3-Benzyl­oxy-16-[(N-methyl-N-phenyl­amino)­methyl­idene]­estra-1,3,5(10)-trien-17-one

In the title compound, C₃₃H₃₅NO₂, the five-membered ring adopts a half-chair conformation. The N-methyl-N-phenyl-substituted keto-enamine moiety shows a comparatively long Csp²-N bond.

S1. Comment

Recently, there has been interest in the annelation of 5- and 6-membered N-containing heteroaromatic rings to the D ring of oestrane derivatives. The title compound, (I), is an excellent starting material for such pyrimidino- and pyrazolo-annelated systems. In order to optimize the reaction conditions for the transformation of (I), a good understanding of the stereoelectronic prerequisites of (I) is important. For this reason, an X-ray crystal structure analysis of (I) was carried out and the results are presented here. \sch

There is one independent molecule of (I) per asymmetric unit cell (Fig. 1). Ring A shows little distortion from planarity, as is evident in other oestrones and oestradiols for which X-ray crystal structure analyses have been carried out. Ring C, with trans fusion to rings B and D, has a chair conformation. As a cyclohexene, ring B in oestranes is usually conformationally more flexible (Bucourt & Hainault, 1967; Matsumoto et al., 2004; Yamamoto et al., 2004). In (I), ring B has a half-chair conformation, as evaluated with the Cremer & Pople (1975) puckering parameters Q = 0.494((3) Å, θ = 46.0 (2)° and ϕ = 160.8 (3)° [for a perfect half-chair conformation, θ = 50.8° and ϕ = k × 60 + 30°; for a perfect chair conformation (the next closest conformation), θ = 0° (Boeyens, 1978)]. This configuration is also in accordance with the relative signs of the endocyclic torsion angles within ring B (see Boeyens, 1978).

Ring D has a half-chair conformation [Q = 0.415 (3) Å and ϕ = 204.7 (3)°], with a pseudo-rotation angle Δ = 6.2 (2)°, and a maximum torsion angle ϕ_m = 42.3 (1)° (Rao et al., 1981) for the atom sequence C13—C14. The important ketoenamine moiety O2—C17—C16—C26—N1 has an E-configurated C16—C26 olefinic bond, with the keto and amino functionalities on opposing sides (Table 1). This mirrors the results of X-ray structure analyses of other ketoenamines (Skinnemoen & Ottersen, 1980; Groselj et al., 2002; Larsen, 1981) and can be explained by electronic repulsion of the keto O atom and amine N atom. The C16—C17 bond [1.481 (3) Å] is significantly longer than in other non-annelated aminomethylidenecyclopentanones (Groselj et al., 2002; Larsen, 1981). Previously, the present authors have observed longer bond lengths for C16—C17 in other oestrane derivatives compared with analogously substituted but non-annelated cyclopentanes (Matsumoto et al., 2004). The other bond lengths involving atoms that define the ketoenamine moiety of (I), C16—C26 [1.346 (3) Å] and C26—N1 [1.369 (3) Å], cannot be compared directly with results from the literature, as X-ray crystal structures of other ketoenamines with a phenyl and an alkyl substituent on the N have not been published to date. A phenyl substituent on N (Skinnemoen & Ottersen, 1980), however, increases the N—C(enamine) bond length compared with an alkyl substituent in mono-N-substituted ketoenamines (Larsen, 1981). In (I), methylidene C16—C26 and keto C17—O2 show some deviation from syn-planarity, with a C26—C16—C17—O2 torsion angle of 6.1 (4)°

In the crystal structure, molecules of (I) pack in four distinct columns arranged in a stepwise fashion. Interactions between molecules are mostly of a dispersive nature, but there are also a number of weak C—H···π interactions (Table 2), the contact distances being in the typical range for reported C—H···π interactions (Nishio & Hirota, 1989; Nishio et al., 1998), where the H atoms are directed towards the π system. Other close contacts that may play a role in the crystal packing are C15—H15···O2(x − 1, y, z) (2.70 Å) and C23—H24···O2(−1/2 − x, −y, 1/2 + z) (2.61 Å).

Table 2. Short-contact geometry for (I) (Å,°). Cg1 denotes the centre of C28—C29—C30—C31—C32—C33, Cg2 the centre of C1—C2—C3—C4—C5—C10 and Cg3 the centre of C20—C21—C22—C-23-C24—C25.

