(6R,9S,13R,14S)-7,8-Dide­hydro-3,7-di­methoxy-17-methyl-6-phenyl­morphinan-4,6-diol

The title compound, C₂₅H₂₉NO₄, (II), was prepared by the reaction of (9S,13R,14S)-7,8-dide­hydro-3,7-di­methoxy-4-hydroxy-17-methyl­morphinan-6-one, (I), with phenyl­magnesium bromide. Compound (II) is a tetracyclic alkaloid with four chiral centers. The piperidine ring adopts a chair conformation, while the other two aliphatic rings are in twisted chair conformations. Compound (II) is the exclusive product, which means that, because of the steric effect, the phenyl anion stereoselectively attacks the opposite side away from the original phenyl group.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.044
• wR factor = 0.106
• Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.03
         From the CIF: _reflns_number_total               3861
         Count of symmetry unique reflns         2201
         Completeness (_total/calc)            175.42%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1660
         Fraction of Friedel pairs measured     0.754
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.

---

S1. Comment

(9S,13R,14S)-7,8-Didehydro-3,7-dimethoxy-4-hydroxy-17-methylmorphinan-6-one, (I), is an important natural product which was used to ease pain, to decrease blood pressure and to diminish inflammation. In order to study the stereochemistry of the reaction of (I) with phenylmagnesium bromide, the crystal structure of the title compound, (II), was determined by X-ray diffraction methods.

The results show that (II) is a tetracyclic alkaloid with four chiral centers. By comparing the structure of (II) with that of (I) (Iijima et al., 1978; Hitotsuyanagi et al., 1994), the newly formed chiral center of (II) was shown to be 6R. The N17/C9/C14/C13/C15/C16 piperidine ring adopts a chair conformation, while the C9–C14 and C5–C8/C14/C13 aliphatic rings adopt twisted chair conformations. Compound (II) is the exclusive product obtained, which means that the phenyl anion stereoselectively attack the opposite side away from the original benzene moiety because of its steric effect. The stereoselectivity of the phenyl anion is greater than that of the hydride anion on (I) (Li et al., 2002).

The C—C bonds within the benzene rings have normal aromatic values. The two methoxy groups are coplanar with the related benzene plane or the ethene plane. The bonds O1—C3 and O4—C7 of 1.390 (5) and 1.374 (4) Å, respectively, are shorter than those of common C—O single bonds [O1—C19 and O4—C18 are 1.402 (8) and 1.410 (4) Å, respectively]. These facts indicate that there exists p-π conjugation between O1 and the benzene ring, as well as O4 and the C7═C8 double bond.

The bond angle of 125.9 (4)° for O1—C3—C2 is larger than that of 113.6 (4)° for O1—C3—C4. It was assumed that this conformation will minimize the van der Waals interaction between the H atom on C2 and the C19 methyl group. The C18 methoxy group presents the same phenomenon. This kind of angle-opened arrangement of methoxy group was also found in r-1,c-2,t-3,t-4–1,3-bis(4-methoxyphenyl)-2,4-bis[2-(5- methylbenzoxazolyl)]cyclobutane (Zhang et al., 2001) and r-1,c-2,t-3,t-4–1,3-bis(4-methoxyphenyl)-2,4-bis[2-(5-phenyl-1,3,4- oxadiazolyl)]cyclobutane (Zheng et al., 2001).

