Salvinorin B meth-oxy-methyl ether.

The title compound [MOM-SalB; systematic name: methyl (2S,4aR,6aR,7R,9S,10aS,10bR)-2-(3-fur-yl)-9-meth-oxy-meth-oxy-6a,10b-dimethyl-4,10-dioxo-2,4a,5,6,7,8,9,10a-octa-hydro-1H-benzo[f]isochromene-7-carboxyl-ate], C(23)H(30)O(8), is a deriv-ative of the κ-opioid salvinorin A with enhanced potency, selectivity, and duration of action. Superimposition of their crystal structures reveals, surprisingly, that the terminal C and O atoms of the MOM group overlap with the corresponding atoms in salvinorin A, which are separated by an additional bond. This counter-intuitive isosterism is possible because the MOM ether adopts the 'classic anomeric' conformation (gauche-gauche), tracing a helix around the planar acetate of salvinorin A. This overlap is not seen in the recently reported structure of the tetra-hydro-pyranyl ether, which is less potent. The classic anomeric conformation is strongly favoured in alk-oxy-methyl ethers, but not in substituted acetals, which may contribute to their reduced potency. This structure may prove useful in evaluating models of the activated κ-opioid receptor.

Related literature

For preparation, see: Béguin et al. (2009 ▶). For amended characterization data, see: Munro et al. (2008 ▶). For structure–activity relationships in vitro, see: Béguin et al. (2012 ▶); Munro et al. (2008 ▶); Prevatt-Smith et al. (2011 ▶). For in vivo pharmacology, see: Baker et al. (2009 ▶); Peet & Baker (2011 ▶); Wang et al. (2008 ▶). For pharmacokinetics and PET imaging of the eth­oxy­methyl ether, see: Hooker et al. (2009 ▶). For structure–activity relationships of salvinorin A, see: Cunningham et al. (2011 ▶). For crystal structures of related compounds, see: Ortega et al. (1982 ▶); Prevatt-Smith et al. (2011 ▶); Tidgewell et al. (2006 ▶). For solid-state and bioactive conformations of acetals, see: Anderson (2000 ▶); Brameld et al. (2008 ▶).

Experimental

Crystal data

C23H30O8

M = 434.47

Monoclinic,

a = 27.8848 (7) Å

b = 6.2415 (2) Å

c = 12.8212 (3) Å

β = 107.351 (1)°

V = 2129.9 (1) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 193 K

0.25 × 0.13 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.975, T max = 0.993

27784 measured reflections

6195 independent reflections

5296 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.108

S = 1.04

6195 reflections

330 parameters

181 restraints

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and pyMOL (DeLano, 2009 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043449/qm2086sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043449/qm2086Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043449/qm2086Isup3.cdx

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043449/qm2086Isup4.cml

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

C23H30O8	F(000) = 928
Mr = 434.47	Dx = 1.355 Mg m−3
Monoclinic, C2	Melting point = 438–440 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 27.8848 (7) Å	Cell parameters from 9071 reflections
b = 6.2415 (2) Å	θ = 3.0–29.5°
c = 12.8212 (3) Å	µ = 0.10 mm−1
β = 107.351 (1)°	T = 193 K
V = 2129.9 (1) Å3	Needle, colourless
Z = 4	0.25 × 0.13 × 0.07 mm

Bruker APEXII CCD diffractometer	6195 independent reflections
Radiation source: fine-focus sealed tube	5296 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 836.6 pixels mm-1	θmax = 30.0°, θmin = 1.9°
ω scans, 2580 0.5° rotations	h = −38→38
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −8→8
Tmin = 0.975, Tmax = 0.993	l = −18→18
27784 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.062P)2 + 0.2734P] where P = (Fo2 + 2Fc2)/3
6195 reflections	(Δ/σ)max = 0.001
330 parameters	Δρmax = 0.28 e Å−3
181 restraints	Δρmin = −0.16 e Å−3

