(Z)-2-(3-Methoxy­benzyl­idene)-1-aza­bicyclo­[2.2.2]octan-3-one

The crystal structure of the title compound, C₁₅H₁₇NO₂, contains two nearly identical but crystallographically independent mol­ecules, each with a double bond connecting an aza­bicyclic ring system to a 3-methoxy­benzyl­idene moiety. The space group is triclinic P. The benzene ring is twisted by 18.44 (5) and 22.35 (4)° with respect to the plane of the double bond connected to the azabicyclic ring system for the two mol­ecules. In addition to C—H...π inter­actions, mol­ecules are held together in the solid state by van der Waals inter­actions.

S1. Comment

1-Azabicyclo[2.2.2]octane ring systems linked to five- or six-membered heteroaromatics are known to be muscarinic agonists (Nilsson et al., 1995). Also, the 5-HT-3 receptor antagonist zacopride contains a 1-azabicyclo[2.2.2]octane moiety (Paulis et al., 1997). In continuation of our work with 1-azabicyclo[2.2.2]octan-3-ones as precursors of medicinal agents, we synthesized a series of 2-(substituted benzylidene/heteroar-3-ylmethylene)-1-azabicyclo[2.2.2]octan-3-ones (Sonar et al., 2004), and their crystal structures were determined in order to confirm the geometry and to establish the conformations of the molecules. The title compound was prepared by condensation of 3-methoxybenzaldeyde with 1-aza-bicyclo[2.2.2]octan-3-one under base catalysis, to afford a single geometrical isomer, viz. (Z)-2-(3-methoxybenzylidene)-1-aza-bicyclo[2.2.2]octan-3-one. In order to confirm the geometry of this compound, and to obtain more detailed information on the structural conformation of the molecule, its X-ray structure determination has been carried out, and the results are presented here.

The asymmetric unit of (I) contains two independent molecules, IA and IB (Fig. 1), with very similar geometries (Table 1). The molecule contains a double bond that connects a 1-azabicyclo[2.2.2]octan-3-one ring system to a 3-methoxybenzylidene group between atoms C7 and C8, and has a Z geometry in which the C1—C7 bond is in the trans position with respect to the C8—C9 bond. The C7═C8 bond is essentially planar, since the r.m.s. deviation from the mean plane passing through atoms N1, C8, C9, C7 and C1 is 0.0270 (5) and 0.0060 (5)° for IA and IB, respectively.

Deviations from the ideal geometry are observed in the bond angles around atoms C1, C7, C8 and C9. While the C7═C8—C9 angle [121.27 (7)° in IA and 121.07 (7)° in IB] is close to the ideal angle of 120°, the C2═C1—C7, C1—C7═C8, N1—C8═C7, C8—C9—C10 and N1—C8—C9 angles [124.25 (7), 130.35 (8), 125.30 (8), 110.88 (7) and 113.24 (7)° in IA, and 123.93 (7), 130.65 (8), 125.36 (8), 110.59 (7) and 113.54 (7)° in IB, respectively] are more distorted, as a consequence of the strain induced by the double-bond linkage at atoms C8 and C9. These deviations in angles contribute to the release of the intramolecular non-bonded interactions within the 1-azabicyclo[2.2.2]octane ring. In both cases, Csp² atoms replace Csp³ atoms, and as a result, atoms N1, C8, C9 and C10 assume a planar configuration [the N1—C8—C9—C10 torsion angle is −4.81 (9)° in IA and −0.55 (9)° in IB], with partial conjugation between the double bond and the carbonyl group, as indicated by the significant shortening of the C8—C9 single bond [1.4807 (12) Å in IA and 1.4883 (12) Å in IB]. The value of the C2═C1—C7═C8 torsion angle [−19.25 (13)° in IA and −21.74 (13)° in IB] indicates a deviation of the phenyl ring from the plane of the double bond connected to the azabicyclic ring. The observed O2—C5 [1.3710 (10) Å in IA and 1.3762 (10) Å in IB] and O2—C15 [1.4287 (11) Å in IA and 1.4255 (11) Å in IB] bond lengths are comparable to values found for aromatic methoxy groups in the literature (Domiano, et al., 1979).