S2. Experimental

Under N₂ protection, a solution of 0.66 g (2 mmol) of (I) in 20 ml of anhydrous THF was added to 8 ml of PhMgBr (1.0 mol l⁻¹ in THF, 8 mmol) solution and stirred at room temperature for 12 h. The reaction mixture was poured into 50 ml of 1.0 mol l⁻¹ NH₄Cl solution and extracted with CHCl₃. After drying over anhydrous Na₂SO₄, the solvent was evaporated, and the residue was purified by column chromatography on silica gel, eluting with 8:0.15:0.05 EtOAc/CH₃OH/Et₃N to give 0.56 g of (II). Yield: 70%, m.p.: 496–498 K, [α]²⁵_D = −41.3° (CHCl₃), IR (KBr): 3200 (m, br), 2929 (s), 1657 (s), 1606 (m), 1485 (s), 1279 (s), 1206 (s), 1153 (m), 1057 (s, br), 853 (m), 802 (m), 731 (m) cm⁻¹; ¹H NMR (CDCl₃) δ: 7.37–7.24 (5H, m), 6.76 (1H, d, 8 Hz), 6.59 (1H, d, 8 Hz), 6.30 (1H, br), 4.71 (1H, s), 3.85 (3H, s), 3.80–3.60 (3H, m), 3.38 (3H, s), 3.20–2.95 (4H, m), 2.40 (1H, s, br), 2.70 (3H, s, br); 2.01–1.95 (3H, m) p.p.m.; ¹³C NMR: 158.02, 147.22, 145.09, 144.44, 130.06, 127.90, 126.40, 125.03, 124.95, 118.69, 108.90, 97.62, 74.94, 57.97, 55.94, 54.52, 50.15, 47.93, 44.40, 42.20, 35.87, 35.61, 24.47 p.p.m.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997) and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. View of the molecular structure of compound (II), with ellipsoids at the 30% probability level.

(6R,9S,13R,14S)-7,8-didehydro-3,7-dimethoxy- 17-methyl-6-phenylmorphinan-4,6-diol

Crystal data

C25H29NO4	F(000) = 872
Mr = 407.49	Dx = 1.232 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 782 reflections
a = 11.710 (4) Å	θ = 2.5–22.6°
b = 13.177 (4) Å	µ = 0.08 mm^−1
c = 14.236 (5) Å	T = 293 K
V = 2196.6 (13) Å^3	Prism, colorless
Z = 4	0.28 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3861 independent reflections
Radiation source: fine-focus sealed tube	2017 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→9
Tmin = 0.976, Tmax = 1.000	k = −15→15
9147 measured reflections	l = −15→16

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0417P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.044	(Δ/σ)max = 0.001
wR(F^2) = 0.106	Δρmax = 0.16 e Å^−3
S = 0.96	Δρmin = −0.14 e Å^−3
3861 reflections	Absolute structure: Flack (1983)
275 parameters	Absolute structure parameter: 0.00 (5)
83 restraints