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 > 2σ(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.34600 (4)	1.0459 (2)	0.20598 (9)	0.0363 (3)
O2	0.37399 (4)	1.1271 (2)	0.02768 (10)	0.0382 (3)
O3	0.28986 (5)	1.1470 (3)	−0.07126 (12)	0.0533 (3)
O4	0.50180 (4)	0.3453 (2)	0.13791 (9)	0.0347 (2)
O5	0.53410 (4)	0.6752 (2)	0.15051 (11)	0.0434 (3)
O6	0.31648 (4)	0.4502 (3)	0.48120 (9)	0.0436 (3)
O7	0.39036 (5)	0.3347 (3)	0.57679 (9)	0.0458 (3)
O8	0.1529 (2)	0.3841 (16)	0.3150 (5)	0.0598 (16)	0.66 (2)
O8*	0.1624 (5)	0.306 (3)	0.3130 (11)	0.065 (3)	0.34 (2)
C1	0.36787 (5)	0.9006 (2)	0.17700 (11)	0.0249 (3)
C2	0.38017 (5)	0.9135 (3)	0.06823 (11)	0.0283 (3)
H2	0.3558	0.8201	0.0142	0.034*
C3	0.43320 (5)	0.8377 (3)	0.07636 (12)	0.0315 (3)
H3A	0.4360	0.8163	0.0019	0.038*
H3B	0.4576	0.9499	0.1126	0.038*
C4	0.44644 (5)	0.6293 (3)	0.14044 (11)	0.0257 (3)
H4	0.4222	0.5171	0.1007	0.031*
C5	0.44100 (5)	0.6503 (2)	0.25776 (11)	0.0228 (2)
C6	0.45549 (5)	0.4362 (3)	0.31852 (12)	0.0267 (3)
H6A	0.4396	0.3176	0.2690	0.032*
H6B	0.4924	0.4176	0.3379	0.032*
C7	0.43961 (5)	0.4217 (3)	0.42203 (11)	0.0274 (3)
H7A	0.4498	0.2813	0.4576	0.033*
H7B	0.4565	0.5355	0.4738	0.033*
C8	0.38318 (5)	0.4474 (2)	0.39397 (11)	0.0244 (3)
H8	0.3678	0.3340	0.3391	0.029*
C9	0.36365 (5)	0.6644 (2)	0.34072 (11)	0.0237 (2)
C10	0.38330 (5)	0.6924 (2)	0.23975 (11)	0.0223 (2)
H10	0.3658	0.5780	0.1877	0.027*
C11	0.30621 (5)	0.6350 (3)	0.30016 (11)	0.0291 (3)
H11A	0.2906	0.7691	0.2645	0.035*
H11B	0.2980	0.5199	0.2445	0.035*
C12	0.28354 (5)	0.5783 (3)	0.39194 (12)	0.0320 (3)
H12	0.2766	0.7162	0.4245	0.038*	0.66 (2)