The mode of packing of compound (I) along the b direction is illustrated in Fig. 2. In addition to C—H···π interactions, molecules are held together in the solid state by van der Waals interactions.

S2. Experimental

A mixture of 3-methoxybenzaldehyde (0.409 g, 3 mmol) and 1-azabicyclo[2.2.2]octan-3-one hydrochloride (0.483 g, 3 mmol) was dissolved in 10% methanolic KOH (10 ml) and the solution refluxed for 5 h. The cooled reaction mixture was poured into crushed ice (100 g), and the yellow solid that separated was collected by filtration and dried. Recrystallization from ethyl acetate afforded (I) as a yellow crystalline product, which was suitable for X-ray analysis. ¹H NMR (300 MHz, CDCl₃, p.p.m.): δ 2.03 (td, J = 7.95 and 2.7 Hz, 4H), 2.63 (p, J = 3 Hz, 1H), 2.95–3.06 (m, 2H), 3.12–3.22 (m, 2H), 3.83 (s, 3H), 6.91 (dd, J = 8.25 and 2.7 Hz, 1H), 6.98 (s, 1H), 7.29 (t, J = 8.1 Hz, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.80 (q, J = 1.5 Hz, 1H). ¹³C NMR (75 MHz, CDCl₃, p.p.m.): δ 26.2, 40.5, 47.7, 55.5, 115.5, 117.2, 125.1, 125.1, 129.4, 135.3, 145.0, 159.4, 206.4.

S3. Refinement

The crystals were non-merohedral twins in which two components with nearly equal abundances of 51.5 and 48.5% were related by a twofold operation in which the components are related by the twin-law matrix (1.00 − 0.18 0.00, 0.00 − 1.00 0.00, 0.00 0.00 − 1.00).

Computing details

Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker–Nonius, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 and local procedures.

Figures

	Fig. 1. A view of the two independent molecules of the title compound, IA and IB, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of (I), viewed along the b axis. H atoms have been omitted for clarity.

(Z)-2-(3-Methoxybenzylidene)-1-azabicyclo[2.2.2]octan-3-one

Crystal data

C15H17NO2	Z = 4
Mr = 243.30	F(000) = 520
Triclinic, P1	Dx = 1.326 Mg m^−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 5.8860 (2) Å	Cell parameters from 6692 reflections
b = 10.4741 (4) Å	θ = 1.0–68.0°
c = 20.2724 (8) Å	µ = 0.70 mm^−1
α = 81.090 (2)°	T = 90 K
β = 89.223 (2)°	Plate fragment, yellow
γ = 80.845 (2)°	0.15 × 0.05 × 0.03 mm
V = 1218.92 (8) Å^3

Data collection

Bruker-Nonius X8 Proteum diffractometer	13961 independent reflections
Radiation source: FR-591 rotating anode	11234 reflections with I > 2σ(I)
Montel graded-multilayer optics monochromator	Rint = 0.057
Detector resolution: 18 pixels mm^-1	θmax = 68.1°, θmin = 2.2°
ω and ϕ scans	h = −7→7
Absorption correction: multi-scan (TWINABS; Bruker–Nonius, 2004)	k = −12→12
Tmin = 0.803, Tmax = 0.979	l = −24→24
13961 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	Only H-atom coordinates refined
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0809P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
13961 reflections	Δρmax = 0.37 e Å^−3
351 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (4)

