6β-Methyl-3,20-dioxopregn-4-en-17-yl acetate

Abstract

The title compound, C₂₄H₃₄O₄, is a precursor of Megestrol acetate. Ring A has a half-chair conformation [Q = 0.446 (3) Å, θ = 54.6 (4)° and ϕ = 9.5 (4)°]. Ring D adopts a 13β-envelope conformation [Q = 0.463 (2) Å and ϕ = 188.2 (3)°].

Related literature  

For the characterization of related structures, see: Evans & Boeyens (1989 ▶). Soriano-Garcia et al. (2005 ▶). Yousuf et al. (2011 ▶). For the physiological properties of the title compound, see: Mishell (1996 ▶).

Experimental  

Crystal data  

• C₂₄H₃₄O₄

• M _r = 386.51

• Orthorhombic,

• a = 10.0411 (3) Å

• b = 11.3123 (3) Å

• c = 18.5549 (7) Å

• V = 2107.61 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 296 K

• 0.56 × 0.52 × 0.31 mm

Data collection  

• Rigaku R-AXIS RAPID/ZJUG diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.946, T _max = 0.975

• 20014 measured reflections

• 2679 independent reflections

• 2108 reflections with I > 2σ(I)

• R _int = 0.035

Refinement  

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.102

• S = 1.00

• 2679 reflections

• 259 parameters

• H-atom parameters constrained

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

6β-methyl-3,20-dioxopregn-4-ene-17-yl acetate and its derivatives (for example, Megestrol acetate) are important progestines used for the treatment of endomentriosis as well as several other applications (Mishell, 1996).

The structure of the title compound is depicted in Fig.1. Ring A (C1—C5, C10) has a slightly distorted half-chair conformation with Q (total puckering amplitude) = 0.446 (3) Å, theta (azimuthal angle) = 54.6 (4) °, φ (phase angle) = 9.5 (4) °, while ring B (C5—C10) and C (C8,C9, C11—C14) are in chair conformation [ring B: Q = 0.521 (2) Å, theta = 12.7 (2) °, φ = 188.7 (13) °; ring C: Q = 0.564 (2) Å, theta = 2.8 (2) °, φ = 267 (4) °] (Evans & Boeyens, 1989). The five-membered ring D exhibits a 13β-envelope conformation with puckering amplitude Q = 0.463 (2) Å and phase angle= 188.2 (3) °. The crystals are isomorphous to 17alpha-Acetoxy-6-methylene-4-pregnene-3,20-dione (Soriano-Garcia et al., 2005). The crystal structure is also similar to 3alpha-Dimethylamino-20-(N-methylacetamido)pregn-5-ene (Yousuf et al., 2011).

Experimental

The title compound was received from Shanghai Xinhualian Pharmaceutical Co., Ltd. Suitable crystals were obtained by slow evaporation of its ethanol solution at room temperature.

Refinement

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.98 Å and U_iso(H) = 1.5U_eq(C), but each group was allowed to rotate freely about its C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.98 Å and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level.

Crystal data

C24H34O4	F(000) = 840
Mr = 386.51	Dx = 1.218 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 14918 reflections
a = 10.0411 (3) Å	θ = 3.0–27.4°
b = 11.3123 (3) Å	µ = 0.08 mm−1
c = 18.5549 (7) Å	T = 296 K
V = 2107.61 (12) Å3	Chunk, colorless
Z = 4	0.56 × 0.52 × 0.31 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer	2679 independent reflections
Radiation source: rolling anode	2108 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 10.00 pixels mm-1	θmax = 27.4°, θmin = 3.0°
ω scans	h = −12→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
Tmin = 0.946, Tmax = 0.975	l = −24→24
20014 measured reflections

Refinement

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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0441P)2 + 0.5695P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
2679 reflections	Δρmax = 0.17 e Å−3
259 parameters	Δρmin = −0.16 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0057 (12)

