16-(3-Pyridyl­methyl­ene)­androst-4-ene-3,17-dione

In the title compound, C₂₅H₂₉NO₂, ring A adopts a slightly distorted half-chair conformation, while rings B and C are in chair conformations. The five-membered ring D adopts a 13β,14α-half-chair conformation. The 3-pyridyl ring has an E configuration with respect to the carbonyl group at position 17. The crystal structure is stabilized by weak intra- and intermolecular C—H...O interactions and van der Waals forces.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.041
• wR factor = 0.108
• Data-to-parameter ratio = 8.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.96
         From the CIF: _reflns_number_total               2172
         Count of symmetry unique reflns         2073
         Completeness (_total/calc)            104.78%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured        99
         Fraction of Friedel pairs measured     0.048
         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

The X-ray investigation of the title compound, (I), was undertaken as a part of our study on the structure and conformation of new synthetic steroid derivatives (Hema et al., 2002; Vasuki et al., 2001; Vasuki, Parthasarathi, Ramamurthi, Dubey & Jindal, 2002a,b; Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Thamotharan et al., 2002a,b). We are particularly interested in studying the conformational flexibilities of the steroids due to various possible substitutions at the C3, C16 and C17 positions, as it is well known that the steroid-receptors are able to modify the mode of binding at ring D to accommodate several different types of C17 substitution (Duax & Norton, 1975).

In (I), ring A has a slightly distorted half-chair conformation, with asymmetry parameters (Duax & Norton, 1975) ΔC₂(C1—C2) = 9.2 (5)° and ΔC_s(C1) = 13.83°, as observed in a similar androstene derivative (Galdecki et al., 1990). Rings B and C adopt chair conformations, while ring D adopts a 13β,14α-half-chair conformation, with pseudo-rotational parameters Δ = 1.2° and ϕ_m = 41.5 (3)° (Altona et al., 1968). The geometry of the rings is trans at the B/C and C/D ring junctions. The C17—C16—C20—C21 torsion angle of 172.5 (3)° indicates that the 3-pyridyl ring has an E configuration with respect to the carbonyl group at position 17. The larger exocyclic angle C15—C16—C20 [132.1 (3)°] compared with C17—C16—C20 [119.2 (3)°] might be a consequence of the steric repulsion between H15B and H22 (H15B···H22 = 2.23 Å). The dihedral angle between the plane of the pyridine ring and the average molecular plane comprising rings A, B, C and D is 5.27 (1)°. The values of the C8—C14—C15 [120.4 (2)°] and C14—C13—C17 [100.6 (2)°] angles are close to the expected values of 119.3 and 99.2°, respectively (Duax & Norton, 1975). The pseudo-torsion angle C19—C10···C13—C18 is observed to be 6.3 (3)°. The C4—C5 (Csp²—Csp²) distance of 1.343 (4) Å confirms the localization of a double bond at this position (Vasuki, Parthasarathi, Ramamurthi, Jindal & Dubey, 2002; Vasuki, Thamotharan et al., 2002a). A short intramolecular C—H···O contact is observed between C20 and O17, with an H20···O17 distance of 2.54 Å. An intermolecular C—H···O contact is observed between C26 and O3ⁱ, with an H26···O3ⁱ distance of 2.53 Å [symmetry code: (i) x, y, z − 1]. The structure is stabilized by van der Waals interactions.

S2. Experimental

The title compound was prepared by dissolving 17-oxo-16-(3-pyridylmethylene)androst-5-en-3β-ol (1 g, 2.66 mmol) in dry toluene (150 ml) under reflux and then adding cyclohexanone (10 ml) to it. Traces of moisture were removed by azeotropic distillation. The distillation was continued at a slow rate during dropwise addition of a solution of aluminium isopropoxide (1 g) in dry toluene (15 ml). The reaction mixture was refluxed for 4 h and left overnight at room temperature. The slurry was filtered and the residue washed thoroughly with dry toluene. The combined filterate and washing were steam distilled until the organic solvent was completely removed. The solid residue was allowed to stand overnight and then filtered, washed, dried and crystallized from methanol to afford crystals of (I) (yield 0.6 g, 59.68%, m.p. 475–481 K).