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
N1A	1.21514 (12)	0.58651 (7)	0.18934 (3)	0.02071 (16)
O1A	0.88957 (11)	0.87491 (6)	0.09349 (3)	0.02785 (16)
O2A	0.59990 (10)	0.27351 (6)	0.00967 (3)	0.02356 (15)
C1A	0.96328 (14)	0.45720 (8)	0.08886 (4)	0.01839 (18)
C2A	1.13872 (14)	0.35759 (9)	0.11730 (4)	0.02057 (19)
H2A	1.2621 (13)	0.3783 (2)	0.1409 (3)	0.025*
C3A	1.13006 (15)	0.22960 (9)	0.11055 (4)	0.02235 (19)
H3A	1.2519 (13)	0.1611 (8)	0.1307 (2)	0.027*
C4A	0.95202 (14)	0.19514 (9)	0.07575 (4)	0.02082 (19)
H4A	0.94801 (15)	0.1024 (10)	0.07180 (6)	0.025*
C5A	0.78012 (14)	0.29404 (9)	0.04671 (4)	0.01905 (18)
C6A	0.78615 (14)	0.42351 (9)	0.05324 (4)	0.01892 (18)
H6A	0.6642 (13)	0.4923 (7)	0.0325 (2)	0.023*
C7A	0.95376 (14)	0.59572 (8)	0.09346 (4)	0.01845 (18)
H7A	0.8539 (10)	0.6562 (6)	0.0599 (3)	0.022*
C8A	1.05940 (13)	0.65378 (8)	0.13614 (4)	0.01840 (18)
C9A	1.00821 (14)	0.79698 (9)	0.13566 (4)	0.02021 (19)
C10A	1.11786 (15)	0.83472 (9)	0.19517 (4)	0.0237 (2)
H10A	1.0780 (4)	0.9300 (10)	0.19634 (4)	0.028*
C11A	1.03147 (15)	0.75405 (9)	0.25772 (4)	0.0259 (2)
H11A	0.8609 (13)	0.77501 (18)	0.26009 (5)	0.031*
H11B	1.0988 (5)	0.77576 (19)	0.2986 (3)	0.031*
C12A	1.10447 (16)	0.60697 (9)	0.25371 (4)	0.0245 (2)
H12A	1.2128 (8)	0.5670 (3)	0.2907 (3)	0.029*
H12B	0.9676 (10)	0.5629 (3)	0.25905 (6)	0.029*
C13A	1.38001 (15)	0.79259 (10)	0.19159 (5)	0.0279 (2)
H13A	1.4557 (6)	0.80661 (15)	0.2329 (3)	0.034*
H13B	1.4430 (5)	0.8456 (4)	0.1527 (3)	0.034*
C14A	1.42751 (15)	0.64595 (10)	0.18430 (5)	0.0271 (2)
H14A	1.5006 (6)	0.63635 (12)	0.1398 (3)	0.032*
H14B	1.5395 (8)	0.5976 (4)	0.2202 (3)	0.032*
C15A	0.58368 (16)	0.14059 (9)	0.00488 (4)	0.0245 (2)
H15A	0.7204 (10)	0.1017 (3)	−0.0187 (3)	0.037*
H15B	0.4416 (10)	0.13748 (10)	−0.0204 (3)	0.037*
H15C	0.5777 (11)	0.0901 (3)	0.0505 (3)	0.037*
N1B	0.73945 (12)	0.33424 (7)	0.30478 (3)	0.01966 (16)
O1B	0.50592 (11)	0.07091 (6)	0.40593 (3)	0.02577 (15)
O2B	0.04008 (10)	0.71057 (6)	0.48627 (3)	0.02361 (14)
C1B	0.45832 (14)	0.48810 (9)	0.40795 (4)	0.01826 (18)
C2B	0.61633 (15)	0.57009 (9)	0.38230 (4)	0.02104 (19)