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	Occ. (<1)
O1	0.3717 (2)	0.0639 (2)	0.8426 (2)	0.0854 (9)
O2	0.22427 (19)	0.08576 (19)	0.98279 (18)	0.0631 (7)
H2	0.2952	0.0901	0.9984	0.076*
O3	0.0416 (2)	−0.05640 (18)	0.89809 (16)	0.0593 (7)
H3	0.0922	−0.0116	0.8920	0.071*
O4	−0.1773 (2)	−0.05356 (19)	0.82172 (17)	0.0671 (8)
C1	0.1483 (4)	0.2160 (3)	0.7274 (3)	0.0626 (11)
H1A	0.1326	0.2475	0.6704	0.075*
C2	0.2492 (4)	0.1642 (3)	0.7382 (3)	0.0693 (12)
H2A	0.3001	0.1590	0.6883	0.083*
C3	0.2746 (3)	0.1205 (3)	0.8224 (3)	0.0612 (11)
C4	0.1975 (3)	0.1274 (3)	0.8981 (3)	0.0496 (9)
C5	−0.0178 (3)	0.0729 (2)	1.0138 (2)	0.0448 (9)
H5A	−0.0756	0.0813	1.0619	0.054*
H5B	0.0526	0.0532	1.0449	0.054*
C6	−0.0550 (3)	−0.0141 (3)	0.9477 (2)	0.0447 (9)
C7	−0.1394 (3)	0.0253 (3)	0.8766 (2)	0.0517 (10)
C8	−0.1695 (3)	0.1214 (3)	0.8682 (3)	0.0548 (10)
H8A	−0.2255	0.1382	0.8246	0.066*
C9	−0.1084 (3)	0.3043 (3)	0.8713 (3)	0.0542 (10)
H9A	−0.1857	0.3221	0.8506	0.065*
C10	−0.0373 (3)	0.2857 (3)	0.7832 (3)	0.0641 (11)
H10A	−0.0846	0.2517	0.7370	0.077*
H10B	−0.0149	0.3507	0.7571	0.077*
C11	0.0695 (3)	0.2223 (3)	0.7998 (3)	0.0527 (10)
C12	0.0904 (3)	0.1740 (3)	0.8851 (2)	0.0457 (9)
C13	0.0011 (3)	0.1753 (3)	0.9651 (2)	0.0413 (8)
C14	−0.1173 (3)	0.2049 (2)	0.9262 (3)	0.0472 (9)
H14A	−0.1677	0.2169	0.9800	0.057*
C15	0.0344 (3)	0.2595 (2)	1.0353 (2)	0.0498 (10)
H15A	−0.0206	0.2613	1.0863	0.060*
H15B	0.1088	0.2446	1.0619	0.060*
C16	0.0378 (3)	0.3625 (2)	0.9871 (3)	0.0571 (10)
H16A	0.0519	0.4147	1.0336	0.069*
H16B	0.1004	0.3636	0.9425	0.069*
N17	−0.0700 (2)	0.3855 (2)	0.9371 (2)	0.0548 (8)
C17	−0.0633 (4)	0.4851 (3)	0.8911 (3)	0.0793 (14)
H17A	−0.0379	0.5350	0.9356	0.119*
H17B	−0.1373	0.5036	0.8677	0.119*
H17C	−0.0102	0.4817	0.8398	0.119*
C18	−0.2516 (4)	−0.0313 (4)	0.7467 (3)	0.0975 (17)
H18A	−0.2706	−0.0928	0.7140	0.146*
H18B	−0.2149	0.0149	0.7041	0.146*
H18C	−0.3201	−0.0007	0.7707	0.146*
C19	0.4514 (13)	0.055 (2)	0.7696 (10)	0.101 (3)	0.46 (3)
H19A	0.4928	0.1178	0.7635	0.152*	0.46 (3)
H19B	0.4123	0.0408	0.7119	0.152*	0.46 (3)
H19C	0.5038	0.0012	0.7835	0.152*	0.46 (3)
C19'	0.4234 (14)	0.0118 (17)	0.7662 (8)	0.101 (3)	0.54 (3)
H19D	0.3917	−0.0552	0.7614	0.152*	0.54 (3)
H19E	0.5042	0.0071	0.7765	0.152*	0.54 (3)
H19F	0.4092	0.0483	0.7090	0.152*	0.54 (3)
C20	−0.1060 (3)	−0.1018 (3)	1.0047 (3)	0.0527 (9)
C21	−0.2216 (4)	−0.1079 (3)	1.0232 (3)	0.0740 (12)
H21A	−0.2698	−0.0568	1.0017	0.089*
C22	−0.2670 (5)	−0.1881 (4)	1.0727 (4)	0.1029 (17)