S2. Experimental

Compound (I) was prepared by reaction of 3-benzyloxy-16-(hydroxymethylidene)-oestra-1,3,5(10)-triene-17-one with N-methyl-N-phenylammonium trifluoroacetate, according to the literature method of Matsumoto et al. (2003). The crystal used for the X-ray structure analysis was obtained by recrystallization of (I) from chloroform-ether-hexane (1:1:1).

S3. Refinement

All H atoms were refined as riding on their parent atoms, with C—H = 0.95 Å, except for those on atoms C18 (H17, H18, H19) and C27 (H28, H29, H30), and atom H27, which had their coordinates freely refined. Please clarify - this statement does not match the data in the CIF tables. All U_iso(H) values were set to 1.2U_eq(O,C). The absolute configuration could not be determined from the X-ray data but was known from the synthetic route.

Computing details

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: PLATON (Spek, 2003) and Mercury (Please provide reference); software used to prepare material for publication: CrystalStructure.

Figures

Fig. 1. A view of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

3-Benzyloxy-16-[(N-methyl-N-phenylamino)methylidene]oestra-1,3,5(10)-trien- 17-one

Crystal data

C33H35NO2	Dx = 1.271 Mg m^−3
Mr = 477.65	Melting point: 204 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5574 reflections
a = 6.1333 (2) Å	θ = 3.3–27.5°
b = 11.4780 (5) Å	µ = 0.08 mm^−1
c = 35.447 (2) Å	T = 123 K
V = 2495.4 (2) Å^3	Needle, colourless
Z = 4	0.13 × 0.08 × 0.06 mm
F(000) = 1024.00

Data collection

Rigaku Saturn70 CCD diffractometer	2156 reflections with F^2 > 2σ(F^2)
Detector resolution: 7.31 pixels mm^-1	Rint = 0.056
ω scans	θmax = 27.5°
Absorption correction: multi-scan (Jacobson, 1998)	h = −7→7
Tmin = 0.908, Tmax = 0.995	k = −14→14
25566 measured reflections	l = −46→45
3276 independent reflections

Refinement

Refinement on F^2	w = 1/[0.578σ(Fo^2)]/(4Fo^2)
R[F^2 > 2σ(F^2)] = 0.034	(Δ/σ)max < 0.001
wR(F^2) = 0.062	Δρmax = 0.25 e Å^−3
S = 1.00	Δρmin = −0.21 e Å^−3
3276 reflections	Extinction correction: Larson (1970), eq. 22
361 parameters	Extinction coefficient: 42.1 (40)
H-atom parameters constrained