H2B	0.7509 (14)	0.5357 (4)	0.3581 (3)	0.025*
C3B	0.58022 (15)	0.69910 (9)	0.39150 (4)	0.0226 (2)
H3B	0.6900 (12)	0.7541 (6)	0.3743 (2)	0.027*
C4B	0.38821 (15)	0.75224 (9)	0.42512 (4)	0.02135 (19)
H4B	0.3644 (3)	0.8428 (10)	0.43050 (7)	0.026*
C5B	0.23231 (14)	0.67114 (8)	0.45064 (4)	0.01900 (18)
C6B	0.26751 (14)	0.54029 (8)	0.44254 (4)	0.01859 (18)
H6B	0.1565 (11)	0.4834 (6)	0.46144 (19)	0.022*
C7B	0.48391 (14)	0.34924 (9)	0.40242 (4)	0.01870 (19)
H7B	0.3996 (9)	0.2987 (5)	0.4349 (3)	0.022*
C8B	0.60572 (14)	0.28037 (8)	0.35951 (4)	0.01825 (18)
C9B	0.60677 (14)	0.13714 (9)	0.36384 (4)	0.01924 (19)
C10B	0.74839 (14)	0.08434 (9)	0.30836 (4)	0.02133 (19)
H10B	0.74982 (14)	−0.0116 (10)	0.31076 (5)	0.026*
C11B	0.63771 (15)	0.16072 (9)	0.24244 (4)	0.0244 (2)
H11C	0.4745 (12)	0.14568 (15)	0.23899 (5)	0.029*
H11D	0.7248 (6)	0.1300 (2)	0.2035 (3)	0.029*
C12B	0.64413 (15)	0.30808 (9)	0.24177 (4)	0.0229 (2)
H12C	0.7380 (7)	0.3396 (3)	0.2045 (3)	0.028*
H12D	0.4882 (11)	0.3567 (4)	0.23472 (7)	0.028*
C13B	0.99396 (15)	0.11562 (9)	0.31349 (4)	0.0248 (2)
H13C	1.0868 (7)	0.0888 (2)	0.2752 (3)	0.030*
H13D	1.0697 (6)	0.0667 (4)	0.3555 (3)	0.030*
C14B	0.97926 (14)	0.26479 (9)	0.31297 (4)	0.0237 (2)
H14C	1.0451 (5)	0.28013 (14)	0.3560 (3)	0.028*
H14D	1.0746 (7)	0.3016 (3)	0.2754 (3)	0.028*
C15B	−0.01329 (15)	0.84673 (9)	0.49029 (4)	0.0252 (2)
H15D	0.1159 (9)	0.8744 (2)	0.5125 (3)	0.038*
H15E	−0.1555 (11)	0.86327 (17)	0.5166 (3)	0.038*
H15F	−0.0374 (11)	0.8973 (3)	0.4447 (3)	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0199 (4)	0.0229 (4)	0.0192 (3)	−0.0018 (3)	−0.0033 (3)	−0.0040 (3)
O1A	0.0312 (3)	0.0213 (4)	0.0302 (3)	−0.0040 (3)	−0.0097 (3)	−0.0005 (3)
O2A	0.0241 (3)	0.0198 (3)	0.0279 (3)	−0.0054 (2)	−0.0072 (2)	−0.0044 (2)
C1A	0.0195 (4)	0.0222 (5)	0.0137 (4)	−0.0047 (3)	0.0027 (3)	−0.0025 (3)
C2A	0.0182 (4)	0.0252 (5)	0.0186 (4)	−0.0028 (3)	−0.0017 (3)	−0.0050 (3)
C3A	0.0220 (4)	0.0235 (5)	0.0198 (4)	0.0014 (4)	−0.0019 (3)	−0.0032 (4)
C4A	0.0244 (5)	0.0195 (5)	0.0186 (4)	−0.0035 (3)	0.0008 (3)	−0.0033 (3)
C5A	0.0192 (4)	0.0234 (5)	0.0155 (4)	−0.0059 (3)	0.0001 (3)	−0.0033 (3)