H12*	0.2744	0.7138	0.4231	0.038*	0.34 (2)
C13	0.2346 (2)	0.4602 (14)	0.3521 (11)	0.0399 (14)	0.66 (2)
C14	0.2245 (3)	0.2544 (13)	0.3026 (9)	0.0608 (16)	0.66 (2)
H14	0.2486	0.1629	0.2865	0.073*	0.66 (2)
C15	0.1763 (4)	0.2117 (11)	0.2826 (5)	0.0577 (16)	0.66 (2)
H15	0.1602	0.0830	0.2510	0.069*	0.66 (2)
C16	0.1899 (2)	0.5337 (15)	0.3570 (8)	0.0508 (17)	0.66 (2)
H16	0.1847	0.6694	0.3853	0.061*	0.66 (2)
C13*	0.2374 (3)	0.442 (2)	0.351 (2)	0.032 (2)	0.34 (2)
C14*	0.2354 (5)	0.241 (2)	0.2978 (16)	0.044 (2)	0.34 (2)
H14*	0.2634	0.1718	0.2848	0.052*	0.34 (2)
C15*	0.1891 (5)	0.165 (2)	0.2686 (15)	0.062 (3)	0.34 (2)
H15*	0.1769	0.0408	0.2264	0.075*	0.34 (2)
C16*	0.1910 (4)	0.481 (3)	0.3591 (14)	0.042 (2)	0.34 (2)
H16*	0.1802	0.6040	0.3898	0.051*	0.34 (2)
C17	0.36481 (6)	0.4082 (3)	0.49147 (12)	0.0321 (3)
C18	0.49892 (5)	0.5576 (3)	0.14339 (12)	0.0295 (3)
C19	0.47495 (5)	0.8301 (3)	0.32085 (12)	0.0293 (3)
H19A	0.5088	0.8135	0.3138	0.044*
H19B	0.4766	0.8225	0.3982	0.044*
H19C	0.4612	0.9692	0.2909	0.044*
C20	0.37823 (6)	0.8467 (3)	0.42559 (12)	0.0314 (3)
H20A	0.3662	0.8125	0.4881	0.047*
H20B	0.3629	0.9810	0.3921	0.047*
H20C	0.4149	0.8623	0.4505	0.047*
C21	0.33854 (7)	1.1533 (4)	−0.07497 (15)	0.0486 (5)
H21A	0.3445	1.2925	−0.1060	0.058*
H21B	0.3433	1.0389	−0.1244	0.058*
C22	0.27678 (9)	1.3292 (5)	−0.0192 (2)	0.0654 (6)
H22A	0.2403	1.3332	−0.0332	0.098*
H22B	0.2877	1.4595	−0.0482	0.098*
H22C	0.2933	1.3206	0.0597	0.098*
C23	0.55100 (6)	0.2564 (3)	0.14724 (16)	0.0407 (4)
H23A	0.5492	0.0996	0.1474	0.061*
H23B	0.5751	0.3056	0.2155	0.061*
H23C	0.5620	0.3039	0.0851	0.061*