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
O1	0.0383 (2)	0.08571 (13)	0.98926 (4)	0.0262 (4)
O2	0.6582 (3)	−0.0018 (2)	0.70353 (4)	0.0367 (5)
N1	0.2056 (3)	0.1999 (2)	0.64259 (5)	0.0238 (5)
C1	0.3696 (4)	0.0208 (2)	0.90733 (6)	0.0234 (6)
C2	0.2939 (4)	0.0261 (2)	0.94396 (6)	0.0246 (6)
C3	0.1018 (4)	0.0857 (2)	0.95189 (6)	0.0219 (6)
C4	−0.0119 (4)	0.1371 (2)	0.92258 (6)	0.0219 (6)
C5	0.0655 (4)	0.1314 (2)	0.88564 (6)	0.0195 (6)
C6	−0.0723 (4)	0.1884 (2)	0.85531 (6)	0.0233 (6)
C7	0.0458 (4)	0.2042 (2)	0.81779 (6)	0.0221 (6)
C8	0.1748 (3)	0.0960 (2)	0.80755 (5)	0.0195 (6)
C9	0.3515 (3)	0.0738 (2)	0.83751 (6)	0.0196 (6)
C10	0.2595 (4)	0.0731 (2)	0.87732 (6)	0.0194 (6)
C11	0.4940 (4)	−0.0329 (2)	0.82769 (6)	0.0230 (6)
C12	0.5911 (4)	−0.0256 (2)	0.78758 (6)	0.0247 (6)
C13	0.4150 (4)	−0.0028 (2)	0.75836 (6)	0.0209 (6)
C14	0.2854 (4)	0.1065 (2)	0.76941 (6)	0.0198 (6)
C15	0.1557 (3)	0.1377 (2)	0.73364 (5)	0.0222 (6)
C16	0.3183 (4)	0.1077 (2)	0.70275 (6)	0.0229 (6)
C17	0.4892 (4)	0.0312 (2)	0.71877 (6)	0.0255 (6)
C18	0.2697 (4)	−0.1114 (2)	0.75318 (6)	0.0285 (7)
C19	−0.1647 (4)	0.1409 (2)	0.99828 (6)	0.0276 (7)
C20	−0.2179 (4)	0.1133 (2)	1.03892 (6)	0.0227 (6)
C21	−0.0744 (4)	0.1419 (2)	1.06732 (6)	0.0297 (7)
C22	−0.1235 (4)	0.1171 (2)	1.10481 (6)	0.0301 (7)
C23	−0.3173 (4)	0.0629 (2)	1.11396 (6)	0.0304 (7)
C24	−0.4635 (4)	0.0344 (2)	1.08532 (7)	0.0295 (7)
C25	−0.4134 (4)	0.0598 (2)	1.04823 (6)	0.0263 (7)
C26	0.3384 (4)	0.1378 (2)	0.66622 (6)	0.0238 (6)
C27	−0.0119 (4)	0.2370 (2)	0.65530 (6)	0.0322 (7)
C28	0.2685 (4)	0.2297 (2)	0.60495 (6)	0.0221 (6)
C29	0.1462 (4)	0.3084 (2)	0.58414 (6)	0.0264 (6)
C30	0.2023 (4)	0.3327 (2)	0.54694 (6)	0.0275 (7)
C31	0.3795 (4)	0.2807 (2)	0.53021 (6)	0.0296 (7)
C32	0.5024 (4)	0.2031 (2)	0.55103 (6)	0.0367 (7)
C33	0.4495 (4)	0.1785 (2)	0.58815 (6)	0.0314 (7)
H1	0.5017	−0.0197	0.9024	0.028*
H2	0.3724	−0.0110	0.9637	0.030*
H3	−0.1446	0.1768	0.9277	0.026*
H4	−0.1975	0.1414	0.8511	0.028*
H5	−0.1165	0.2630	0.8641	0.028*
H6	−0.0587	0.2190	0.7986	0.027*
H7	0.1427	0.2684	0.8197	0.027*
H8	0.0785	0.0312	0.8070	0.023*
H9	0.4461	0.1393	0.8364	0.023*
H10	0.6104	−0.0375	0.8453	0.028*
H11	0.4072	−0.1012	0.8294	0.028*
H12	0.6943	0.0361	0.7868	0.029*
H13	0.6618	−0.0971	0.7818	0.030*
H14	0.3906	0.1666	0.7722	0.024*
H15	0.0269	0.0922	0.7316	0.027*
H16	0.1186	0.2180	0.7332	0.027*
H17	0.1471	−0.0922	0.7380	0.034*
H18	0.2216	−0.1376	0.7772	0.035*
H19	0.3510	−0.1715	0.7412	0.035*
H20	−0.1519	0.2228	0.9951	0.033*
H21	−0.2766	0.1121	0.9823	0.033*
H22	0.0597	0.1787	1.0613	0.036*
H23	−0.0234	0.1377	1.1242	0.036*
H24	−0.3504	0.0453	1.1395	0.037*
H25	−0.5978	−0.0025	1.0913	0.035*
H26	−0.5139	0.0403	1.0289	0.032*
H27	0.4689	0.1111	0.6547	0.028*
H28	−0.0100	0.3180	0.6608	0.039*
H29	−0.1155	0.2220	0.6360	0.039*
H30	−0.0507	0.1947	0.6774	0.039*
H31	0.0241	0.3459	0.5953	0.032*
H32	0.1166	0.3861	0.5328	0.033*