C6A	0.0194 (4)	0.0207 (5)	0.0156 (4)	−0.0017 (3)	−0.0004 (3)	−0.0010 (3)
C7A	0.0161 (4)	0.0226 (5)	0.0155 (4)	−0.0021 (3)	0.0017 (3)	−0.0008 (3)
C8A	0.0167 (4)	0.0214 (5)	0.0167 (4)	−0.0033 (3)	0.0012 (3)	−0.0013 (3)
C9A	0.0173 (4)	0.0230 (5)	0.0205 (4)	−0.0052 (3)	0.0003 (3)	−0.0019 (4)
C10A	0.0258 (5)	0.0204 (5)	0.0259 (4)	−0.0034 (4)	−0.0045 (3)	−0.0067 (4)
C11A	0.0233 (5)	0.0345 (6)	0.0208 (4)	−0.0020 (4)	−0.0016 (3)	−0.0094 (4)
C12A	0.0272 (5)	0.0291 (5)	0.0171 (4)	−0.0063 (4)	−0.0028 (3)	−0.0015 (4)
C13A	0.0238 (5)	0.0346 (6)	0.0275 (5)	−0.0117 (4)	−0.0051 (4)	−0.0032 (4)
C14A	0.0168 (4)	0.0354 (6)	0.0299 (5)	−0.0033 (4)	−0.0025 (3)	−0.0082 (4)
C15A	0.0263 (5)	0.0209 (5)	0.0282 (5)	−0.0062 (4)	−0.0031 (4)	−0.0065 (4)
N1B	0.0206 (4)	0.0212 (4)	0.0173 (3)	−0.0037 (3)	0.0026 (3)	−0.0031 (3)
O1B	0.0298 (3)	0.0229 (4)	0.0251 (3)	−0.0078 (3)	0.0046 (3)	−0.0020 (3)
O2B	0.0245 (3)	0.0189 (3)	0.0280 (3)	−0.0029 (2)	0.0055 (2)	−0.0066 (2)
C1B	0.0199 (4)	0.0219 (5)	0.0134 (4)	−0.0042 (3)	−0.0026 (3)	−0.0030 (3)
C2B	0.0214 (4)	0.0254 (5)	0.0175 (4)	−0.0063 (4)	0.0015 (3)	−0.0043 (3)
C3B	0.0262 (5)	0.0259 (5)	0.0177 (4)	−0.0107 (4)	0.0017 (3)	−0.0027 (3)
C4B	0.0274 (5)	0.0192 (5)	0.0183 (4)	−0.0053 (4)	−0.0025 (3)	−0.0035 (3)
C5B	0.0198 (4)	0.0228 (5)	0.0141 (4)	−0.0020 (3)	−0.0014 (3)	−0.0032 (3)
C6B	0.0205 (4)	0.0205 (5)	0.0155 (4)	−0.0059 (3)	−0.0012 (3)	−0.0023 (3)
C7B	0.0177 (4)	0.0241 (5)	0.0144 (4)	−0.0053 (3)	−0.0014 (3)	−0.0011 (3)
C8B	0.0170 (4)	0.0206 (5)	0.0170 (4)	−0.0035 (3)	−0.0013 (3)	−0.0016 (3)
C9B	0.0163 (4)	0.0237 (5)	0.0177 (4)	−0.0040 (3)	−0.0024 (3)	−0.0021 (3)
C10B	0.0235 (5)	0.0174 (5)	0.0236 (4)	−0.0030 (3)	0.0008 (3)	−0.0054 (3)
C11B	0.0243 (5)	0.0308 (6)	0.0199 (4)	−0.0061 (4)	0.0002 (3)	−0.0074 (4)
C12B	0.0236 (5)	0.0278 (5)	0.0158 (4)	−0.0008 (4)	0.0001 (3)	−0.0017 (3)
C13B	0.0197 (4)	0.0260 (5)	0.0274 (5)	−0.0008 (4)	0.0019 (3)	−0.0034 (4)
C14B	0.0179 (4)	0.0287 (5)	0.0255 (4)	−0.0055 (4)	0.0012 (3)	−0.0056 (4)
C15B	0.0291 (5)	0.0190 (5)	0.0275 (4)	−0.0020 (4)	0.0030 (4)	−0.0059 (4)