S3. Refinement

All H atoms were placed geometrically and refined using a riding model, with C—H = 0.93–0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H and 1.2U_eq(C) for all others. The absolute configuration was assigned to correspond with that of a known chiral centre in a starting molecule, namely 17-oxo-16-(3-pyridylmethylene)androst-5-ene-3β-ol.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP97 (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.

16-(3-Pyridylmethylene) androst-4-ene-3,17-dione

Crystal data

C25H29NO2	F(000) = 808
Mr = 375.49	Dx = 1.207 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 11.4545 (12) Å	θ = 10–15°
b = 12.207 (2) Å	µ = 0.08 mm^−1
c = 14.784 (3) Å	T = 293 K
V = 2067.2 (6) Å^3	Plate, white
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection

Enraf-Nonius CAD4 diffractometer	1671 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.008
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω–2θ scans	h = −2→13
Absorption correction: ψ scan (North et al., 1968)	k = −5→14
Tmin = 0.993, Tmax = 1.000	l = −10→17
2222 measured reflections	2 standard reflections every 120 min
2172 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.4599P] where P = (Fo^2 + 2Fc^2)/3
2172 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

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
C1	0.7002 (3)	0.3282 (3)	0.3994 (2)	0.0555 (9)
H1A	0.6842	0.4035	0.3825	0.067*
H1B	0.6333	0.2844	0.3818	0.067*
C2	0.7144 (4)	0.3220 (3)	0.5016 (2)	0.0665 (11)
H2A	0.7740	0.3734	0.5207	0.080*
H2B	0.6416	0.3428	0.5304	0.080*
C3	0.7475 (3)	0.2098 (3)	0.5311 (2)	0.0637 (10)
C4	0.8229 (3)	0.1483 (3)	0.4706 (2)	0.0615 (9)
H4	0.8512	0.0809	0.4902	0.074*
C5	0.8540 (3)	0.1831 (3)	0.3878 (2)	0.0521 (9)
C6	0.9417 (4)	0.1197 (3)	0.3328 (2)	0.0706 (11)
H6A	0.9574	0.0503	0.3624	0.085*
H6B	1.0142	0.1605	0.3302	0.085*
C7	0.8987 (3)	0.0981 (3)	0.2370 (2)	0.0580 (9)
H7A	0.9603	0.0633	0.2024	0.070*
H7B	0.8327	0.0484	0.2391	0.070*
C8	0.8623 (3)	0.2036 (2)	0.19031 (19)	0.0431 (7)
H8	0.9311	0.2507	0.1835	0.052*
C9	0.7701 (3)	0.2646 (2)	0.24678 (18)	0.0406 (7)
H9	0.7035	0.2145	0.2511	0.049*
C10	0.8079 (3)	0.2881 (2)	0.34651 (19)	0.0457 (7)
C11	0.7233 (3)	0.3677 (3)	0.1983 (2)	0.0566 (9)
H11A	0.6592	0.3978	0.2333	0.068*
H11B	0.7847	0.4224	0.1962	0.068*
C12	0.6809 (3)	0.3451 (3)	0.10173 (19)	0.0561 (9)
H12A	0.6115	0.2996	0.1036	0.067*
H12B	0.6607	0.4137	0.0724	0.067*
C13	0.7758 (3)	0.2874 (2)	0.04786 (19)	0.0457 (8)
C14	0.8101 (3)	0.1818 (2)	0.09692 (18)	0.0412 (7)
H14	0.7370	0.1421	0.1077	0.049*
C15	0.8776 (3)	0.1141 (2)	0.02682 (18)	0.0473 (8)
H15A	0.9595	0.1345	0.0255	0.057*
H15B	0.8711	0.0363	0.0390	0.057*
C16	0.8166 (3)	0.1448 (3)	−0.06125 (19)	0.0461 (7)
C17	0.7398 (3)	0.2419 (3)	−0.0438 (2)	0.0517 (8)
C18	0.8799 (4)	0.3637 (3)	0.0289 (2)	0.0647 (10)
H18A	0.9384	0.3246	−0.0045	0.097*
H18B	0.9123	0.3886	0.0852	0.097*
