(E)-3-(1-Naphthyl-amino)-methyl-ene-(+)-camphor.

In the crystal structure of the title ketoamine {systematic name: (E)-1,7,7-trimethyl-3-[(1-naphthyl-amino)-methyl-idene]bicyclo-[2.2.1]heptan-2-one}, C(21)H(23)NO, there are two independent mol-ecules in the asymmetric unit. Both mol-ecules have an E configuration about the alkene function. The main conformational difference between the mol-ecules is in the orientation of the plane of the naphthyl rings with respect to the camphor fragment. The torsion angle about the enamine C-N bond is 21.3 (7)° for mol-ecule A, but -24.4 (8)° for mol-ecule B. Inter-molecular N-H⋯O hydrogen bonds between the amino and ketone groups of adjacent independent mol-ecules sustain the crystal, and the resulting extended chains, containing an alternating sequence of the two independent mol-ecules, run parallel to the [001] direction and can be described by a graph-set motif of C(2) (2)(12).

Related literature

For the conformations of β-class="Chemical">ketoamines, see: Zharkova et al. (2009 ▶). For chiral class="Gene">pan class="Chemical">camphor-derived β-amino­ketonate ligands, see: Everett & Powers (1970 ▶); Casella et al. (1979 ▶). For reactions involving amino­ketonate complexes, see: Hsu, Chang et al. (2004 ▶); Hsu, Li et al. (2007 ▶); Lai et al. (2005 ▶); Pan et al. (2008 ▶); Wang et al. (2006 ▶). For the coordination chemistry of β-amino­ketonate ligands, see: Lesikar et al. (2008 ▶); Sedai et al. (2008 ▶). For the synthesis of (+)-hy­droxy­methyl­enecamphor, see: Lintvedt & Fatta (1968 ▶). For related (1-naphthyl­amino)­methyl­ene structures, see: Li et al. (2009 ▶); Özek et al. (2005 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

pan class="Chemical">C21H23NO

M = 305.42

Monoclinic,

a = 23.807 (2) Å

b = 11.9688 (12) Å

c = 12.0192 (8) Å

β = 95.672 (5)°

V = 3408.1 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.07 mm−1

T = 160 K

0.25 × 0.20 × 0.12 mm

Data collection

Nonius KappaCCD area-detector diffractometer

21618 measured reflections

3170 independent reflections

2227 reflections with I > 2σ(I)

R int = 0.092

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.155

S = 1.05

3170 reflections

428 parameters

1 restraint

pan class="Disease">H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.17 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810052487/span class="Gene">u2235sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052487/span class="Gene">u2235Isup2.hkl

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

C21H23NO	F(000) = 1312
Mr = 305.42	Dx = 1.190 Mg m−3
Monoclinic, C2	Melting point: 352 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 23.807 (2) Å	Cell parameters from 3158 reflections
b = 11.9688 (12) Å	θ = 2.0–25.0°
c = 12.0192 (8) Å	µ = 0.07 mm−1
β = 95.672 (5)°	T = 160 K
V = 3408.1 (5) Å3	Prism, yellow
Z = 8	0.25 × 0.20 × 0.12 mm

Nonius KappaCCD area-detector diffractometer	2227 reflections with I > 2σ(I)
Radiation source: Nonius FR590 sealed tube generator	Rint = 0.092
horizontally mounted graphite crystal	θmax = 25.0°, θmin = 2.5°
Detector resolution: 9 pixels mm-1	h = 0→28
ω scans with κ offsets	k = 0→14
21618 measured reflections	l = −14→14
3170 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.155	w = 1/[σ2(Fo2) + (0.0737P)2 + 1.1311P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3170 reflections	Δρmax = 0.24 e Å−3
428 parameters	Δρmin = −0.17 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0040 (7)