Geometric parameters (Å, º)

N1A—C8A	1.4443 (10)	N1B—C8B	1.4465 (10)
N1A—C14A	1.4782 (11)	N1B—C14B	1.4803 (11)
N1A—C12A	1.4807 (11)	N1B—C12B	1.4827 (10)
O1A—C9A	1.2261 (10)	O1B—C9B	1.2230 (10)
O2A—C5A	1.3710 (10)	O2B—C5B	1.3762 (10)
O2A—C15A	1.4287 (11)	O2B—C15B	1.4255 (11)
C1A—C6A	1.3962 (12)	C1B—C6B	1.3978 (12)
C1A—C2A	1.4051 (12)	C1B—C2B	1.4055 (12)
C1A—C7A	1.4604 (12)	C1B—C7B	1.4598 (12)
C2A—C3A	1.3773 (13)	C2B—C3B	1.3754 (13)
C2A—H2A	0.947 (10)	C2B—H2B	0.975 (10)
C3A—C4A	1.3947 (12)	C3B—C4B	1.3958 (13)
C3A—H3A	0.974 (11)	C3B—H3B	0.959 (11)
C4A—C5A	1.3918 (12)	C4B—C5B	1.3893 (12)
C4A—H4A	0.991 (10)	C4B—H4B	0.960 (10)
C5A—C6A	1.3888 (12)	C5B—C6B	1.3881 (12)
C6A—H6A	0.980 (10)	C6B—H6B	0.987 (10)
C7A—C8A	1.3426 (12)	C7B—C8B	1.3431 (12)
C7A—H7A	0.984 (10)	C7B—H7B	0.963 (10)
C8A—C9A	1.4807 (12)	C8B—C9B	1.4883 (12)
C9A—C10A	1.5094 (11)	C9B—C10B	1.5120 (11)
C10A—C11A	1.5388 (12)	C10B—C13B	1.5404 (12)
C10A—C13A	1.5399 (12)	C10B—C11B	1.5416 (12)
C10A—H10A	0.992 (10)	C10B—H10B	0.998 (11)
C11A—C12A	1.5466 (13)	C11B—C12B	1.5479 (13)
C11A—H11A	0.995 (7)	C11B—H11C	1.003 (7)
C11A—H11B	0.995 (7)	C11B—H11D	1.003 (7)
C12A—H12A	0.987 (7)	C12B—H12C	0.977 (7)
C12A—H12B	0.987 (7)	C12B—H12D	0.977 (7)
C13A—C14A	1.5465 (13)	C13B—C14B	1.5493 (12)
C13A—H13A	0.995 (7)	C13B—H13C	0.994 (7)
C13A—H13B	0.995 (7)	C13B—H13D	0.994 (7)
C14A—H14A	1.006 (7)	C14B—H14C	1.004 (7)
C14A—H14B	1.006 (7)	C14B—H14D	1.004 (7)
C15A—H15A	0.994 (6)	C15B—H15D	0.992 (6)
C15A—H15B	0.994 (6)	C15B—H15E	0.992 (6)
C15A—H15C	0.994 (6)	C15B—H15F	0.992 (6)
C8A—N1A—C14A	108.57 (7)	C8B—N1B—C14B	108.30 (6)
C8A—N1A—C12A	108.08 (6)	C8B—N1B—C12B	108.11 (6)
C14A—N1A—C12A	108.39 (7)	C14B—N1B—C12B	108.32 (6)
C5A—O2A—C15A	116.68 (6)	C5B—O2B—C15B	116.86 (7)
C6A—C1A—C2A	118.72 (8)	C6B—C1B—C2B	118.79 (8)
C6A—C1A—C7A	117.03 (7)	C6B—C1B—C7B	117.25 (7)
C2A—C1A—C7A	124.25 (7)	C2B—C1B—C7B	123.93 (7)
C3A—C2A—C1A	119.59 (8)	C3B—C2B—C1B	119.66 (8)
C3A—C2A—H2A	120.2	C3B—C2B—H2B	120.2
C1A—C2A—H2A	120.2	C1B—C2B—H2B	120.2
C2A—C3A—C4A	121.96 (8)	C2B—C3B—C4B	121.80 (8)
C2A—C3A—H3A	119.0	C2B—C3B—H3B	119.1
C4A—C3A—H3A	119.0	C4B—C3B—H3B	119.1
C5A—C4A—C3A	118.45 (8)	C5B—C4B—C3B	118.55 (8)
C5A—C4A—H4A	120.8	C5B—C4B—H4B	120.7