H18C	0.8539	0.4256	−0.0057	0.097*
C19	0.9056 (4)	0.3756 (3)	0.3514 (2)	0.0711 (11)
H19A	0.8781	0.4428	0.3252	0.107*
H19B	0.9727	0.3504	0.3186	0.107*
H19C	0.9265	0.3880	0.4135	0.107*
C20	0.8271 (3)	0.1066 (2)	−0.1461 (2)	0.0507 (8)
H20	0.7771	0.1389	−0.1879	0.061*
C21	0.9047 (3)	0.0222 (2)	−0.1834 (2)	0.0470 (7)
C22	0.9693 (3)	−0.0521 (3)	−0.1341 (2)	0.0568 (9)
H22	0.9640	−0.0532	−0.0713	0.068*
C23	1.0417 (3)	−0.1248 (3)	−0.1782 (3)	0.0671 (10)
H23	1.0857	−0.1757	−0.1460	0.081*
C24	1.0475 (4)	−0.1204 (4)	−0.2702 (3)	0.0774 (12)
H24	1.0972	−0.1694	−0.2992	0.093*
N25	0.9868 (3)	−0.0509 (3)	−0.3218 (2)	0.0773 (10)
C26	0.9163 (3)	0.0179 (3)	−0.2770 (2)	0.0596 (9)
H26	0.8718	0.0664	−0.3111	0.072*
O3	0.7173 (3)	0.1743 (3)	0.60509 (17)	0.0922 (9)
O17	0.6663 (2)	0.2791 (2)	−0.09451 (16)	0.0810 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.071 (2)	0.0531 (19)	0.0425 (16)	0.0081 (19)	0.0031 (18)	−0.0037 (16)
C2	0.089 (3)	0.063 (2)	0.0475 (19)	0.006 (2)	0.0070 (19)	−0.0039 (17)
C3	0.077 (3)	0.071 (2)	0.0430 (19)	−0.004 (2)	−0.0034 (19)	0.0019 (18)
C4	0.080 (2)	0.0519 (19)	0.0532 (19)	0.007 (2)	−0.011 (2)	0.0030 (17)
C5	0.056 (2)	0.054 (2)	0.0456 (18)	0.0048 (17)	−0.0083 (16)	−0.0015 (15)
C6	0.076 (3)	0.076 (3)	0.059 (2)	0.029 (2)	−0.009 (2)	0.000 (2)
C7	0.068 (2)	0.055 (2)	0.0516 (19)	0.0205 (18)	−0.0011 (18)	−0.0025 (16)
C8	0.0413 (17)	0.0419 (16)	0.0461 (16)	0.0000 (14)	0.0063 (14)	−0.0010 (14)
C9	0.0418 (16)	0.0412 (15)	0.0387 (15)	−0.0015 (14)	0.0017 (13)	−0.0032 (13)
C10	0.0497 (18)	0.0428 (16)	0.0447 (16)	−0.0014 (16)	−0.0018 (15)	−0.0046 (14)
C11	0.070 (2)	0.0526 (17)	0.0469 (17)	0.0218 (18)	0.0018 (17)	−0.0007 (15)
C12	0.066 (2)	0.058 (2)	0.0442 (16)	0.0248 (19)	0.0031 (18)	0.0026 (16)
C13	0.0544 (19)	0.0408 (16)	0.0419 (17)	0.0082 (15)	0.0063 (15)	0.0021 (14)
C14	0.0408 (16)	0.0402 (16)	0.0426 (15)	0.0019 (15)	0.0061 (15)	−0.0015 (14)
C15	0.0551 (19)	0.0423 (17)	0.0445 (17)	0.0032 (16)	0.0047 (16)	−0.0022 (15)
C16	0.0492 (18)	0.0466 (17)	0.0425 (16)	0.0013 (16)	0.0062 (15)	0.0011 (14)
C17	0.056 (2)	0.0546 (19)	0.0442 (18)	0.0070 (18)	0.0055 (17)	0.0007 (16)
C18	0.088 (3)	0.0456 (18)	0.061 (2)	−0.0004 (19)	0.014 (2)	0.0084 (17)
C19	0.072 (2)	0.072 (2)	0.069 (2)	−0.018 (2)	−0.013 (2)	−0.006 (2)
C20	0.0541 (19)	0.0508 (19)	0.0472 (17)	−0.0027 (17)	0.0003 (16)	−0.0006 (15)
C21	0.0482 (17)	0.0429 (17)	0.0501 (18)	−0.0073 (16)	0.0034 (16)	−0.0089 (15)
C22	0.066 (2)	0.051 (2)	0.053 (2)	−0.0014 (19)	−0.0037 (18)	−0.0115 (16)
C23	0.064 (2)	0.049 (2)	0.088 (3)	0.0075 (19)	−0.010 (2)	−0.017 (2)
C24	0.071 (3)	0.071 (3)	0.090 (3)	0.000 (2)	0.016 (2)	−0.038 (3)
N25	0.082 (2)	0.077 (2)	0.073 (2)	−0.002 (2)	0.017 (2)	−0.0260 (19)
C26	0.068 (2)	0.060 (2)	0.051 (2)	−0.006 (2)	0.0080 (18)	−0.0147 (18)
O3	0.118 (2)	0.100 (2)	0.0584 (15)	0.007 (2)	0.0156 (17)	0.0191 (15)
O17	0.0878 (19)	0.102 (2)	0.0530 (13)	0.0429 (18)	−0.0105 (15)	−0.0059 (14)