	U11	U22	U33	U12	U13	U23
O1	0.0463 (6)	0.0288 (5)	0.0338 (6)	0.0112 (5)	0.0120 (5)	0.0024 (4)
O2	0.0313 (5)	0.0392 (6)	0.0420 (6)	0.0014 (5)	0.0073 (4)	0.0178 (5)
O3	0.0365 (6)	0.0615 (9)	0.0539 (8)	0.0058 (6)	0.0015 (5)	−0.0023 (7)
O4	0.0311 (5)	0.0329 (5)	0.0440 (6)	0.0031 (4)	0.0170 (5)	−0.0081 (5)
O5	0.0319 (5)	0.0406 (7)	0.0629 (8)	−0.0012 (5)	0.0221 (5)	0.0062 (6)
O6	0.0355 (6)	0.0683 (8)	0.0309 (6)	0.0052 (6)	0.0160 (5)	0.0144 (6)
O7	0.0433 (6)	0.0649 (8)	0.0291 (6)	0.0023 (6)	0.0105 (5)	0.0140 (6)
O8	0.0397 (17)	0.096 (4)	0.0512 (16)	−0.019 (2)	0.0254 (14)	−0.016 (2)
O8*	0.047 (4)	0.086 (7)	0.072 (5)	−0.019 (4)	0.032 (3)	0.007 (4)
C1	0.0239 (6)	0.0249 (6)	0.0237 (6)	−0.0013 (5)	0.0039 (5)	−0.0001 (5)
C2	0.0283 (6)	0.0299 (7)	0.0266 (6)	−0.0006 (6)	0.0081 (5)	0.0056 (6)
C3	0.0312 (7)	0.0364 (7)	0.0297 (7)	0.0035 (6)	0.0135 (6)	0.0075 (6)
C4	0.0252 (6)	0.0288 (7)	0.0250 (6)	−0.0006 (5)	0.0103 (5)	0.0000 (5)
C5	0.0239 (6)	0.0211 (6)	0.0239 (6)	−0.0001 (5)	0.0077 (5)	0.0000 (5)
C6	0.0291 (7)	0.0223 (6)	0.0301 (7)	0.0026 (5)	0.0109 (5)	0.0021 (5)
C7	0.0289 (6)	0.0265 (6)	0.0269 (6)	0.0026 (5)	0.0082 (5)	0.0051 (5)
C8	0.0284 (6)	0.0227 (6)	0.0228 (6)	−0.0021 (5)	0.0086 (5)	−0.0002 (5)
C9	0.0257 (6)	0.0239 (6)	0.0227 (6)	0.0010 (5)	0.0094 (5)	−0.0004 (5)
C10	0.0247 (6)	0.0215 (6)	0.0213 (6)	−0.0004 (5)	0.0078 (5)	−0.0006 (5)
C11	0.0267 (6)	0.0371 (7)	0.0254 (7)	0.0017 (6)	0.0107 (5)	0.0028 (6)
C12	0.0308 (7)	0.0376 (8)	0.0306 (7)	0.0020 (6)	0.0137 (6)	0.0021 (6)
C13	0.045 (3)	0.040 (2)	0.037 (3)	−0.006 (2)	0.015 (3)	0.007 (2)
C14	0.060 (3)	0.046 (2)	0.083 (3)	0.001 (3)	0.033 (3)	0.001 (2)
C15	0.064 (4)	0.057 (3)	0.063 (2)	−0.024 (3)	0.035 (2)	−0.015 (2)
C16	0.043 (2)	0.071 (4)	0.042 (3)	−0.007 (2)	0.0173 (18)	−0.008 (3)
C13*	0.022 (3)	0.043 (5)	0.037 (5)	0.005 (3)	0.018 (3)	0.003 (4)
C14*	0.035 (3)	0.031 (3)	0.070 (4)	−0.011 (3)	0.024 (3)	−0.017 (3)
C15*	0.046 (5)	0.049 (4)	0.098 (6)	−0.022 (4)	0.031 (4)	−0.010 (4)
C16*	0.034 (4)	0.067 (5)	0.038 (4)	0.007 (3)	0.030 (3)	0.012 (4)
C17	0.0345 (7)	0.0362 (8)	0.0271 (7)	−0.0030 (6)	0.0114 (6)	0.0015 (6)
C18	0.0281 (7)	0.0346 (7)	0.0285 (7)	0.0012 (6)	0.0126 (6)	0.0014 (6)
C19	0.0300 (7)	0.0259 (6)	0.0309 (7)	−0.0046 (6)	0.0073 (5)	−0.0023 (6)
C20	0.0402 (8)	0.0281 (7)	0.0273 (7)	−0.0001 (6)	0.0121 (6)	−0.0041 (6)
C21	0.0445 (9)	0.0660 (12)	0.0357 (9)	0.0152 (9)	0.0126 (7)	0.0210 (9)
C22	0.0532 (12)	0.0669 (14)	0.0752 (15)	0.0227 (11)	0.0176 (11)	0.0014 (13)
C23	0.0338 (8)	0.0450 (9)	0.0468 (10)	0.0088 (7)	0.0172 (7)	−0.0058 (7)

