0.9700
C5—C6	1.498 (3)	C15—H15B	0.9700
C5—C10	1.526 (3)	C16—C17	1.518 (4)
C6—C7	1.522 (3)	C16—H16A	0.9700
C6—H6A	0.9700	C16—H16B	0.9700
C6—H6B	0.9700	C18—H18A	0.9600
C7—C8	1.523 (3)	C18—H18B	0.9600
C7—H7A	0.9700	C18—H18C	0.9600
C7—H7B	0.9700	C19—H19A	0.9600
C8—C14	1.523 (3)	C19—H19B	0.9600
C8—C9	1.549 (3)	C19—H19C	0.9600
C8—H8	0.9800	C41—C42	1.480 (3)
C9—C11	1.541 (3)	C42—H42A	0.9600
C9—C10	1.569 (3)	C42—H42B	0.9600
C9—H9	0.9800	C42—H42C	0.9600
C41—O4—C4	114.84 (17)	C9—C11—H11B	108.8
C2—C1—C10	113.44 (18)	H11A—C11—H11B	107.7
C2—C1—H1A	108.9	C13—C12—C11	110.33 (17)
C10—C1—H1A	108.9	C13—C12—H12A	109.6
C2—C1—H1B	108.9	C11—C12—H12A	109.6
C10—C1—H1B	108.9	C13—C12—H12B	109.6
H1A—C1—H1B	107.7	C11—C12—H12B	109.6
C3—C2—C1	111.2 (2)	H12A—C12—H12B	108.1
C3—C2—H2A	109.4	C12—C13—C17	116.68 (19)
C1—C2—H2A	109.4	C12—C13—C14	108.73 (17)
C3—C2—H2B	109.4	C17—C13—C14	101.35 (17)
C1—C2—H2B	109.4	C12—C13—C18	111.2 (2)
H2A—C2—H2B	108.0	C17—C13—C18	104.83 (18)
O3—C3—C4	121.7 (2)	C14—C13—C18	113.80 (19)
O3—C3—C2	122.9 (2)	C8—C14—C13	113.10 (18)
C4—C3—C2	115.29 (19)	C8—C14—C15	120.89 (18)
C5—C4—O4	119.9 (2)	C13—C14—C15	103.89 (18)
C5—C4—C3	125.2 (2)	C8—C14—H14	106.0
O4—C4—C3	114.60 (18)	C13—C14—H14	106.0
C4—C5—C6	121.0 (2)	C15—C14—H14	106.0
C4—C5—C10	121.6 (2)	C14—C15—C16	102.60 (18)
C6—C5—C10	117.43 (18)	C14—C15—H15A	111.2
C5—C6—C7	113.01 (18)	C16—C15—H15A	111.2
C5—C6—H6A	109.0	C14—C15—H15B	111.2
C7—C6—H6A	109.0	C16—C15—H15B	111.2
C5—C6—H6B	109.0	H15A—C15—H15B	109.2
C7—C6—H6B	109.0	C17—C16—C15	105.55 (19)
H6A—C6—H6B	107.8	C17—C16—H16A	110.6
C6—C7—C8	111.9 (2)	C15—C16—H16A	110.6
C6—C7—H7A	109.2	C17—C16—H16B	110.6
C8—C7—H7A	109.2	C15—C16—H16B	110.6
C6—C7—H7B	109.2	H16A—C16—H16B	108.8
C8—C7—H7B	109.2	O17—C17—C16	125.4 (2)
H7A—C7—H7B	107.9	O17—C17—C13	126.0 (2)
C7—C8—C14	111.73 (19)	C16—C17—C13	108.6 (2)
C7—C8—C9	109.17 (17)	C13—C18—H18A	109.5
C14—C8—C9	108.69 (16)	C13—C18—H18B	109.5
C7—C8—H8	109.1	H18A—C18—H18B	109.5
C14—C8—H8	109.1	C13—C18—H18C	109.5
C9—C8—H8	109.1	H18A—C18—H18C	109.5
C11—C9—C8	113.28 (16)	H18B—C18—H18C	109.5
C11—C9—C10	112.26 (17)	C10—C19—H19A	109.5
C8—C9—C10	112.53 (16)	C10—C19—H19B	109.5
C11—C9—H9	106.0	H19A—C19—H19B	109.5
C8—C9—H9	106.0	C10—C19—H19C	109.5
C10—C9—H9	106.0	H19A—C19—H19C	109.5