H33	0.4165	0.2977	0.5048	0.036*
H34	0.6250	0.1663	0.5398	0.044*
H35	0.5375	0.1261	0.6023	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0238 (9)	0.0360 (10)	0.0187 (8)	0.0053 (9)	0.0015 (7)	−0.0006 (8)
O2	0.0282 (9)	0.0543 (12)	0.0277 (10)	0.0146 (10)	0.0041 (9)	0.0012 (9)
N1	0.0186 (10)	0.0307 (11)	0.0220 (10)	0.0016 (10)	0.0012 (9)	0.0014 (9)
C1	0.0192 (12)	0.0284 (13)	0.0225 (12)	0.0031 (12)	−0.0024 (11)	−0.0026 (10)
C2	0.0224 (12)	0.0292 (13)	0.0222 (12)	0.0042 (12)	−0.0057 (11)	−0.0001 (11)
C3	0.0240 (12)	0.0243 (12)	0.0175 (11)	−0.0025 (12)	0.0008 (11)	−0.0018 (10)
C4	0.0196 (12)	0.0216 (12)	0.0246 (12)	0.0008 (11)	0.0006 (11)	−0.0012 (10)
C5	0.0167 (11)	0.0200 (12)	0.0217 (12)	−0.0004 (11)	−0.0017 (10)	−0.0001 (10)
C6	0.0221 (12)	0.0259 (13)	0.0220 (12)	0.0034 (12)	−0.0011 (11)	−0.0012 (10)
C7	0.0193 (12)	0.0234 (12)	0.0236 (12)	0.0016 (11)	−0.0029 (11)	0.0004 (10)
C8	0.0182 (11)	0.0205 (12)	0.0199 (11)	0.0001 (11)	−0.0019 (10)	−0.0014 (10)
C9	0.0137 (11)	0.0230 (12)	0.0223 (11)	0.0001 (11)	−0.0019 (10)	−0.0000 (10)
C10	0.0181 (12)	0.0207 (12)	0.0194 (12)	−0.0028 (11)	−0.0019 (10)	−0.0004 (10)
C11	0.0198 (12)	0.0267 (13)	0.0224 (12)	0.0021 (11)	−0.0022 (10)	0.0014 (11)
C12	0.0213 (12)	0.029 (1)	0.0234 (12)	0.0057 (12)	0.0000 (11)	−0.0007 (11)
C13	0.0205 (11)	0.0237 (13)	0.0186 (11)	0.0006 (11)	0.0003 (10)	−0.0001 (10)
C14	0.0184 (11)	0.0196 (12)	0.0213 (12)	−0.0014 (11)	0.0001 (10)	−0.0006 (10)
C15	0.0205 (12)	0.0243 (13)	0.0219 (12)	0.0006 (12)	0.0006 (11)	0.0012 (10)
C16	0.0194 (12)	0.0271 (13)	0.0221 (12)	0.0008 (11)	−0.0012 (11)	0.0000 (10)
C17	0.0244 (13)	0.030 (1)	0.0224 (12)	−0.0010 (12)	0.0014 (11)	−0.0029 (11)
C18	0.0297 (13)	0.0259 (13)	0.030 (1)	0.0010 (12)	−0.0000 (12)	−0.0052 (11)
C19	0.0250 (13)	0.033 (1)	0.0254 (13)	0.0035 (13)	0.0016 (12)	−0.0020 (11)
C20	0.0249 (12)	0.0234 (12)	0.0197 (12)	0.0027 (12)	0.0020 (11)	−0.0002 (10)
C21	0.030 (1)	0.030 (1)	0.0288 (13)	−0.0036 (13)	−0.0027 (13)	−0.0007 (12)
C22	0.035 (2)	0.030 (1)	0.0257 (13)	0.005 (1)	−0.0049 (12)	−0.0054 (11)
C23	0.042 (2)	0.0274 (13)	0.0219 (12)	0.006 (1)	0.0057 (13)	0.0020 (11)
C24	0.028 (1)	0.027 (1)	0.033 (1)	−0.0034 (13)	0.0071 (13)	0.0007 (12)
C25	0.0256 (13)	0.0288 (13)	0.0247 (13)	−0.0025 (12)	−0.0039 (12)	−0.0042 (11)
C26	0.0202 (12)	0.0265 (13)	0.0246 (12)	0.0020 (12)	−0.0015 (11)	−0.0014 (11)
C27	0.0243 (13)	0.043 (2)	0.029 (1)	0.0062 (13)	0.0017 (12)	0.0018 (12)
C28	0.0249 (13)	0.0236 (13)	0.0179 (12)	−0.0038 (12)	−0.0003 (11)	−0.0017 (10)
C29	0.0261 (13)	0.0273 (13)	0.0260 (13)	0.0057 (12)	−0.0004 (12)	−0.0014 (11)
C30	0.031 (1)	0.0271 (13)	0.0243 (13)	0.0029 (12)	−0.0074 (12)	0.0003 (11)
C31	0.034 (1)	0.033 (1)	0.0217 (13)	0.0020 (13)	0.0009 (12)	0.0020 (11)
C32	0.040 (2)	0.041 (2)	0.028 (1)	0.015 (1)	0.009 (1)	0.0070 (13)
C33	0.0291 (13)	0.037 (2)	0.028 (1)	0.0084 (13)	0.0012 (13)	0.0096 (12)