H22A	−0.3450	−0.1901	1.0849	0.124*
C23	−0.1995 (7)	−0.2637 (4)	1.1035 (4)	0.117 (2)
H23A	−0.2313	−0.3187	1.1351	0.140*
C24	−0.0833 (6)	−0.2597 (4)	1.0885 (4)	0.1162 (19)
H24A	−0.0361	−0.3104	1.1120	0.139*
C25	−0.0365 (4)	−0.1779 (3)	1.0371 (3)	0.0830 (14)
H25A	0.0415	−0.1756	1.0252	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0539 (18)	0.114 (2)	0.089 (2)	0.0108 (18)	0.0150 (16)	−0.0243 (19)
O2	0.0401 (14)	0.0801 (19)	0.0692 (19)	0.0019 (13)	−0.0025 (13)	0.0092 (16)
O3	0.0634 (16)	0.0525 (14)	0.0621 (17)	−0.0011 (13)	0.0172 (14)	−0.0089 (14)
O4	0.088 (2)	0.0581 (17)	0.0555 (17)	−0.0117 (15)	−0.0199 (15)	−0.0076 (15)
C1	0.075 (3)	0.065 (3)	0.047 (2)	−0.011 (2)	0.009 (2)	0.001 (2)
C2	0.067 (3)	0.081 (3)	0.060 (3)	−0.013 (3)	0.021 (2)	−0.010 (3)
C3	0.043 (2)	0.067 (3)	0.073 (3)	−0.003 (2)	0.012 (2)	−0.016 (2)
C4	0.045 (2)	0.052 (2)	0.052 (3)	−0.0075 (19)	0.002 (2)	−0.004 (2)
C5	0.046 (2)	0.047 (2)	0.042 (2)	−0.0004 (17)	0.0034 (17)	0.0023 (19)
C6	0.047 (2)	0.043 (2)	0.044 (2)	0.0019 (18)	0.0052 (18)	−0.0010 (18)
C7	0.055 (3)	0.053 (3)	0.047 (2)	−0.009 (2)	−0.0022 (19)	−0.002 (2)
C8	0.052 (2)	0.057 (3)	0.056 (3)	−0.003 (2)	−0.0111 (19)	0.007 (2)
C9	0.051 (2)	0.047 (2)	0.065 (3)	0.0010 (19)	−0.001 (2)	0.007 (2)
C10	0.072 (3)	0.058 (3)	0.062 (3)	−0.002 (2)	−0.002 (2)	0.012 (2)
C11	0.057 (3)	0.055 (2)	0.046 (2)	−0.0063 (19)	0.005 (2)	0.001 (2)
C12	0.044 (2)	0.046 (2)	0.047 (2)	−0.0061 (18)	0.0023 (17)	−0.003 (2)
C13	0.035 (2)	0.044 (2)	0.044 (2)	−0.0052 (16)	−0.0009 (16)	−0.0010 (18)
C14	0.039 (2)	0.048 (2)	0.055 (2)	−0.0012 (18)	−0.0010 (17)	0.0049 (19)
C15	0.044 (2)	0.050 (2)	0.055 (2)	−0.0028 (18)	−0.0013 (18)	−0.003 (2)
C16	0.051 (2)	0.049 (2)	0.071 (3)	−0.0078 (18)	0.001 (2)	−0.006 (2)
N17	0.050 (2)	0.0397 (18)	0.075 (2)	−0.0008 (15)	0.0004 (17)	0.0038 (17)
C17	0.083 (3)	0.049 (2)	0.106 (4)	−0.001 (2)	0.010 (3)	0.013 (3)
C18	0.089 (4)	0.093 (4)	0.110 (4)	0.008 (3)	−0.044 (3)	−0.023 (3)
C19	0.087 (4)	0.101 (5)	0.115 (3)	0.010 (3)	0.022 (3)	−0.009 (3)
C19'	0.087 (4)	0.101 (5)	0.115 (3)	0.010 (3)	0.022 (3)	−0.009 (3)
C20	0.065 (3)	0.047 (2)	0.046 (2)	−0.0085 (19)	0.0001 (19)	−0.0022 (19)
C21	0.074 (3)	0.078 (3)	0.070 (3)	−0.009 (2)	0.018 (2)	0.007 (2)
C22	0.109 (4)	0.109 (4)	0.091 (4)	−0.045 (4)	0.023 (3)	0.009 (3)
C23	0.167 (6)	0.077 (4)	0.106 (5)	−0.039 (4)	0.035 (4)	0.009 (3)
C24	0.161 (5)	0.072 (3)	0.116 (4)	0.006 (4)	0.022 (4)	0.032 (3)
C25	0.098 (3)	0.061 (3)	0.089 (4)	0.003 (3)	0.008 (3)	0.021 (3)