C3A—C4A—H4A	120.8	C3B—C4B—H4B	120.7
O2A—C5A—C6A	115.62 (7)	O2B—C5B—C6B	115.35 (7)
O2A—C5A—C4A	124.12 (8)	O2B—C5B—C4B	124.21 (8)
C6A—C5A—C4A	120.26 (7)	C6B—C5B—C4B	120.42 (8)
C5A—C6A—C1A	121.02 (8)	C5B—C6B—C1B	120.76 (8)
C5A—C6A—H6A	119.5	C5B—C6B—H6B	119.6
C1A—C6A—H6A	119.5	C1B—C6B—H6B	119.6
C8A—C7A—C1A	130.35 (8)	C8B—C7B—C1B	130.65 (8)
C8A—C7A—H7A	114.8	C8B—C7B—H7B	114.7
C1A—C7A—H7A	114.8	C1B—C7B—H7B	114.7
C7A—C8A—N1A	125.30 (8)	C7B—C8B—N1B	125.36 (8)
C7A—C8A—C9A	121.27 (7)	C7B—C8B—C9B	121.07 (7)
N1A—C8A—C9A	113.24 (7)	N1B—C8B—C9B	113.54 (7)
O1A—C9A—C8A	124.99 (7)	O1B—C9B—C8B	125.02 (7)
O1A—C9A—C10A	124.12 (8)	O1B—C9B—C10B	124.39 (8)
C8A—C9A—C10A	110.88 (7)	C8B—C9B—C10B	110.59 (7)
C9A—C10A—C11A	106.81 (7)	C9B—C10B—C13B	108.42 (7)
C9A—C10A—C13A	108.14 (7)	C9B—C10B—C11B	106.21 (7)
C11A—C10A—C13A	107.83 (7)	C13B—C10B—C11B	108.42 (7)
C9A—C10A—H10A	111.3	C9B—C10B—H10B	111.2
C11A—C10A—H10A	111.3	C13B—C10B—H10B	111.2
C13A—C10A—H10A	111.3	C11B—C10B—H10B	111.2
C10A—C11A—C12A	108.69 (7)	C10B—C11B—C12B	108.36 (7)
C10A—C11A—H11A	110.0	C10B—C11B—H11C	110.0
C12A—C11A—H11A	110.0	C12B—C11B—H11C	110.0
C10A—C11A—H11B	110.0	C10B—C11B—H11D	110.0
C12A—C11A—H11B	110.0	C12B—C11B—H11D	110.0
H11A—C11A—H11B	108.3	H11C—C11B—H11D	108.4
N1A—C12A—C11A	111.73 (7)	N1B—C12B—C11B	112.32 (7)
N1A—C12A—H12A	109.3	N1B—C12B—H12C	109.1
C11A—C12A—H12A	109.3	C11B—C12B—H12C	109.1
N1A—C12A—H12B	109.3	N1B—C12B—H12D	109.1
C11A—C12A—H12B	109.3	C11B—C12B—H12D	109.1
H12A—C12A—H12B	107.9	H12C—C12B—H12D	107.9
C10A—C13A—C14A	108.28 (7)	C10B—C13B—C14B	108.69 (7)
C10A—C13A—H13A	110.0	C10B—C13B—H13C	110.0
C14A—C13A—H13A	110.0	C14B—C13B—H13C	110.0
C10A—C13A—H13B	110.0	C10B—C13B—H13D	110.0
C14A—C13A—H13B	110.0	C14B—C13B—H13D	110.0
H13A—C13A—H13B	108.4	H13C—C13B—H13D	108.3
N1A—C14A—C13A	112.16 (7)	N1B—C14B—C13B	111.98 (7)
N1A—C14A—H14A	109.2	N1B—C14B—H14C	109.2
C13A—C14A—H14A	109.2	C13B—C14B—H14C	109.2
N1A—C14A—H14B	109.2	N1B—C14B—H14D	109.2
C13A—C14A—H14B	109.2	C13B—C14B—H14D	109.2
H14A—C14A—H14B	107.9	H14C—C14B—H14D	107.9
O2A—C15A—H15A	109.5	O2B—C15B—H15D	109.5
O2A—C15A—H15B	109.5	O2B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
O2A—C15A—H15C	109.5	O2B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