Geometric parameters (Å, º)

O1—C3	1.381 (3)	C29—C30	1.391 (3)
O1—C19	1.433 (3)	C30—C31	1.374 (3)
O2—C17	1.229 (3)	C31—C32	1.380 (3)
N1—C26	1.369 (3)	C32—C33	1.384 (3)
N1—C27	1.471 (3)	C1—H1	0.9500
N1—C28	1.431 (3)	C2—H2	0.9499
C1—C2	1.380 (3)	C4—H3	0.9500
C1—C10	1.396 (3)	C6—H4	0.9500
C2—C3	1.391 (3)	C6—H5	0.9500
C3—C4	1.383 (3)	C7—H6	0.9500
C4—C5	1.394 (3)	C7—H7	0.9500
C5—C6	1.516 (3)	C8—H8	0.9500
C5—C10	1.397 (3)	C9—H9	0.9500
C6—C7	1.525 (3)	C11—H10	0.9501
C7—C8	1.516 (3)	C11—H11	0.9500
C8—C9	1.538 (3)	C12—H12	0.9501
C8—C14	1.517 (3)	C12—H13	0.9500
C9—C10	1.520 (3)	C14—H14	0.9500
C9—C11	1.545 (3)	C15—H15	0.9500
C11—C12	1.544 (3)	C15—H16	0.9500
C12—C13	1.519 (3)	C18—H17	0.9500
C13—C14	1.535 (3)	C18—H18	0.9498
C13—C17	1.526 (3)	C18—H19	0.9501
C13—C18	1.544 (3)	C19—H20	0.9499
C14—C15	1.539 (3)	C19—H21	0.9501
C15—C16	1.520 (3)	C21—H22	0.9500
C16—C17	1.481 (3)	C22—H23	0.9501
C16—C26	1.346 (3)	C23—H24	0.9500
C17—O2	1.229 (3)	C24—H25	0.9500
C17—C13	1.526 (3)	C25—H26	0.9500
C17—C16	1.481 (3)	C26—H27	0.9501
C19—C20	1.511 (3)	C27—H28	0.9500
C20—C21	1.377 (3)	C27—H29	0.9499
C20—C25	1.387 (3)	C27—H30	0.9501
C21—C22	1.392 (3)	C29—H31	0.9501
C22—C23	1.380 (4)	C30—H32	0.9500
C23—C24	1.394 (3)	C31—H33	0.9500
C24—C25	1.381 (3)	C32—H34	0.9500
C28—C29	1.386 (3)	C33—H35	0.9500
C28—C33	1.390 (3)
O1—C3—C2	115.6 (2)	C3—C4—H3	119.5405
O1—C3—C4	125.3 (2)	H3—C4—C5	119.5354
C19—O1—C3	117.3 (2)	C5—C6—H4	108.3651
O1—C19—C20	107.9 (2)	C5—C6—H5	108.3546
O2—C17—C13	125.3 (2)	H4—C6—C7	108.3952
O2—C17—C16	127.7 (2)	H5—C6—C7	108.3465
N1—C26—C16	131.9 (2)	C6—C7—H6	109.0092
C27—N1—C26	120.2 (2)	C6—C7—H7	109.1251
C28—N1—C26	122.3 (2)	H5—C6—H4	109.4529
C28—N1—C27	117.4 (2)	H6—C7—C8	109.0994
N1—C28—C29	120.4 (2)	H7—C7—C8	109.0365
N1—C28—C33	120.9 (2)	C7—C8—H8	108.7504
C1—C2—C3	119.8 (2)	H7—C7—H6	109.4621
C10—C1—C2	122.4 (2)	C8—C9—H9	105.6977
C1—C10—C5	117.2 (2)	H8—C8—C9	108.8014
C1—C10—C9	122.0 (2)	C8—C14—H14	105.5421
C2—C3—C4	119.0 (2)	H8—C8—C14	108.7779
C3—C4—C5	120.9 (2)	H9—C9—C10	105.6956
C4—C5—C10	120.7 (2)	H9—C9—C11	105.7656
C4—C5—C6	117.1 (2)	C9—C11—H10	108.6893
C10—C5—C6	122.1 (2)	C9—C11—H11	108.8037
C5—C6—C7	113.9 (2)	C11—C12—H12	109.0020
C5—C10—C9	120.6 (2)	C11—C12—H13	109.0403