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	0.9284 (2)	−0.06142 (15)	0.53897 (13)	0.0759 (7)
O2	0.6725 (3)	0.92350 (17)	0.70081 (12)	0.0713 (6)
O3	0.49550 (16)	0.66587 (14)	0.65423 (9)	0.0439 (4)
O4	0.3669 (2)	0.82806 (18)	0.65415 (12)	0.0655 (6)
C1	0.8845 (3)	0.1906 (2)	0.65614 (14)	0.0475 (6)
H1A	0.9083	0.2115	0.7052	0.057*
H1B	0.7889	0.1785	0.6547	0.057*
C2	0.9537 (3)	0.0745 (2)	0.63640 (16)	0.0572 (7)
H2A	1.0487	0.0825	0.6445	0.069*
H2B	0.9210	0.0120	0.6676	0.069*
C3	0.9299 (3)	0.0410 (2)	0.55974 (17)	0.0533 (7)
C4	0.9105 (3)	0.1385 (2)	0.50972 (15)	0.0499 (6)
H4	0.8976	0.1195	0.4615	0.060*
C5	0.9097 (2)	0.2534 (2)	0.52737 (13)	0.0407 (5)
C6	0.8994 (3)	0.3438 (2)	0.46795 (14)	0.0461 (6)
H6	0.8611	0.3028	0.4263	0.055*
C7	0.8027 (3)	0.4433 (2)	0.48694 (13)	0.0447 (6)
H7A	0.8107	0.5055	0.4512	0.054*
H7B	0.7124	0.4130	0.4848	0.054*
C8	0.8270 (2)	0.49588 (19)	0.56153 (12)	0.0368 (5)
H8	0.9157	0.5320	0.5629	0.044*
C9	0.8186 (2)	0.39747 (19)	0.61904 (12)	0.0373 (5)
H9	0.7299	0.3622	0.6139	0.045*
C10	0.9205 (2)	0.29462 (19)	0.60597 (13)	0.0388 (5)
C11	0.8245 (3)	0.4476 (2)	0.69591 (12)	0.0441 (6)
H11A	0.8099	0.3838	0.7299	0.053*
H11B	0.9129	0.4791	0.7045	0.053*
C12	0.7216 (3)	0.5454 (2)	0.71000 (13)	0.0443 (6)
H12A	0.6327	0.5120	0.7083	0.053*
H12B	0.7354	0.5779	0.7578	0.053*
C13	0.7333 (2)	0.64437 (19)	0.65394 (13)	0.0362 (5)
C14	0.7224 (2)	0.58932 (19)	0.57819 (12)	0.0360 (5)
H14	0.6363	0.5487	0.5768	0.043*
C15	0.7092 (3)	0.69619 (19)	0.52808 (13)	0.0436 (6)
H15A	0.6611	0.6753	0.4846	0.052*
H15B	0.7961	0.7267	0.5149	0.052*
C16	0.6308 (3)	0.7875 (2)	0.57264 (13)	0.0441 (6)
H16A	0.5437	0.8007	0.5515	0.053*
H16B	0.6782	0.8622	0.5740	0.053*
C17	0.6167 (2)	0.7366 (2)	0.64927 (13)	0.0393 (5)
C22	1.0348 (3)	0.3910 (3)	0.44369 (17)	0.0646 (8)
H18A	1.0727	0.4386	0.4814	0.097*
H18B	1.0237	0.4383	0.4011	0.097*
H18C	1.0931	0.3260	0.4334	0.097*
C19	1.0656 (2)	0.3338 (2)	0.62124 (16)	0.0507 (6)
H19A	1.0760	0.3491	0.6718	0.076*
H19B	1.0848	0.4045	0.5945	0.076*
H19C	1.1257	0.2723	0.6068	0.076*
C18	0.8651 (3)	0.7121 (2)	0.66410 (15)	0.0493 (6)
H20A	0.8674	0.7463	0.7114	0.074*
H20B	0.8715	0.7735	0.6286	0.074*
H20C	0.9386	0.6585	0.6586	0.074*
C20	0.6198 (3)	0.8284 (2)	0.70979 (15)	0.0507 (6)
C21	0.5662 (4)	0.7928 (3)	0.78251 (15)	0.0689 (9)
H22A	0.6221	0.8248	0.8197	0.103*
H22B	0.5651	0.7081	0.7861	0.103*
H22C	0.4773	0.8227	0.7880	0.103*