Geometric parameters (Å, º)

O1—C3	1.390 (5)	C13—C14	1.543 (4)
O1—C19	1.402 (8)	C13—C15	1.544 (4)
O1—C19'	1.423 (8)	C14—H14A	0.9800
O2—C4	1.361 (4)	C15—C16	1.521 (4)
O2—H2	0.8611	C15—H15A	0.9700
O3—C6	1.445 (4)	C15—H15B	0.9700
O3—H3	0.8405	C16—N17	1.480 (4)
O4—C7	1.374 (4)	C16—H16A	0.9700
O4—C18	1.410 (4)	C16—H16B	0.9700
C1—C2	1.373 (5)	N17—C17	1.468 (4)
C1—C11	1.385 (5)	C17—H17A	0.9600
C1—H1A	0.9300	C17—H17B	0.9600
C2—C3	1.363 (5)	C17—H17C	0.9600
C2—H2A	0.9300	C18—H18A	0.9600
C3—C4	1.409 (5)	C18—H18B	0.9600
C4—C12	1.409 (5)	C18—H18C	0.9600
C5—C13	1.533 (4)	C19—H19A	0.9600
C5—C6	1.546 (4)	C19—H19B	0.9600
C5—H5A	0.9700	C19—H19C	0.9600
C5—H5B	0.9700	C19'—H19D	0.9600
C6—C7	1.508 (5)	C19'—H19E	0.9600
C6—C20	1.533 (5)	C19'—H19F	0.9600
C7—C8	1.319 (5)	C20—C25	1.371 (5)
C8—C14	1.505 (5)	C20—C21	1.382 (5)
C8—H8A	0.9300	C21—C22	1.378 (6)
C9—N17	1.492 (4)	C21—H21A	0.9300
C9—C10	1.525 (5)	C22—C23	1.345 (7)
C9—C14	1.529 (4)	C22—H22A	0.9300
C9—H9A	0.9800	C23—C24	1.378 (8)
C10—C11	1.522 (5)	C23—H23A	0.9300
C10—H10A	0.9700	C24—C25	1.414 (6)
C10—H10B	0.9700	C24—H24A	0.9300
C11—C12	1.393 (4)	C25—H25A	0.9300
C12—C13	1.546 (4)
C3—O1—C19	115.8 (6)	C8—C14—H14A	107.6
C3—O1—C19'	116.7 (6)	C9—C14—H14A	107.6
C19—O1—C19'	27.1 (8)	C13—C14—H14A	107.6
C4—O2—H2	115.1	C16—C15—C13	110.8 (3)
C6—O3—H3	109.3	C16—C15—H15A	109.5
C7—O4—C18	118.2 (3)	C13—C15—H15A	109.5
C2—C1—C11	121.3 (4)	C16—C15—H15B	109.5
C2—C1—H1A	119.3	C13—C15—H15B	109.5
C11—C1—H1A	119.3	H15A—C15—H15B	108.1
C3—C2—C1	119.7 (4)	N17—C16—C15	112.2 (3)
C2—C3—O1	125.9 (4)	N17—C16—H16A	109.2
C2—C3—C4	120.4 (4)	C15—C16—H16A	109.2
O1—C3—C4	113.6 (4)	N17—C16—H16B	109.2
O2—C4—C12	119.8 (3)	C15—C16—H16B	109.2
O2—C4—C3	120.3 (3)	H16A—C16—H16B	107.9
C12—C4—C3	119.8 (4)	C17—N17—C16	110.6 (3)
C13—C5—C6	114.7 (3)	C17—N17—C9	112.1 (3)
C13—C5—H5A	108.6	C16—N17—C9	114.3 (3)
C6—C5—H5A	108.6	N17—C17—H17A	109.5
C13—C5—H5B	108.6	N17—C17—H17B	109.5