C6A—C1A—C2A—C3A	−1.20 (11)	C6B—C1B—C2B—C3B	−0.15 (11)
C7A—C1A—C2A—C3A	179.36 (7)	C7B—C1B—C2B—C3B	−178.35 (7)
C1A—C2A—C3A—C4A	0.40 (12)	C1B—C2B—C3B—C4B	−0.82 (12)
C2A—C3A—C4A—C5A	0.58 (12)	C2B—C3B—C4B—C5B	0.98 (12)
C15A—O2A—C5A—C6A	−177.09 (7)	C15B—O2B—C5B—C6B	−174.35 (7)
C15A—O2A—C5A—C4A	4.08 (11)	C15B—O2B—C5B—C4B	7.28 (11)
C3A—C4A—C5A—O2A	178.03 (7)	C3B—C4B—C5B—O2B	178.14 (7)
C3A—C4A—C5A—C6A	−0.74 (12)	C3B—C4B—C5B—C6B	−0.16 (12)
O2A—C5A—C6A—C1A	−178.94 (7)	O2B—C5B—C6B—C1B	−179.24 (7)
C4A—C5A—C6A—C1A	−0.06 (12)	C4B—C5B—C6B—C1B	−0.80 (12)
C2A—C1A—C6A—C5A	1.04 (11)	C2B—C1B—C6B—C5B	0.96 (11)
C7A—C1A—C6A—C5A	−179.48 (7)	C7B—C1B—C6B—C5B	179.28 (7)
C6A—C1A—C7A—C8A	161.30 (8)	C6B—C1B—C7B—C8B	160.04 (9)
C2A—C1A—C7A—C8A	−19.25 (13)	C2B—C1B—C7B—C8B	−21.74 (13)
C1A—C7A—C8A—N1A	0.43 (14)	C1B—C7B—C8B—N1B	−2.41 (14)
C1A—C7A—C8A—C9A	−174.31 (7)	C1B—C7B—C8B—C9B	179.61 (7)
C14A—N1A—C8A—C7A	129.30 (9)	C14B—N1B—C8B—C7B	123.55 (9)
C12A—N1A—C8A—C7A	−113.33 (9)	C12B—N1B—C8B—C7B	−119.29 (9)
C14A—N1A—C8A—C9A	−55.59 (8)	C14B—N1B—C8B—C9B	−58.34 (8)
C12A—N1A—C8A—C9A	61.78 (9)	C12B—N1B—C8B—C9B	58.82 (8)
C7A—C8A—C9A—O1A	−8.26 (13)	C7B—C8B—C9B—O1B	−1.78 (12)
N1A—C8A—C9A—O1A	176.40 (8)	N1B—C8B—C9B—O1B	−179.99 (7)
C7A—C8A—C9A—C10A	170.53 (7)	C7B—C8B—C9B—C10B	177.65 (7)
N1A—C8A—C9A—C10A	−4.81 (9)	N1B—C8B—C9B—C10B	−0.55 (9)
O1A—C9A—C10A—C11A	123.20 (9)	O1B—C9B—C10B—C13B	−122.97 (9)
C8A—C9A—C10A—C11A	−55.60 (9)	C8B—C9B—C10B—C13B	57.60 (9)
O1A—C9A—C10A—C13A	−120.98 (9)	O1B—C9B—C10B—C11B	120.69 (9)
C8A—C9A—C10A—C13A	60.22 (9)	C8B—C9B—C10B—C11B	−58.75 (8)
C9A—C10A—C11A—C12A	59.83 (9)	C9B—C10B—C11B—C12B	59.59 (8)
C13A—C10A—C11A—C12A	−56.20 (9)	C13B—C10B—C11B—C12B	−56.75 (9)
C8A—N1A—C12A—C11A	−54.97 (9)	C8B—N1B—C12B—C11B	−55.70 (9)
C14A—N1A—C12A—C11A	62.52 (9)	C14B—N1B—C12B—C11B	61.44 (8)
C10A—C11A—C12A—N1A	−5.17 (9)	C10B—C11B—C12B—N1B	−3.39 (9)
C9A—C10A—C13A—C14A	−53.06 (9)	C9B—C10B—C13B—C14B	−54.70 (9)
C11A—C10A—C13A—C14A	62.09 (9)	C11B—C10B—C13B—C14B	60.21 (8)
C8A—N1A—C14A—C13A	60.90 (9)	C8B—N1B—C14B—C13B	59.27 (8)
C12A—N1A—C14A—C13A	−56.28 (9)	C12B—N1B—C14B—C13B	−57.75 (8)
C10A—C13A—C14A—N1A	−5.45 (10)	C10B—C13B—C14B—N1B	−2.53 (9)