O1—C1	1.2112 (17)	C9—C11	1.5404 (19)
O2—C21	1.400 (2)	C9—C20	1.543 (2)
O2—C2	1.4225 (18)	C9—C10	1.5586 (17)
O3—C21	1.373 (2)	C10—H10	1.0000
O3—C22	1.420 (3)	C11—C12	1.5340 (19)
O4—C18	1.3305 (19)	C11—H11A	0.9900
O4—C23	1.4513 (18)	C11—H11B	0.9900
O5—C18	1.2067 (19)	C12—C13*	1.500 (3)
O6—C17	1.3404 (18)	C12—C13	1.501 (2)
O6—C12	1.4715 (19)	C12—H12	1.0000
O7—C17	1.2040 (19)	C12—H12*	1.0000
O8—C16	1.377 (3)	C13—C16	1.346 (3)
O8—C15	1.385 (3)	C13—C14	1.423 (3)
O8*—C16*	1.378 (3)	C14—C15	1.320 (3)
O8*—C15*	1.380 (3)	C14—H14	0.9500
C1—C10	1.5214 (18)	C15—H15	0.9500
C1—C2	1.5344 (18)	C16—H16	0.9500
C2—C3	1.5263 (19)	C13*—C16*	1.349 (3)
C2—H2	1.0000	C13*—C14*	1.423 (3)
C3—C4	1.524 (2)	C14*—C15*	1.320 (3)
C3—H3A	0.9900	C14*—H14*	0.9500
C3—H3B	0.9900	C15*—H15*	0.9500
C4—C18	1.5198 (19)	C16*—H16*	0.9500
C4—C5	1.5617 (18)	C19—H19A	0.9800
C4—H4	1.0000	C19—H19B	0.9800
C5—C19	1.5340 (19)	C19—H19C	0.9800
C5—C6	1.5390 (19)	C20—H20A	0.9800
C5—C10	1.5778 (17)	C20—H20B	0.9800
C6—C7	1.5216 (19)	C20—H20C	0.9800
C6—H6A	0.9900	C21—H21A	0.9900
C6—H6B	0.9900	C21—H21B	0.9900
C7—C8	1.5147 (19)	C22—H22A	0.9800
C7—H7A	0.9900	C22—H22B	0.9800
C7—H7B	0.9900	C22—H22C	0.9800
C8—C17	1.5054 (18)	C23—H23A	0.9800
C8—C9	1.5415 (19)	C23—H23B	0.9800
C8—H8	1.0000	C23—H23C	0.9800
C21—O2—C2	115.33 (14)	O6—C12—C13	106.9 (5)
C21—O3—C22	112.85 (17)	O6—C12—C11	114.68 (11)
C18—O4—C23	116.56 (13)	C13*—C12—C11	111.9 (9)
C17—O6—C12	123.97 (11)	C13—C12—C11	113.2 (5)
C16—O8—C15	106.2 (4)	O6—C12—H12	107.2
C16*—O8*—C15*	111.6 (8)	C13—C12—H12	107.2
O1—C1—C10	124.47 (12)	C11—C12—H12	107.2
O1—C1—C2	120.59 (12)	O6—C12—H12*	108.8
C10—C1—C2	114.89 (11)	C13*—C12—H12*	108.8
O2—C2—C3	108.95 (11)	C11—C12—H12*	108.8
O2—C2—C1	110.23 (12)	C16—C13—C14	105.5 (4)
C3—C2—C1	113.35 (11)	C16—C13—C12	125.2 (5)
O2—C2—H2	108.1	C14—C13—C12	129.3 (6)
C3—C2—H2	108.1	C15—C14—C13	108.8 (4)
C1—C2—H2	108.1	C15—C14—H14	125.6
C4—C3—C2	112.05 (11)	C13—C14—H14	125.6
C4—C3—H3A	109.2	C14—C15—O8	109.2 (4)
C2—C3—H3A	109.2	C14—C15—H15	125.4
C4—C3—H3B	109.2	O8—C15—H15	125.4
C2—C3—H3B	109.2	C13—C16—O8	110.3 (4)
H3A—C3—H3B	107.9	C13—C16—H16	124.8