C6—C5—H5B	108.6	H17A—C17—H17B	109.5
H5A—C5—H5B	107.6	N17—C17—H17C	109.5
O3—C6—C7	108.5 (3)	H17A—C17—H17C	109.5
O3—C6—C20	105.9 (3)	H17B—C17—H17C	109.5
C7—C6—C20	111.1 (3)	O4—C18—H18A	109.5
O3—C6—C5	111.3 (3)	O4—C18—H18B	109.5
C7—C6—C5	109.7 (3)	H18A—C18—H18B	109.5
C20—C6—C5	110.3 (3)	O4—C18—H18C	109.5
C8—C7—O4	126.0 (3)	H18A—C18—H18C	109.5
C8—C7—C6	124.5 (3)	H18B—C18—H18C	109.5
O4—C7—C6	109.4 (3)	O1—C19—H19A	109.5
C7—C8—C14	122.9 (3)	O1—C19—H19B	109.5
C7—C8—H8A	118.5	H19A—C19—H19B	109.5
C14—C8—H8A	118.5	O1—C19—H19C	109.5
N17—C9—C10	117.9 (3)	H19A—C19—H19C	109.5
N17—C9—C14	108.3 (3)	H19B—C19—H19C	109.5
C10—C9—C14	108.6 (3)	O1—C19'—H19D	109.5
N17—C9—H9A	107.2	O1—C19'—H19E	109.5
C10—C9—H9A	107.2	H19D—C19'—H19E	109.5
C14—C9—H9A	107.2	O1—C19'—H19F	109.5
C11—C10—C9	114.2 (3)	H19D—C19'—H19F	109.5
C11—C10—H10A	108.7	H19E—C19'—H19F	109.5
C9—C10—H10A	108.7	C25—C20—C21	118.3 (4)
C11—C10—H10B	108.7	C25—C20—C6	119.9 (4)
C9—C10—H10B	108.7	C21—C20—C6	121.8 (4)
H10A—C10—H10B	107.6	C22—C21—C20	121.4 (5)
C1—C11—C12	120.3 (4)	C22—C21—H21A	119.3
C1—C11—C10	117.7 (3)	C20—C21—H21A	119.3
C12—C11—C10	122.0 (3)	C23—C22—C21	120.5 (5)
C11—C12—C4	118.1 (3)	C23—C22—H22A	119.7
C11—C12—C13	121.2 (3)	C21—C22—H22A	119.7
C4—C12—C13	120.7 (3)	C22—C23—C24	120.1 (5)
C5—C13—C14	104.8 (2)	C22—C23—H23A	120.0
C5—C13—C15	112.1 (3)	C24—C23—H23A	120.0
C14—C13—C15	106.1 (3)	C23—C24—C25	119.5 (6)
C5—C13—C12	114.9 (3)	C23—C24—H24A	120.2
C14—C13—C12	110.3 (3)	C25—C24—H24A	120.2
C15—C13—C12	108.3 (3)	C20—C25—C24	120.1 (5)
C8—C14—C9	111.9 (3)	C20—C25—H25A	119.9
C8—C14—C13	112.1 (3)	C24—C25—H25A	119.9
C9—C14—C13	109.8 (3)
C11—C1—C2—C3	−2.0 (6)	C4—C12—C13—C5	−47.2 (4)
C1—C2—C3—O1	178.2 (4)	C11—C12—C13—C14	17.3 (4)
C1—C2—C3—C4	0.6 (6)	C4—C12—C13—C14	−165.4 (3)
C19—O1—C3—C2	2.5 (15)	C11—C12—C13—C15	−98.4 (3)
C19'—O1—C3—C2	−27.8 (13)	C4—C12—C13—C15	79.0 (4)
C19—O1—C3—C4	−179.7 (14)	C7—C8—C14—C9	146.2 (4)