Experimental. Solvent used: EtOH. Cooling Device: Oxford Cryosystems Cryostream 700. Crystal mount: glued on a glass fibre. Mosaicity: 1.498 (4)°. Frames collected: 273. Seconds exposure per frame: 88. Degrees rotation per frame: 1.4. Crystal-Detector distance: 30.0 mm.Spectroscopic data:1H-NMR (400 MHz, CDCl3): δ 10.77 (d, J = 12.0 Hz, 1H), 8.09 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 12.0 Hz, 1H), 7.54–7.45 (m, 3H), 7.40–7.36 (t, 1H), 7.20 (d, J = 12.0 Hz, 1H), 7.11 (d, J = 8.0 Hz, 1H), 2.53–2.52 (d, J = 4.0 Hz, 1H), 2.11–2.05 (m, 1H), 1.73–1.66 (m, 1H), 1.49–1.41 (m, 2H), 1.03 (s, 3H), 0.94 (s,3H), 0.89 (s, 3H); 13C {1H}-NMR (101 MHz, CDCl3): δ 209.4, 136.9, 134.5, 132.9, 128.5, 126.4, 126.2, 125.9, 123.9, 121.9, 120.7, 116.3, 107.6, 58.9, 49.9, 49.1, 30.4, 28.5, 20.7, 19.1, 9.2; FT—IR (ν, cm- 1, KBr): 3300 (N—H), 1681 (C=O).

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.