C6—C7—C8	111.1 (2)	H10—C11—C12	108.6074
C7—C8—C14	112.4 (2)	H11—C11—C12	108.7450
C7—C8—C9	109.7 (2)	H11—C11—H10	109.4641
C14—C8—C9	108.3 (2)	H12—C12—C13	108.9135
C8—C9—C10	112.4 (2)	H13—C12—C13	109.1103
C8—C9—C11	112.0 (2)	H13—C12—H12	109.4658
C8—C14—C13	113.2 (2)	C13—C14—H14	105.5812
C8—C14—C15	121.4 (2)	C13—C18—H17	109.6272
C11—C9—C10	114.5 (2)	C13—C18—H19	109.6343
C9—C11—C12	112.5 (2)	C13—C18—H18	109.1494
C11—C12—C13	111.3 (2)	H14—C14—C15	105.5336
C12—C13—C14	109.6 (2)	C14—C15—H15	111.3998
C12—C13—C17	117.3 (2)	C14—C15—H16	111.3592
C12—C13—C18	110.6 (2)	H15—C15—C16	111.4781
C17—C13—C14	100.4 (2)	H16—C15—C16	111.3420
C18—C13—C14	113.0 (2)	H16—C15—H15	109.4591
C13—C14—C15	104.3 (2)	C16—C26—H27	114.1622
C13—C17—C16	107.0 (2)	H19—C18—H17	109.4601
C18—C13—C17	105.6 (2)	H18—C18—H17	109.4765
C14—C15—C16	101.6 (2)	H19—C18—H18	109.4795
C15—C16—C17	108.8 (2)	H20—C19—C20	109.7992
C15—C16—C26	134.0 (2)	H21—C19—C20	109.9334
C26—C16—C17	117.2 (2)	H21—C19—H20	109.4703
C19—C20—C21	120.6 (2)	C20—C21—H22	119.6291
C19—C20—C25	120.4 (2)	C20—C25—H26	119.5757
C25—C20—C21	118.9 (2)	H22—C21—C22	119.6011
C20—C21—C22	120.8 (2)	C21—C22—H23	119.9114
C20—C25—C24	120.8 (2)	H23—C22—C23	119.9274
C21—C22—C23	120.2 (2)	C22—C23—H24	120.2831
C22—C23—C24	119.3 (2)	C23—C24—H25	119.9605
C23—C24—C25	120.0 (2)	H24—C23—C24	120.4534
C33—C28—C29	118.7 (2)	C24—C25—H26	119.5948
C28—C29—C30	120.1 (2)	H25—C24—C25	120.0074
C28—C33—C32	120.5 (2)	H29—C27—H28	109.4713
C29—C30—C31	121.2 (2)	H30—C27—H28	109.4712
C30—C31—C32	118.8 (2)	H30—C27—H29	109.4713
C31—C32—C33	120.8 (2)	C28—C29—H31	119.9682
O1—C19—H20	109.8190	C28—C33—H35	119.6972
O1—C19—H21	109.8870	H31—C29—C30	119.9673
N1—C26—H27	113.9249	C29—C30—H32	119.4316
N1—C27—H28	109.6070	H32—C30—C31	119.3887
N1—C27—H29	109.4710	C30—C31—H33	120.6055
N1—C27—H30	109.3353	C31—C32—H34	119.6486
C1—C2—H2	120.1434	H33—C31—C32	120.6311
H1—C1—C2	118.8038	C32—C33—H35	119.7717
H1—C1—C10	118.8453	H34—C32—C33	119.5684
H2—C2—C3	120.0747
C19—O1—C3—C2	−176.8 (2)	C11—C12—C13—C17	167.9 (2)
C19—O1—C3—C4	1.6 (3)	C11—C12—C13—C18	−70.9 (2)
C3—O1—C19—C20	170.9 (2)	C12—C13—C14—C8	−59.8 (2)
C27—N1—C26—C16	−6.1 (4)	C12—C13—C14—C15	166.1 (2)