Geometric parameters (Å, º)

C1—C2	1.523 (4)	C12—H12B	0.97
C1—C10	1.539 (4)	C13—C17	1.521 (4)
C1—H1A	0.97	C13—C14	1.531 (4)
C1—H1B	0.97	C13—C18	1.539 (5)
C2—C3	1.487 (5)	C14—C15	1.534 (4)
C2—H2A	0.97	C14—H14	0.98
C2—H2B	0.97	C15—C16	1.525 (4)
C3—O3	1.226 (4)	C15—H15A	0.97
C3—C4	1.453 (5)	C15—H15B	0.97
C4—C5	1.343 (4)	C16—C20	1.343 (4)
C4—H4	0.93	C16—C17	1.499 (4)
C5—C6	1.506 (5)	C17—O17	1.215 (4)
C5—C10	1.515 (4)	C18—H18A	0.96
C6—C7	1.522 (4)	C18—H18B	0.96
C6—H6A	0.97	C18—H18C	0.96
C6—H6B	0.97	C19—H19A	0.96
C7—C8	1.519 (4)	C19—H19B	0.96
C7—H7A	0.97	C19—H19C	0.96
C7—H7B	0.97	C20—C21	1.469 (4)
C8—C14	1.528 (4)	C20—H20	0.93
C8—C9	1.539 (4)	C21—C22	1.380 (4)
C8—H8	0.98	C21—C26	1.391 (4)
C9—C11	1.545 (4)	C22—C23	1.380 (5)
C9—C10	1.563 (4)	C22—H22	0.93
C9—H9	0.98	C23—C24	1.363 (5)
C10—C19	1.549 (5)	C23—H23	0.93
C11—C12	1.533 (4)	C24—N25	1.336 (5)
C11—H11A	0.97	C24—H24	0.93
C11—H11B	0.97	N25—C26	1.339 (4)
C12—C13	1.521 (4)	C26—H26	0.93
C12—H12A	0.97
C2—C1—C10	113.8 (3)	C11—C12—H12A	109.6
C2—C1—H1A	108.8	C13—C12—H12B	109.6
C10—C1—H1A	108.8	C11—C12—H12B	109.6
C2—C1—H1B	108.8	H12A—C12—H12B	108.1
C10—C1—H1B	108.8	C12—C13—C17	116.2 (3)
H1A—C1—H1B	107.7	C12—C13—C14	109.0 (2)
C3—C2—C1	111.4 (3)	C17—C13—C14	100.6 (2)
C3—C2—H2A	109.4	C12—C13—C18	111.6 (3)
C1—C2—H2A	109.4	C17—C13—C18	105.6 (2)
C3—C2—H2B	109.4	C14—C13—C18	113.4 (3)
C1—C2—H2B	109.4	C8—C14—C13	112.5 (2)
H2A—C2—H2B	108.0	C8—C14—C15	120.4 (2)
O3—C3—C4	122.3 (3)	C13—C14—C15	105.2 (2)
O3—C3—C2	121.0 (4)	C8—C14—H14	105.9
C4—C3—C2	116.6 (3)	C13—C14—H14	105.9
C5—C4—C3	123.7 (3)	C15—C14—H14	105.9
C5—C4—H4	118.1	C16—C15—C14	102.3 (2)
C3—C4—H4	118.1	C16—C15—H15A	111.3
C4—C5—C6	120.4 (3)	C14—C15—H15A	111.3
C4—C5—C10	122.8 (3)	C16—C15—H15B	111.3