	x	y	z	Uiso*/Ueq
O1	0.68329 (13)	0.4955 (3)	0.5734 (2)	0.0597 (10)
N1	0.76542 (16)	0.5821 (4)	0.2820 (3)	0.0467 (10)
H1	0.7453 (18)	0.563 (4)	0.204 (4)	0.056*
C1	0.82420 (18)	0.6018 (4)	0.2844 (4)	0.0457 (12)
C2	0.8445 (2)	0.6690 (4)	0.1988 (4)	0.0454 (12)
C3	0.8088 (2)	0.7267 (5)	0.1164 (4)	0.0542 (14)
H3	0.7691	0.7240	0.1190	0.065*
C4	0.8307 (2)	0.7866 (5)	0.0329 (4)	0.0624 (15)
H4	0.8064	0.8257	−0.0211	0.075*
C5	0.8888 (3)	0.7892 (5)	0.0282 (5)	0.0674 (16)
H5	0.9036	0.8278	−0.0316	0.081*
C6	0.9245 (2)	0.7388 (5)	0.1057 (4)	0.0584 (15)
H6	0.9641	0.7438	0.1009	0.070*
C7	0.9041 (2)	0.6780 (5)	0.1950 (4)	0.0508 (13)
C8	0.9406 (2)	0.6296 (5)	0.2821 (5)	0.0575 (14)
H8	0.9802	0.6378	0.2817	0.069*
C9	0.9198 (2)	0.5715 (5)	0.3664 (4)	0.0569 (13)
H9	0.9449	0.5412	0.4251	0.068*
C10	0.86094 (19)	0.5562 (4)	0.3669 (4)	0.0514 (13)
H10	0.8468	0.5140	0.4250	0.062*
C11	0.74053 (18)	0.5505 (4)	0.3731 (4)	0.0435 (12)
H11	0.7592	0.5701	0.4439	0.052*
C12	0.69145 (18)	0.4934 (4)	0.3731 (3)	0.0436 (12)
C13	0.65587 (19)	0.4306 (4)	0.2821 (3)	0.0454 (12)
H13	0.6557	0.4624	0.2051	0.054*
C14	0.6757 (2)	0.3084 (4)	0.2953 (4)	0.0574 (14)
H141	0.7173	0.3028	0.2978	0.069*
H142	0.6583	0.2611	0.2336	0.069*
C15	0.6547 (2)	0.2746 (5)	0.4094 (4)	0.0595 (14)
H151	0.6869	0.2576	0.4654	0.071*
H152	0.6297	0.2084	0.4008	0.071*
C16	0.62158 (19)	0.3793 (4)	0.4453 (3)	0.0469 (12)
C17	0.66827 (19)	0.4636 (4)	0.4773 (4)	0.0467 (13)
C18	0.59773 (18)	0.4275 (4)	0.3300 (3)	0.0459 (12)
C19	0.5713 (2)	0.5429 (5)	0.3385 (4)	0.0590 (14)
H191	0.5393	0.5382	0.3836	0.088*
H192	0.5581	0.5699	0.2634	0.088*
H193	0.5995	0.5948	0.3738	0.088*
C20	0.5540 (2)	0.3515 (5)	0.2652 (4)	0.0624 (15)
H201	0.5440	0.3824	0.1903	0.094*
H202	0.5202	0.3469	0.3051	0.094*
H203	0.5700	0.2766	0.2586	0.094*
C21	0.5823 (2)	0.3569 (6)	0.5342 (4)	0.0631 (15)
H211	0.5603	0.4243	0.5460	0.095*
H212	0.6044	0.3362	0.6042	0.095*
H213	0.5566	0.2956	0.5099	0.095*
O2	0.69132 (15)	0.5802 (3)	1.0744 (3)	0.0673 (11)
N2	0.76421 (18)	0.5057 (4)	0.7714 (3)	0.0564 (12)
H2	0.743 (2)	0.502 (5)	0.712 (4)	0.068*
C31	0.8225 (2)	0.4882 (5)	0.7702 (4)	0.0512 (13)
C32	0.8415 (2)	0.4213 (5)	0.6840 (4)	0.0554 (14)
C33	0.8049 (2)	0.3591 (5)	0.6054 (4)	0.0588 (14)
H33	0.7653	0.3617	0.6100	0.071*
C34	0.8253 (3)	0.2968 (5)	0.5246 (5)	0.0674 (16)
H34	0.7998	0.2569	0.4732	0.081*
C35	0.8829 (3)	0.2900 (6)	0.5154 (5)	0.0750 (17)
H35	0.8965	0.2475	0.4569	0.090*
C36	0.9189 (3)	0.3432 (5)	0.5889 (5)	0.0700 (16)
H36	0.9582	0.3376	0.5822	0.084*
C37	0.8998 (2)	0.4094 (5)	0.6788 (5)	0.0572 (14)
C38	0.9397 (2)	0.4604 (5)	0.7578 (5)	0.0621 (15)
H38	0.9791	0.4515	0.7537	0.075*
C39	0.9195 (2)	0.5234 (5)	0.8409 (5)	0.0708 (17)
H39	0.9455	0.5581	0.8952	0.085*
C40	0.8608 (2)	0.5376 (5)	0.8472 (4)	0.0582 (14)
H40	0.8480	0.5817	0.9054	0.070*
C41	0.7408 (2)	0.5355 (5)	0.8651 (4)	0.0575 (14)
H41	0.7626	0.5197	0.9339	0.069*
C42	0.68961 (18)	0.5857 (4)	0.8730 (4)	0.0452 (12)
C43	0.6461 (2)	0.6346 (5)	0.7896 (4)	0.0547 (14)
H43	0.6592	0.6503	0.7146	0.066*
C44	0.5941 (2)	0.5569 (6)	0.7881 (4)	0.0674 (16)
H441	0.5651	0.5764	0.7263	0.081*
H442	0.6049	0.4775	0.7811	0.081*
C45	0.5733 (2)	0.5810 (5)	0.9029 (4)	0.0621 (14)
H451	0.5747	0.5127	0.9495	0.075*
H452	0.5341	0.6097	0.8944	0.075*
C46	0.6151 (2)	0.6717 (5)	0.9562 (4)	0.0524 (13)
C47	0.6699 (2)	0.6078 (4)	0.9813 (4)	0.0458 (12)
C48	0.62762 (19)	0.7388 (5)	0.8533 (4)	0.0556 (14)
C49	0.6746 (2)	0.8251 (5)	0.8770 (5)	0.0661 (15)
H491	0.6821	0.8616	0.8070	0.099*
H492	0.7090	0.7877	0.9098	0.099*
H493	0.6630	0.8812	0.9295	0.099*
C50	0.5761 (2)	0.8006 (6)	0.7922 (5)	0.0802 (18)
H501	0.5461	0.7466	0.7704	0.120*
H502	0.5875	0.8377	0.7253	0.120*
H503	0.5622	0.8565	0.8423	0.120*
C51	0.5939 (3)	0.7335 (6)	1.0546 (4)	0.0796 (18)
H511	0.6229	0.7860	1.0858	0.119*
H512	0.5857	0.6796	1.1123	0.119*
H513	0.5594	0.7747	1.0292	0.119*