C23	0.3771 (3)	0.7220 (3)	0.65162 (15)	0.0502 (6)
C24	0.2663 (3)	0.6356 (3)	0.6461 (2)	0.0717 (9)
H24A	0.1828	0.6766	0.6486	0.108*
H24B	0.2722	0.5800	0.6851	0.108*
H24C	0.2724	0.5943	0.6010	0.108*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0979 (17)	0.0353 (10)	0.0944 (16)	−0.0064 (10)	0.0245 (14)	−0.0033 (10)
O2	0.0876 (16)	0.0496 (11)	0.0766 (14)	−0.0048 (11)	0.0016 (13)	−0.0149 (10)
O3	0.0355 (9)	0.0459 (9)	0.0503 (9)	0.0016 (7)	0.0036 (8)	0.0031 (8)
O4	0.0601 (12)	0.0629 (12)	0.0734 (13)	0.0205 (10)	0.0049 (12)	0.0007 (11)
C1	0.0506 (14)	0.0424 (12)	0.0495 (14)	0.0014 (11)	0.0012 (13)	0.0087 (11)
C2	0.0604 (17)	0.0420 (13)	0.0692 (19)	0.0045 (12)	0.0028 (14)	0.0098 (13)
C3	0.0484 (15)	0.0385 (13)	0.0729 (19)	−0.0019 (11)	0.0133 (14)	0.0025 (13)
C4	0.0523 (16)	0.0423 (13)	0.0552 (15)	−0.0034 (11)	0.0058 (13)	−0.0045 (11)
C5	0.0352 (13)	0.0393 (11)	0.0474 (13)	−0.0006 (10)	0.0043 (11)	0.0000 (10)
C6	0.0541 (15)	0.0419 (12)	0.0424 (13)	0.0001 (11)	0.0059 (12)	−0.0013 (10)
C7	0.0543 (15)	0.0425 (12)	0.0373 (12)	0.0042 (12)	0.0007 (11)	0.0025 (10)
C8	0.0384 (12)	0.0354 (11)	0.0365 (12)	−0.0014 (9)	0.0027 (10)	0.0020 (9)
C9	0.0364 (12)	0.0365 (11)	0.0389 (12)	−0.0004 (9)	0.0011 (10)	0.0024 (9)
C10	0.0379 (13)	0.0354 (11)	0.0432 (13)	−0.0005 (10)	0.0006 (10)	0.0024 (10)
C11	0.0502 (14)	0.0445 (13)	0.0377 (12)	0.0076 (11)	0.0003 (11)	0.0037 (10)
C12	0.0511 (15)	0.0468 (13)	0.0350 (12)	0.0062 (11)	0.0044 (11)	0.0055 (10)
C13	0.0370 (12)	0.0376 (11)	0.0341 (11)	0.0020 (9)	0.0009 (10)	0.0020 (9)
C14	0.0389 (12)	0.0350 (11)	0.0341 (12)	−0.0006 (9)	−0.0001 (10)	0.0038 (9)
C15	0.0525 (14)	0.0392 (12)	0.0390 (12)	0.0024 (11)	0.0031 (11)	0.0067 (10)
C16	0.0476 (14)	0.0396 (12)	0.0452 (13)	0.0045 (11)	0.0028 (11)	0.0075 (10)
C17	0.0389 (12)	0.0382 (11)	0.0407 (12)	−0.0004 (10)	0.0004 (11)	−0.0006 (10)
C22	0.070 (2)	0.0561 (16)	0.0677 (19)	0.0004 (14)	0.0255 (16)	0.0074 (15)
C19	0.0370 (13)	0.0499 (14)	0.0651 (17)	0.0009 (11)	−0.0039 (12)	−0.0018 (13)
C18	0.0437 (14)	0.0479 (13)	0.0563 (16)	−0.0037 (11)	−0.0046 (12)	−0.0065 (12)
C20	0.0540 (15)	0.0480 (14)	0.0502 (15)	0.0101 (13)	−0.0013 (13)	−0.0058 (12)
C21	0.087 (2)	0.074 (2)	0.0448 (16)	0.0202 (18)	0.0032 (16)	−0.0082 (14)
C23	0.0421 (14)	0.0628 (17)	0.0457 (14)	0.0108 (12)	0.0045 (12)	0.0053 (13)
C24	0.0409 (15)	0.088 (2)	0.086 (2)	−0.0019 (15)	0.0033 (16)	0.0111 (19)