C28—N1—C26—C16	174.8 (2)	C17—C13—C14—C8	176.1 (2)
C26—N1—C28—C29	−169.3 (2)	C17—C13—C14—C15	42.0 (2)
C26—N1—C28—C33	12.3 (3)	C18—C13—C14—C8	64.0 (2)
C27—N1—C28—C29	11.6 (3)	C18—C13—C14—C15	−70.0 (2)
C27—N1—C28—C33	−166.7 (2)	C12—C13—C17—O2	31.5 (3)
C10—C1—C2—C3	−0.4 (3)	C12—C13—C17—C16	−149.6 (2)
C2—C1—C10—C5	−0.4 (3)	C14—C13—C17—O2	150.1 (2)
C2—C1—C10—C9	175.8 (2)	C14—C13—C17—C16	−31.0 (2)
C1—C2—C3—O1	179.6 (2)	C18—C13—C17—O2	−92.2 (3)
C1—C2—C3—C4	1.1 (3)	C18—C13—C17—C16	86.7 (2)
O1—C3—C4—C5	−179.5 (2)	C8—C14—C15—C16	−166.3 (2)
C2—C3—C4—C5	−1.1 (3)	C13—C14—C15—C16	−37.0 (2)
C3—C4—C5—C6	178.9 (2)	C14—C15—C16—C17	17.4 (2)
C3—C4—C5—C10	0.3 (3)	C14—C15—C16—C26	−160.8 (2)
C4—C5—C6—C7	166.3 (2)	C15—C16—C17—O2	−172.4 (2)
C10—C5—C6—C7	−15.2 (3)	C15—C16—C17—C13	8.7 (2)
C4—C5—C10—C1	0.4 (3)	C26—C16—C17—O2	6.1 (4)
C4—C5—C10—C9	−175.9 (2)	C26—C16—C17—C13	−172.8 (2)
C6—C5—C10—C1	−178.1 (2)	C15—C16—C26—N1	−6.5 (4)
C6—C5—C10—C9	5.6 (3)	C17—C16—C26—N1	175.4 (2)
C5—C6—C7—C8	43.4 (2)	O1—C19—C20—C21	57.2 (3)
C6—C7—C8—C9	−62.3 (2)	O1—C19—C20—C25	−123.5 (2)
C6—C7—C8—C14	177.2 (2)	C19—C20—C21—C22	179.6 (2)
C7—C8—C9—C10	51.7 (2)	C25—C20—C21—C22	0.3 (3)
C7—C8—C9—C11	−177.8 (2)	C19—C20—C25—C24	−179.9 (2)
C14—C8—C9—C10	174.7 (2)	C21—C20—C25—C24	−0.6 (3)
C14—C8—C9—C11	−54.8 (2)	C20—C21—C22—C23	0.3 (4)
C7—C8—C14—C13	−179.4 (2)	C21—C22—C23—C24	−0.6 (4)
C7—C8—C14—C15	−54.1 (3)	C22—C23—C24—C25	0.3 (3)
C9—C8—C14—C13	59.2 (2)	C23—C24—C25—C20	0.3 (3)
C9—C8—C14—C15	−175.5 (2)	N1—C28—C29—C30	−176.9 (2)
C8—C9—C10—C1	159.9 (2)	C33—C28—C29—C30	1.5 (3)
C8—C9—C10—C5	−23.9 (3)	N1—C28—C33—C32	176.5 (2)
C11—C9—C10—C1	30.7 (3)	C29—C28—C33—C32	−1.9 (3)
C11—C9—C10—C5	−153.2 (2)	C28—C29—C30—C31	−0.6 (4)
C8—C9—C11—C12	52.9 (2)	C29—C30—C31—C32	0.0 (3)
C10—C9—C11—C12	−177.7 (2)	C30—C31—C32—C33	−0.4 (4)
C9—C11—C12—C13	−52.5 (2)	C31—C32—C33—C28	1.4 (4)
C11—C12—C13—C14	54.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	H···A	D···A	D—H···A
C15—H15···O2^i	2.70	3.607 (3)	161
C23—H24···O2^ii	2.61	3.395 (3)	141
C1—H1···Cg1^iii	2.99	3.685 (3)	131
C29—H31···Cg2^iv	2.97	3.694 (3)	134
C32—H34···Cg3^v	2.56	3.456 (3)	158
C33—H35···Cg3^v	2.73	3.582 (3)	149

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