	U11	U22	U33	U12	U13	U23
O1	0.059 (2)	0.080 (3)	0.0400 (18)	−0.0056 (19)	0.0018 (15)	−0.0112 (19)
N1	0.043 (2)	0.055 (3)	0.041 (2)	−0.004 (2)	−0.0013 (17)	0.000 (2)
C1	0.038 (3)	0.045 (3)	0.054 (3)	−0.002 (2)	0.004 (2)	−0.004 (2)
C2	0.051 (3)	0.041 (3)	0.046 (3)	−0.009 (3)	0.014 (2)	−0.011 (2)
C3	0.055 (3)	0.053 (3)	0.054 (3)	−0.014 (3)	0.007 (2)	−0.008 (3)
C4	0.076 (4)	0.063 (4)	0.048 (3)	−0.022 (3)	0.005 (3)	−0.002 (3)
C5	0.078 (4)	0.072 (4)	0.054 (3)	−0.037 (4)	0.019 (3)	−0.012 (3)
C6	0.055 (3)	0.063 (4)	0.061 (3)	−0.022 (3)	0.021 (3)	−0.017 (3)
C7	0.047 (3)	0.046 (3)	0.061 (3)	−0.008 (3)	0.010 (2)	−0.017 (3)
C8	0.040 (3)	0.049 (3)	0.085 (4)	−0.005 (3)	0.013 (3)	−0.015 (3)
C9	0.049 (3)	0.040 (3)	0.079 (3)	0.004 (3)	−0.005 (3)	−0.003 (3)
C10	0.047 (3)	0.043 (3)	0.065 (3)	−0.005 (3)	0.009 (2)	−0.003 (3)
C11	0.045 (3)	0.044 (3)	0.041 (2)	−0.001 (2)	0.002 (2)	−0.003 (2)
C12	0.040 (3)	0.050 (3)	0.041 (2)	−0.001 (2)	0.0016 (19)	0.001 (2)
C13	0.048 (3)	0.054 (3)	0.035 (2)	−0.007 (2)	0.0080 (19)	0.005 (2)
C14	0.064 (3)	0.057 (4)	0.053 (3)	−0.006 (3)	0.013 (2)	−0.007 (3)
C15	0.071 (3)	0.049 (3)	0.059 (3)	−0.006 (3)	0.008 (3)	0.004 (3)
C16	0.050 (3)	0.050 (3)	0.041 (2)	−0.008 (3)	0.007 (2)	0.001 (2)
C17	0.045 (3)	0.054 (3)	0.040 (3)	0.006 (2)	0.000 (2)	0.000 (2)
C18	0.045 (3)	0.051 (3)	0.041 (2)	−0.011 (2)	0.0043 (19)	−0.001 (2)
C19	0.047 (3)	0.066 (4)	0.063 (3)	−0.003 (3)	−0.001 (2)	0.002 (3)
C20	0.046 (3)	0.085 (4)	0.057 (3)	−0.024 (3)	0.009 (2)	−0.013 (3)
C21	0.063 (3)	0.078 (4)	0.051 (3)	−0.007 (3)	0.019 (2)	0.001 (3)
O2	0.077 (2)	0.076 (3)	0.0455 (18)	−0.020 (2)	−0.0127 (17)	0.0087 (19)
N2	0.049 (3)	0.064 (3)	0.055 (2)	0.006 (2)	0.0027 (19)	−0.001 (2)
C31	0.049 (3)	0.047 (3)	0.058 (3)	0.002 (3)	0.006 (2)	0.000 (3)
C32	0.054 (3)	0.040 (3)	0.072 (3)	0.005 (3)	0.007 (3)	0.017 (3)
C33	0.058 (3)	0.052 (4)	0.066 (3)	−0.003 (3)	0.004 (3)	0.009 (3)
C34	0.089 (5)	0.054 (4)	0.060 (3)	0.013 (3)	0.011 (3)	0.002 (3)
C35	0.095 (5)	0.065 (4)	0.066 (4)	0.010 (4)	0.013 (3)	0.006 (3)
C36	0.067 (4)	0.062 (4)	0.084 (4)	0.017 (3)	0.022 (3)	0.020 (4)
C37	0.048 (3)	0.045 (3)	0.079 (3)	0.005 (3)	0.009 (3)	0.017 (3)
C38	0.056 (3)	0.051 (4)	0.082 (4)	0.006 (3)	0.020 (3)	0.013 (3)
C39	0.058 (4)	0.051 (4)	0.101 (4)	−0.011 (3)	−0.004 (3)	0.015 (4)
C40	0.051 (3)	0.052 (3)	0.072 (3)	0.003 (3)	0.006 (3)	0.002 (3)
C41	0.061 (3)	0.063 (4)	0.048 (3)	−0.010 (3)	0.001 (2)	0.003 (3)
C42	0.039 (3)	0.053 (3)	0.043 (3)	0.004 (2)	0.003 (2)	0.000 (2)
C43	0.057 (3)	0.064 (4)	0.042 (3)	0.004 (3)	0.000 (2)	0.007 (3)
C44	0.056 (3)	0.083 (4)	0.060 (3)	0.013 (3)	−0.012 (2)	−0.004 (3)
C45	0.046 (3)	0.063 (4)	0.078 (3)	0.005 (3)	0.010 (3)	0.002 (3)
C46	0.055 (3)	0.053 (3)	0.051 (3)	0.004 (3)	0.015 (2)	0.001 (2)
C47	0.050 (3)	0.047 (3)	0.039 (3)	−0.004 (2)	−0.004 (2)	0.003 (2)
C48	0.050 (3)	0.058 (4)	0.060 (3)	0.011 (3)	0.007 (2)	0.012 (3)
C49	0.066 (3)	0.058 (4)	0.076 (3)	−0.002 (3)	0.016 (3)	0.009 (3)
C50	0.073 (4)	0.083 (5)	0.085 (4)	0.021 (4)	0.009 (3)	0.013 (4)
C51	0.093 (4)	0.077 (5)	0.073 (4)	0.002 (4)	0.031 (3)	−0.006 (3)