Geometric parameters (Å, º)

O1—C3	1.221 (3)	C12—C13	1.533 (3)
O2—C20	1.210 (3)	C12—H12A	0.9700
O3—C23	1.348 (3)	C12—H12B	0.9700
O3—C17	1.459 (3)	C13—C18	1.540 (3)
O4—C23	1.205 (3)	C13—C14	1.541 (3)
C1—C2	1.530 (3)	C13—C17	1.571 (3)
C1—C10	1.544 (3)	C14—C15	1.531 (3)
C1—H1A	0.9700	C14—H14	0.9800
C1—H1B	0.9700	C15—C16	1.539 (3)
C2—C3	1.491 (4)	C15—H15A	0.9700
C2—H2A	0.9700	C15—H15B	0.9700
C2—H2B	0.9700	C16—C17	1.540 (3)
C3—C4	1.455 (4)	C16—H16A	0.9700
C4—C5	1.341 (3)	C16—H16B	0.9700
C4—H4	0.9300	C17—C20	1.530 (3)
C5—C6	1.508 (3)	C22—H18A	0.9600
C5—C10	1.535 (3)	C22—H18B	0.9600
C6—C7	1.527 (3)	C22—H18C	0.9600
C6—C22	1.529 (4)	C19—H19A	0.9600
C6—H6	0.9800	C19—H19B	0.9600
C7—C8	1.526 (3)	C19—H19C	0.9600
C7—H7A	0.9700	C18—H20A	0.9600
C7—H7B	0.9700	C18—H20B	0.9600
C8—C14	1.522 (3)	C18—H20C	0.9600
C8—C9	1.544 (3)	C20—C21	1.508 (4)
C8—H8	0.9800	C21—H22A	0.9600
C9—C11	1.536 (3)	C21—H22B	0.9600
C9—C10	1.568 (3)	C21—H22C	0.9600
C9—H9	0.9800	C23—C24	1.485 (4)
C10—C19	1.549 (3)	C24—H24A	0.9600
C11—C12	1.536 (3)	C24—H24B	0.9600
C11—H11A	0.9700	C24—H24C	0.9600
C11—H11B	0.9700
C23—O3—C17	118.33 (17)	C12—C13—C14	108.56 (18)
C2—C1—C10	113.8 (2)	C18—C13—C14	111.9 (2)
C2—C1—H1A	108.8	C12—C13—C17	117.73 (19)
C10—C1—H1A	108.8	C18—C13—C17	108.48 (18)
C2—C1—H1B	108.8	C14—C13—C17	99.50 (18)
C10—C1—H1B	108.8	C8—C14—C15	119.02 (19)
H1A—C1—H1B	107.7	C8—C14—C13	114.65 (19)
C3—C2—C1	112.0 (2)	C15—C14—C13	103.95 (17)
C3—C2—H2A	109.2	C8—C14—H14	106.1
C1—C2—H2A	109.2	C15—C14—H14	106.1
C3—C2—H2B	109.2	C13—C14—H14	106.1
C1—C2—H2B	109.2	C14—C15—C16	104.36 (18)
H2A—C2—H2B	107.9	C14—C15—H15A	110.9
O1—C3—C4	121.1 (3)	C16—C15—H15A	110.9
O1—C3—C2	123.0 (3)	C14—C15—H15B	110.9
C4—C3—C2	115.9 (2)	C16—C15—H15B	110.9
C5—C4—C3	125.5 (3)	H15A—C15—H15B	108.9
C5—C4—H4	117.3	C15—C16—C17	106.98 (18)
C3—C4—H4	117.3	C15—C16—H16A	110.3