C6—C5—C10	116.7 (3)	C14—C15—H15B	111.3
C5—C6—C7	112.0 (3)	H15A—C15—H15B	109.2
C5—C6—H6A	109.2	C20—C16—C17	119.2 (3)
C7—C6—H6A	109.2	C20—C16—C15	132.1 (3)
C5—C6—H6B	109.2	C17—C16—C15	108.4 (2)
C7—C6—H6B	109.2	O17—C17—C16	126.5 (3)
H6A—C6—H6B	107.9	O17—C17—C13	127.0 (3)
C8—C7—C6	111.4 (3)	C16—C17—C13	106.5 (3)
C8—C7—H7A	109.3	C13—C18—H18A	109.5
C6—C7—H7A	109.3	C13—C18—H18B	109.5
C8—C7—H7B	109.3	H18A—C18—H18B	109.5
C6—C7—H7B	109.3	C13—C18—H18C	109.5
H7A—C7—H7B	108.0	H18A—C18—H18C	109.5
C7—C8—C14	111.8 (2)	H18B—C18—H18C	109.5
C7—C8—C9	110.6 (2)	C10—C19—H19A	109.5
C14—C8—C9	107.8 (2)	C10—C19—H19B	109.5
C7—C8—H8	108.9	H19A—C19—H19B	109.5
C14—C8—H8	108.9	C10—C19—H19C	109.5
C9—C8—H8	108.9	H19A—C19—H19C	109.5
C8—C9—C11	112.4 (2)	H19B—C19—H19C	109.5
C8—C9—C10	114.3 (2)	C16—C20—C21	130.4 (3)
C11—C9—C10	112.5 (2)	C16—C20—H20	114.8
C8—C9—H9	105.6	C21—C20—H20	114.8
C11—C9—H9	105.6	C22—C21—C26	116.7 (3)
C10—C9—H9	105.6	C22—C21—C20	126.0 (3)
C5—C10—C1	110.1 (3)	C26—C21—C20	117.3 (3)
C5—C10—C19	108.2 (3)	C21—C22—C23	119.7 (3)
C1—C10—C19	109.6 (3)	C21—C22—H22	120.2
C5—C10—C9	108.7 (2)	C23—C22—H22	120.2
C1—C10—C9	108.4 (3)	C24—C23—C22	118.4 (4)
C19—C10—C9	111.8 (3)	C24—C23—H23	120.8
C12—C11—C9	113.3 (3)	C22—C23—H23	120.8
C12—C11—H11A	108.9	N25—C24—C23	124.7 (4)
C9—C11—H11A	108.9	N25—C24—H24	117.6
C12—C11—H11B	108.9	C23—C24—H24	117.6
C9—C11—H11B	108.9	C24—N25—C26	115.4 (3)
H11A—C11—H11B	107.7	N25—C26—C21	125.0 (4)
C13—C12—C11	110.1 (3)	N25—C26—H26	117.5
C13—C12—H12A	109.6	C21—C26—H26	117.5
C10—C1—C2—C3	−54.5 (5)	C9—C8—C14—C15	−175.3 (2)
C1—C2—C3—O3	−149.2 (4)	C12—C13—C14—C8	−62.9 (3)
C1—C2—C3—C4	34.6 (5)	C17—C13—C14—C8	174.5 (2)
O3—C3—C4—C5	177.4 (4)	C18—C13—C14—C8	62.1 (3)
C2—C3—C4—C5	−6.4 (5)	C12—C13—C14—C15	164.2 (2)