O1—C17	1.235 (5)	O2—C47	1.229 (5)
N1—C11	1.351 (6)	N2—C41	1.353 (6)
N1—C1	1.416 (6)	N2—C31	1.404 (6)
N1—H1	1.03 (4)	N2—H2	0.83 (5)
C1—C10	1.370 (6)	C31—C40	1.368 (7)
C1—C2	1.427 (6)	C31—C32	1.419 (7)
C2—C3	1.419 (7)	C32—C37	1.404 (7)
C2—C7	1.429 (6)	C32—C33	1.430 (7)
C3—C4	1.378 (7)	C33—C34	1.353 (7)
C3—H3	0.9500	C33—H33	0.9500
C4—C5	1.391 (8)	C34—C35	1.390 (8)
C4—H4	0.9500	C34—H34	0.9500
C5—C6	1.341 (8)	C35—C36	1.331 (8)
C5—H5	0.9500	C35—H35	0.9500
C6—C7	1.421 (7)	C36—C37	1.449 (8)
C6—H6	0.9500	C36—H36	0.9500
C7—C8	1.416 (7)	C37—C38	1.413 (8)
C8—C9	1.362 (7)	C38—C39	1.375 (7)
C8—H8	0.9500	C38—H38	0.9500
C9—C10	1.414 (6)	C39—C40	1.418 (7)
C9—H9	0.9500	C39—H39	0.9500
C10—H10	0.9500	C40—H40	0.9500
C11—C12	1.353 (6)	C41—C42	1.371 (7)
C11—H11	0.9500	C41—H41	0.9500
C12—C17	1.462 (6)	C42—C47	1.451 (6)
C12—C13	1.516 (6)	C42—C43	1.488 (6)
C13—C14	1.541 (7)	C43—C44	1.547 (8)
C13—C18	1.551 (6)	C43—C48	1.551 (7)
C13—H13	1.0000	C43—H43	1.0000
C14—C15	1.559 (7)	C44—C45	1.540 (7)
C14—H141	0.9900	C44—H441	0.9900
C14—H142	0.9900	C44—H442	0.9900
C15—C16	1.563 (7)	C45—C46	1.566 (8)
C15—H151	0.9900	C45—H451	0.9900
C15—H152	0.9900	C45—H452	0.9900
C16—C21	1.512 (6)	C46—C47	1.516 (7)
C16—C17	1.522 (7)	C46—C51	1.523 (7)
C16—C18	1.555 (6)	C46—C48	1.528 (7)
C18—C19	1.526 (7)	C48—C49	1.529 (7)
C18—C20	1.535 (6)	C48—C50	1.553 (7)
C19—H191	0.9800	C49—H491	0.9800
C19—H192	0.9800	C49—H492	0.9800
C19—H193	0.9800	C49—H493	0.9800
C20—H201	0.9800	C50—H501	0.9800
C20—H202	0.9800	C50—H502	0.9800
C20—H203	0.9800	C50—H503	0.9800
C21—H211	0.9800	C51—H511	0.9800
C21—H212	0.9800	C51—H512	0.9800
C21—H213	0.9800	C51—H513	0.9800
C11—N1—C1	122.8 (4)	C41—N2—C31	122.4 (4)
C11—N1—H1	118 (3)	C41—N2—H2	117 (4)
C1—N1—H1	115 (2)	C31—N2—H2	120 (4)
C10—C1—N1	120.5 (4)	C40—C31—N2	121.5 (5)
C10—C1—C2	120.6 (4)	C40—C31—C32	119.9 (5)
N1—C1—C2	118.9 (4)	N2—C31—C32	118.6 (4)
C3—C2—C1	123.7 (4)	C37—C32—C31	118.6 (5)
C3—C2—C7	118.0 (5)	C37—C32—C33	117.4 (5)
C1—C2—C7	118.3 (5)	C31—C32—C33	124.0 (5)