C4—C5—C6	118.7 (2)	C17—C16—H16A	110.3
C4—C5—C10	121.7 (2)	C15—C16—H16B	110.3
C6—C5—C10	119.59 (19)	C17—C16—H16B	110.3
C5—C6—C7	112.0 (2)	H16A—C16—H16B	108.6
C5—C6—C22	113.0 (2)	O3—C17—C20	110.0 (2)
C7—C6—C22	112.1 (2)	O3—C17—C16	109.87 (19)
C5—C6—H6	106.4	C20—C17—C16	114.95 (19)
C7—C6—H6	106.4	O3—C17—C13	104.72 (16)
C22—C6—H6	106.4	C20—C17—C13	113.3 (2)
C8—C7—C6	113.3 (2)	C16—C17—C13	103.33 (19)
C8—C7—H7A	108.9	C6—C22—H18A	109.5
C6—C7—H7A	108.9	C6—C22—H18B	109.5
C8—C7—H7B	108.9	H18A—C22—H18B	109.5
C6—C7—H7B	108.9	C6—C22—H18C	109.5
H7A—C7—H7B	107.7	H18A—C22—H18C	109.5
C14—C8—C7	110.18 (19)	H18B—C22—H18C	109.5
C14—C8—C9	108.82 (18)	C10—C19—H19A	109.5
C7—C8—C9	109.70 (18)	C10—C19—H19B	109.5
C14—C8—H8	109.4	H19A—C19—H19B	109.5
C7—C8—H8	109.4	C10—C19—H19C	109.5
C9—C8—H8	109.4	H19A—C19—H19C	109.5
C11—C9—C8	111.91 (18)	H19B—C19—H19C	109.5
C11—C9—C10	113.11 (19)	C13—C18—H20A	109.5
C8—C9—C10	113.10 (18)	C13—C18—H20B	109.5
C11—C9—H9	106.0	H20A—C18—H20B	109.5
C8—C9—H9	106.0	C13—C18—H20C	109.5
C10—C9—H9	106.0	H20A—C18—H20C	109.5
C5—C10—C1	108.96 (19)	H20B—C18—H20C	109.5
C5—C10—C19	109.1 (2)	O2—C20—C21	121.1 (3)
C1—C10—C19	109.2 (2)	O2—C20—C17	120.7 (2)
C5—C10—C9	109.04 (19)	C21—C20—C17	117.9 (2)
C1—C10—C9	108.65 (19)	C20—C21—H22A	109.5
C19—C10—C9	111.90 (19)	C20—C21—H22B	109.5
C12—C11—C9	113.5 (2)	H22A—C21—H22B	109.5
C12—C11—H11A	108.9	C20—C21—H22C	109.5
C9—C11—H11A	108.9	H22A—C21—H22C	109.5
C12—C11—H11B	108.9	H22B—C21—H22C	109.5
C9—C11—H11B	108.9	O4—C23—O3	122.9 (3)
H11A—C11—H11B	107.7	O4—C23—C24	126.4 (3)
C13—C12—C11	111.03 (19)	O3—C23—C24	110.7 (2)
C13—C12—H12A	109.4	C23—C24—H24A	109.5
C11—C12—H12A	109.4	C23—C24—H24B	109.5
C13—C12—H12B	109.4	H24A—C24—H24B	109.5
C11—C12—H12B	109.4	C23—C24—H24C	109.5
H12A—C12—H12B	108.0	H24A—C24—H24C	109.5
C12—C13—C18	110.2 (2)	H24B—C24—H24C	109.5
C10—C1—C2—C3	−54.3 (3)	C11—C12—C13—C14	54.6 (3)