C3—C4—C5—C6	174.1 (3)	C17—C13—C14—C15	41.6 (3)
C3—C4—C5—C10	−3.6 (5)	C18—C13—C14—C15	−70.7 (3)
C4—C5—C6—C7	130.3 (4)	C8—C14—C15—C16	−161.8 (3)
C10—C5—C6—C7	−51.9 (4)	C13—C14—C15—C16	−33.6 (3)
C5—C6—C7—C8	53.8 (4)	C14—C15—C16—C20	−173.2 (3)
C6—C7—C8—C14	−175.5 (3)	C14—C15—C16—C17	12.3 (3)
C6—C7—C8—C9	−55.4 (4)	C20—C16—C17—O17	15.6 (5)
C7—C8—C9—C11	−175.5 (3)	C15—C16—C17—O17	−169.0 (3)
C14—C8—C9—C11	−53.0 (3)	C20—C16—C17—C13	−161.9 (3)
C7—C8—C9—C10	54.7 (3)	C15—C16—C17—C13	13.5 (3)
C14—C8—C9—C10	177.1 (2)	C12—C13—C17—O17	31.7 (5)
C4—C5—C10—C1	−15.5 (4)	C14—C13—C17—O17	149.2 (3)
C6—C5—C10—C1	166.8 (3)	C18—C13—C17—O17	−92.7 (4)
C4—C5—C10—C19	104.3 (4)	C12—C13—C17—C16	−150.8 (3)
C6—C5—C10—C19	−73.4 (4)	C14—C13—C17—C16	−33.4 (3)
C4—C5—C10—C9	−134.1 (3)	C18—C13—C17—C16	84.8 (3)
C6—C5—C10—C9	48.2 (4)	C17—C16—C20—C21	172.5 (3)
C2—C1—C10—C5	44.0 (4)	C15—C16—C20—C21	−1.6 (6)
C2—C1—C10—C19	−74.9 (4)	C16—C20—C21—C22	13.7 (6)
C2—C1—C10—C9	162.8 (3)	C16—C20—C21—C26	−164.9 (3)
C8—C9—C10—C5	−49.4 (3)	C26—C21—C22—C23	0.7 (5)
C11—C9—C10—C5	−179.2 (3)	C20—C21—C22—C23	−177.9 (3)
C8—C9—C10—C1	−169.1 (2)	C21—C22—C23—C24	0.2 (5)
C11—C9—C10—C1	61.2 (3)	C22—C23—C24—N25	−0.6 (7)
C8—C9—C10—C19	70.0 (3)	C23—C24—N25—C26	−0.1 (6)
C11—C9—C10—C19	−59.8 (4)	C24—N25—C26—C21	1.2 (5)
C8—C9—C11—C12	51.8 (4)	C22—C21—C26—N25	−1.5 (5)
C10—C9—C11—C12	−177.5 (3)	C20—C21—C26—N25	177.2 (3)
C9—C11—C12—C13	−53.0 (4)	C17—C16—C20—H20	−7.5
C11—C12—C13—C17	169.7 (3)	C15—C16—C20—H20	178.4
C11—C12—C13—C14	57.0 (3)	C22—C21—C20—H20	−166.3
C11—C12—C13—C18	−69.0 (3)	C26—C21—C20—H20	15.1
C7—C8—C14—C13	−178.5 (3)	C18—C13—C14—H14	177.4
C9—C8—C14—C13	59.7 (3)	H9—C9—C8—H8	179.5
C7—C8—C14—C15	−53.6 (4)	C19—C10—C13—C18	6.3 (3)