C19'—O1—C3—C4	150.1 (12)	C7—C8—C14—C13	22.2 (5)
C2—C3—C4—O2	−178.4 (3)	N17—C9—C14—C8	172.9 (3)
O1—C3—C4—O2	3.6 (5)	C10—C9—C14—C8	−58.0 (4)
C2—C3—C4—C12	4.1 (5)	N17—C9—C14—C13	−61.9 (3)
O1—C3—C4—C12	−173.9 (3)	C10—C9—C14—C13	67.2 (4)
C13—C5—C6—O3	80.0 (3)	C5—C13—C14—C8	−52.1 (4)
C13—C5—C6—C7	−40.1 (4)	C15—C13—C14—C8	−170.9 (3)
C13—C5—C6—C20	−162.8 (3)	C12—C13—C14—C8	72.1 (3)
C18—O4—C7—C8	2.8 (6)	C5—C13—C14—C9	−177.2 (3)
C18—O4—C7—C6	−176.0 (3)	C15—C13—C14—C9	64.0 (3)
O3—C6—C7—C8	−117.0 (4)	C12—C13—C14—C9	−53.0 (4)
C20—C6—C7—C8	127.0 (4)	C5—C13—C15—C16	−172.8 (3)
C5—C6—C7—C8	4.8 (5)	C14—C13—C15—C16	−59.0 (3)
O3—C6—C7—O4	61.8 (3)	C12—C13—C15—C16	59.4 (3)
C20—C6—C7—O4	−54.2 (4)	C13—C15—C16—N17	53.7 (4)
C5—C6—C7—O4	−176.4 (3)	C15—C16—N17—C17	−179.7 (3)
O4—C7—C8—C14	−175.1 (3)	C15—C16—N17—C9	−52.0 (4)
C6—C7—C8—C14	3.5 (6)	C10—C9—N17—C17	58.5 (4)
N17—C9—C10—C11	79.8 (4)	C14—C9—N17—C17	−177.8 (3)
C14—C9—C10—C11	−43.8 (4)	C10—C9—N17—C16	−68.4 (4)
C2—C1—C11—C12	−1.3 (6)	C14—C9—N17—C16	55.3 (4)
C2—C1—C11—C10	177.0 (4)	O3—C6—C20—C25	30.6 (4)
C9—C10—C11—C1	−169.5 (3)	C7—C6—C20—C25	148.3 (3)
C9—C10—C11—C12	8.8 (5)	C5—C6—C20—C25	−89.9 (4)
C1—C11—C12—C4	5.8 (5)	O3—C6—C20—C21	−148.0 (3)
C10—C11—C12—C4	−172.4 (3)	C7—C6—C20—C21	−30.4 (5)
C1—C11—C12—C13	−176.8 (3)	C5—C6—C20—C21	91.5 (4)
C10—C11—C12—C13	5.0 (5)	C25—C20—C21—C22	−0.1 (6)
O2—C4—C12—C11	175.3 (3)	C6—C20—C21—C22	178.6 (4)
C3—C4—C12—C11	−7.2 (5)	C20—C21—C22—C23	−0.8 (8)
O2—C4—C12—C13	−2.1 (5)	C21—C22—C23—C24	2.2 (9)
C3—C4—C12—C13	175.4 (3)	C22—C23—C24—C25	−2.6 (9)
C6—C5—C13—C14	63.6 (3)	C21—C20—C25—C24	−0.4 (6)
C6—C5—C13—C15	178.2 (3)	C6—C20—C25—C24	−179.1 (4)
C6—C5—C13—C12	−57.6 (4)	C23—C24—C25—C20	1.7 (8)
C11—C12—C13—C5	135.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.84	2.39	3.088 (4)	141
O2—H2···N17^i	0.86	1.85	2.692 (4)	164

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