C5—C10—C1	110.22 (17)	H19B—C19—H19C	109.5
C5—C10—C19	108.71 (17)	O41—C41—O4	122.3 (2)
C1—C10—C19	110.0 (2)	O41—C41—C42	126.4 (2)
C5—C10—C9	107.30 (16)	O4—C41—C42	111.3 (2)
C1—C10—C9	108.73 (16)	C41—C42—H42A	109.5
C19—C10—C9	111.83 (17)	C41—C42—H42B	109.5
C12—C11—C9	113.65 (18)	H42A—C42—H42B	109.5
C12—C11—H11A	108.8	C41—C42—H42C	109.5
C9—C11—H11A	108.8	H42A—C42—H42C	109.5
C12—C11—H11B	108.8	H42B—C42—H42C	109.5
C10—C1—C2—C3	−56.0 (3)	C8—C9—C10—C1	−173.61 (18)
C1—C2—C3—O3	−150.6 (2)	C11—C9—C10—C19	−64.5 (2)
C1—C2—C3—C4	33.0 (3)	C8—C9—C10—C19	64.7 (2)
C41—O4—C4—C5	−106.1 (2)	C8—C9—C11—C12	48.8 (2)
C41—O4—C4—C3	80.0 (2)	C10—C9—C11—C12	177.61 (18)
O3—C3—C4—C5	−178.2 (2)	C9—C11—C12—C13	−52.8 (3)
C2—C3—C4—C5	−1.7 (3)	C11—C12—C13—C17	171.83 (19)
O3—C3—C4—O4	−4.7 (3)	C11—C12—C13—C14	58.1 (2)
C2—C3—C4—O4	171.77 (19)	C11—C12—C13—C18	−68.0 (2)
O4—C4—C5—C6	−3.0 (3)	C7—C8—C14—C13	177.81 (19)
C3—C4—C5—C6	170.2 (2)	C9—C8—C14—C13	57.3 (2)
O4—C4—C5—C10	178.55 (17)	C7—C8—C14—C15	−58.2 (3)
C3—C4—C5—C10	−8.3 (3)	C9—C8—C14—C15	−178.7 (2)
C4—C5—C6—C7	132.7 (2)	C12—C13—C14—C8	−63.0 (2)
C10—C5—C6—C7	−48.7 (3)	C17—C13—C14—C8	173.56 (17)
C5—C6—C7—C8	50.7 (3)	C18—C13—C14—C8	61.6 (2)
C6—C7—C8—C14	−176.56 (18)	C12—C13—C14—C15	164.16 (19)
C6—C7—C8—C9	−56.3 (2)	C17—C13—C14—C15	40.7 (2)
C7—C8—C9—C11	−171.32 (19)	C18—C13—C14—C15	−71.3 (2)
C14—C8—C9—C11	−49.2 (2)	C8—C14—C15—C16	−169.1 (2)
C7—C8—C9—C10	60.0 (2)	C13—C14—C15—C16	−40.9 (3)
C14—C8—C9—C10	−177.90 (17)	C14—C15—C16—C17	24.5 (3)
C4—C5—C10—C1	−14.1 (3)	C15—C16—C17—O17	−179.5 (3)
C6—C5—C10—C1	167.4 (2)	C15—C16—C17—C13	0.6 (3)
C4—C5—C10—C19	106.6 (2)	C12—C13—C17—O17	36.9 (3)
C6—C5—C10—C19	−72.0 (2)	C14—C13—C17—O17	154.7 (2)
C4—C5—C10—C9	−132.3 (2)	C18—C13—C17—O17	−86.6 (3)
C6—C5—C10—C9	49.2 (2)	C12—C13—C17—C16	−143.2 (2)
C2—C1—C10—C5	45.7 (3)	C14—C13—C17—C16	−25.3 (2)
C2—C1—C10—C19	−74.2 (3)	C18—C13—C17—C16	93.3 (2)
C2—C1—C10—C9	163.0 (2)	C4—O4—C41—O41	0.4 (4)
C11—C9—C10—C5	176.38 (17)	C4—O4—C41—C42	179.7 (2)
C8—C9—C10—C5	−54.4 (2)	C19—C10—C13—C18	−0.06 (19)
C11—C9—C10—C1	57.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O4	0.97	2.34	2.808 (3)	109
C6—H6B···O3^i	0.97	2.42	3.358 (3)	164
C11—H11B···O41^ii	0.97	2.54	3.459 (3)	159

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1/2, −y+1, z+1/2.