C18—C4—C3	109.94 (11)	O8—C16—H16	124.8
C18—C4—C5	111.73 (11)	C16*—C13*—C14*	107.1 (6)
C3—C4—C5	111.70 (11)	C16*—C13*—C12	128.0 (8)
C18—C4—H4	107.8	C14*—C13*—C12	124.9 (8)
C3—C4—H4	107.8	C15*—C14*—C13*	110.3 (8)
C5—C4—H4	107.8	C15*—C14*—H14*	124.8
C19—C5—C6	109.92 (11)	C13*—C14*—H14*	124.8
C19—C5—C4	110.34 (10)	C14*—C15*—O8*	104.9 (9)
C6—C5—C4	109.16 (11)	C14*—C15*—H15*	127.6
C19—C5—C10	113.43 (11)	O8*—C15*—H15*	127.6
C6—C5—C10	108.71 (10)	C13*—C16*—O8*	105.6 (7)
C4—C5—C10	105.12 (10)	C13*—C16*—H16*	127.2
C7—C6—C5	113.11 (11)	O8*—C16*—H16*	127.2
C7—C6—H6A	109.0	O7—C17—O6	117.96 (13)
C5—C6—H6A	109.0	O7—C17—C8	124.09 (14)
C7—C6—H6B	109.0	O6—C17—C8	117.89 (12)
C5—C6—H6B	109.0	O5—C18—O4	123.31 (13)
H6A—C6—H6B	107.8	O5—C18—C4	125.31 (14)
C8—C7—C6	109.78 (11)	O4—C18—C4	111.38 (12)
C8—C7—H7A	109.7	C5—C19—H19A	109.5
C6—C7—H7A	109.7	C5—C19—H19B	109.5
C8—C7—H7B	109.7	H19A—C19—H19B	109.5
C6—C7—H7B	109.7	C5—C19—H19C	109.5
H7A—C7—H7B	108.2	H19A—C19—H19C	109.5
C17—C8—C7	111.86 (11)	H19B—C19—H19C	109.5
C17—C8—C9	110.35 (11)	C9—C20—H20A	109.5
C7—C8—C9	113.75 (11)	C9—C20—H20B	109.5
C17—C8—H8	106.8	H20A—C20—H20B	109.5
C7—C8—H8	106.8	C9—C20—H20C	109.5
C9—C8—H8	106.8	H20A—C20—H20C	109.5
C11—C9—C8	103.83 (11)	H20B—C20—H20C	109.5
C11—C9—C20	110.78 (11)	O3—C21—O2	113.10 (14)
C8—C9—C20	110.59 (11)	O3—C21—H21A	109.0
C11—C9—C10	108.70 (10)	O2—C21—H21A	109.0
C8—C9—C10	107.52 (10)	O3—C21—H21B	109.0
C20—C9—C10	114.80 (11)	O2—C21—H21B	109.0
C1—C10—C9	114.89 (11)	H21A—C21—H21B	107.8
C1—C10—C5	109.55 (10)	O3—C22—H22A	109.5
C9—C10—C5	117.10 (10)	O3—C22—H22B	109.5
C1—C10—H10	104.6	H22A—C22—H22B	109.5
C9—C10—H10	104.6	O3—C22—H22C	109.5
C5—C10—H10	104.6	H22A—C22—H22C	109.5
C12—C11—C9	113.17 (11)	H22B—C22—H22C	109.5
C12—C11—H11A	108.9	O4—C23—H23A	109.5
C9—C11—H11A	108.9	O4—C23—H23B	109.5
C12—C11—H11B	108.9	H23A—C23—H23B	109.5
C9—C11—H11B	108.9	O4—C23—H23C	109.5
H11A—C11—H11B	107.8	H23A—C23—H23C	109.5
O6—C12—C13*	103.5 (10)	H23B—C23—H23C	109.5
C21—O2—C2—C3	114.88 (14)	C20—C9—C11—C12	−60.11 (16)
C21—O2—C2—C1	−120.16 (14)	C10—C9—C11—C12	172.88 (12)
O1—C1—C2—O2	14.32 (18)	C17—O6—C12—C13*	130.8 (6)