C1—C2—C3—O1	−151.0 (3)	C11—C12—C13—C17	166.5 (2)
C1—C2—C3—C4	30.0 (3)	C7—C8—C14—C15	−58.9 (3)
O1—C3—C4—C5	179.6 (3)	C9—C8—C14—C15	−179.2 (2)
C2—C3—C4—C5	−1.4 (4)	C7—C8—C14—C13	177.23 (19)
C3—C4—C5—C6	175.1 (2)	C9—C8—C14—C13	56.9 (2)
C3—C4—C5—C10	−4.2 (4)	C12—C13—C14—C8	−58.6 (2)
C4—C5—C6—C7	137.0 (3)	C18—C13—C14—C8	63.3 (2)
C10—C5—C6—C7	−43.6 (3)	C17—C13—C14—C8	177.79 (18)
C4—C5—C6—C22	−95.2 (3)	C12—C13—C14—C15	169.82 (19)
C10—C5—C6—C22	84.1 (3)	C18—C13—C14—C15	−68.3 (2)
C5—C6—C7—C8	49.1 (3)	C17—C13—C14—C15	46.2 (2)
C22—C6—C7—C8	−79.2 (3)	C8—C14—C15—C16	−162.4 (2)
C6—C7—C8—C14	−176.85 (19)	C13—C14—C15—C16	−33.4 (2)
C6—C7—C8—C9	−57.1 (3)	C14—C15—C16—C17	6.7 (3)
C14—C8—C9—C11	−52.1 (3)	C23—O3—C17—C20	58.0 (3)
C7—C8—C9—C11	−172.7 (2)	C23—O3—C17—C16	−69.5 (2)
C14—C8—C9—C10	178.72 (19)	C23—O3—C17—C13	−179.9 (2)
C7—C8—C9—C10	58.1 (3)	C15—C16—C17—O3	−89.6 (2)
C4—C5—C10—C1	−18.7 (3)	C15—C16—C17—C20	145.7 (2)
C6—C5—C10—C1	161.9 (2)	C15—C16—C17—C13	21.8 (2)
C4—C5—C10—C19	100.4 (3)	C12—C13—C17—O3	−43.0 (3)
C6—C5—C10—C19	−79.0 (3)	C18—C13—C17—O3	−169.06 (19)
C4—C5—C10—C9	−137.2 (2)	C14—C13—C17—O3	73.86 (19)
C6—C5—C10—C9	43.5 (3)	C12—C13—C17—C20	76.9 (3)
C2—C1—C10—C5	47.2 (3)	C18—C13—C17—C20	−49.1 (3)
C2—C1—C10—C19	−71.8 (3)	C14—C13—C17—C20	−166.2 (2)
C2—C1—C10—C9	165.9 (2)	C12—C13—C17—C16	−158.1 (2)
C11—C9—C10—C5	−178.3 (2)	C18—C13—C17—C16	75.9 (2)
C8—C9—C10—C5	−49.8 (2)	C14—C13—C17—C16	−41.2 (2)
C11—C9—C10—C1	63.1 (3)	O3—C17—C20—O2	−148.1 (3)
C8—C9—C10—C1	−168.4 (2)	C16—C17—C20—O2	−23.4 (4)
C11—C9—C10—C19	−57.5 (3)	C13—C17—C20—O2	95.1 (3)
C8—C9—C10—C19	71.0 (3)	O3—C17—C20—C21	37.2 (3)
C8—C9—C11—C12	52.9 (3)	C16—C17—C20—C21	161.9 (3)
C10—C9—C11—C12	−177.95 (19)	C13—C17—C20—C21	−79.6 (3)
C9—C11—C12—C13	−54.2 (3)	C17—O3—C23—O4	−9.2 (4)
C11—C12—C13—C18	−68.4 (2)	C17—O3—C23—C24	171.3 (2)