C10—C1—C2—O2	−167.98 (11)	C17—O6—C12—C13	134.9 (4)
O1—C1—C2—C3	136.74 (15)	C17—O6—C12—C11	8.6 (2)
C10—C1—C2—C3	−45.56 (16)	C9—C11—C12—O6	−32.17 (18)
O2—C2—C3—C4	168.32 (12)	C9—C11—C12—C13*	−149.7 (8)
C1—C2—C3—C4	45.19 (17)	C9—C11—C12—C13	−155.2 (4)
C2—C3—C4—C18	178.41 (12)	O6—C12—C13—C16	116.8 (10)
C2—C3—C4—C5	−56.95 (16)	C11—C12—C13—C16	−115.9 (10)
C18—C4—C5—C19	65.23 (14)	O6—C12—C13—C14	−63.2 (12)
C3—C4—C5—C19	−58.40 (14)	C11—C12—C13—C14	64.0 (12)
C18—C4—C5—C6	−55.66 (14)	C16—C13—C14—C15	−1.4 (9)
C3—C4—C5—C6	−179.29 (11)	C12—C13—C14—C15	178.7 (12)
C18—C4—C5—C10	−172.13 (12)	C13—C14—C15—O8	1.2 (9)
C3—C4—C5—C10	64.24 (13)	C16—O8—C15—C14	−0.6 (8)
C19—C5—C6—C7	72.79 (14)	C14—C13—C16—O8	1.0 (9)
C4—C5—C6—C7	−166.06 (11)	C12—C13—C16—O8	−179.0 (11)
C10—C5—C6—C7	−51.90 (14)	C15—O8—C16—C13	−0.3 (9)
C5—C6—C7—C8	59.29 (15)	O6—C12—C13*—C16*	112 (2)
C6—C7—C8—C17	173.22 (12)	C11—C12—C13*—C16*	−123.9 (19)
C6—C7—C8—C9	−60.92 (15)	O6—C12—C13*—C14*	−67.1 (19)
C17—C8—C9—C11	−63.99 (13)	C11—C12—C13*—C14*	57 (2)
C7—C8—C9—C11	169.34 (11)	C16*—C13*—C14*—C15*	3.1 (17)
C17—C8—C9—C20	54.87 (14)	C12—C13*—C14*—C15*	−178 (2)
C7—C8—C9—C20	−71.79 (14)	C13*—C14*—C15*—O8*	−5.8 (16)
C17—C8—C9—C10	−179.08 (11)	C16*—O8*—C15*—C14*	6.7 (16)
C7—C8—C9—C10	54.26 (14)	C14*—C13*—C16*—O8*	1.1 (16)
O1—C1—C10—C9	6.55 (19)	C12—C13*—C16*—O8*	−178 (2)
C2—C1—C10—C9	−171.04 (11)	C15*—O8*—C16*—C13*	−4.9 (17)
O1—C1—C10—C5	−127.68 (14)	C12—O6—C17—O7	167.27 (17)
C2—C1—C10—C5	54.72 (14)	C12—O6—C17—C8	−15.2 (2)
C11—C9—C10—C1	68.63 (14)	C7—C8—C17—O7	−10.3 (2)
C8—C9—C10—C1	−179.56 (11)	C9—C8—C17—O7	−138.04 (17)
C20—C9—C10—C1	−56.05 (15)	C7—C8—C17—O6	172.30 (14)
C11—C9—C10—C5	−160.70 (11)	C9—C8—C17—O6	44.60 (18)
C8—C9—C10—C5	−48.89 (14)	C23—O4—C18—O5	3.4 (2)
C20—C9—C10—C5	74.63 (15)	C23—O4—C18—C4	−176.09 (12)
C19—C5—C10—C1	58.93 (13)	C3—C4—C18—O5	36.7 (2)
C6—C5—C10—C1	−178.48 (11)	C5—C4—C18—O5	−87.90 (17)
C4—C5—C10—C1	−61.70 (13)	C3—C4—C18—O4	−143.75 (13)
C19—C5—C10—C9	−74.18 (14)	C5—C4—C18—O4	91.63 (15)
C6—C5—C10—C9	48.42 (15)	C22—O3—C21—O2	69.8 (2)
C4—C5—C10—C9	165.19 (11)	C2—O2—C21—O3	76.5 (2)
C8—C9—C11—C12	58.63 (15)