C4—C3—C2	121.2 (5)	C34—C33—C32	121.5 (5)
C4—C3—H3	119.4	C34—C33—H33	119.2
C2—C3—H3	119.4	C32—C33—H33	119.2
C3—C4—C5	119.4 (5)	C33—C34—C35	121.1 (6)
C3—C4—H4	120.3	C33—C34—H34	119.4
C5—C4—H4	120.3	C35—C34—H34	119.4
C6—C5—C4	121.8 (5)	C36—C35—C34	119.7 (6)
C6—C5—H5	119.1	C36—C35—H35	120.1
C4—C5—H5	119.1	C34—C35—H35	120.1
C5—C6—C7	121.0 (5)	C35—C36—C37	121.9 (6)
C5—C6—H6	119.5	C35—C36—H36	119.1
C7—C6—H6	119.5	C37—C36—H36	119.1
C8—C7—C6	122.5 (5)	C32—C37—C38	121.9 (5)
C8—C7—C2	118.9 (5)	C32—C37—C36	118.2 (5)
C6—C7—C2	118.5 (5)	C38—C37—C36	119.9 (5)
C9—C8—C7	121.3 (5)	C39—C38—C37	117.7 (5)
C9—C8—H8	119.4	C39—C38—H38	121.1
C7—C8—H8	119.4	C37—C38—H38	121.1
C8—C9—C10	120.1 (5)	C38—C39—C40	121.5 (5)
C8—C9—H9	119.9	C38—C39—H39	119.3
C10—C9—H9	119.9	C40—C39—H39	119.3
C1—C10—C9	120.5 (5)	C31—C40—C39	120.5 (5)
C1—C10—H10	119.7	C31—C40—H40	119.8
C9—C10—H10	119.7	C39—C40—H40	119.8
N1—C11—C12	126.1 (4)	N2—C41—C42	128.0 (5)
N1—C11—H11	116.9	N2—C41—H41	116.0
C12—C11—H11	116.9	C42—C41—H41	116.0
C11—C12—C17	121.5 (4)	C41—C42—C47	120.8 (4)
C11—C12—C13	132.2 (4)	C41—C42—C43	133.6 (4)
C17—C12—C13	105.4 (4)	C47—C42—C43	105.5 (4)
C12—C13—C14	104.7 (4)	C42—C43—C44	105.9 (4)
C12—C13—C18	101.5 (3)	C42—C43—C48	101.3 (4)
C14—C13—C18	102.4 (4)	C44—C43—C48	102.9 (4)
C12—C13—H13	115.5	C42—C43—H43	115.0
C14—C13—H13	115.5	C44—C43—H43	115.0
C18—C13—H13	115.5	C48—C43—H43	115.0
C13—C14—C15	102.4 (4)	C45—C44—C43	101.8 (4)
C13—C14—H141	111.3	C45—C44—H441	111.4
C15—C14—H141	111.3	C43—C44—H441	111.4
C13—C14—H142	111.3	C45—C44—H442	111.4
C15—C14—H142	111.3	C43—C44—H442	111.4
H141—C14—H142	109.2	H441—C44—H442	109.3
C14—C15—C16	104.5 (4)	C44—C45—C46	104.4 (4)
C14—C15—H151	110.9	C44—C45—H451	110.9
C16—C15—H151	110.9	C46—C45—H451	110.9
C14—C15—H152	110.9	C44—C45—H452	110.9
C16—C15—H152	110.9	C46—C45—H452	110.9
H151—C15—H152	108.9	H451—C45—H452	108.9
C21—C16—C17	115.2 (4)	C47—C46—C51	115.8 (4)
C21—C16—C18	119.9 (4)	C47—C46—C48	101.1 (4)
C17—C16—C18	99.9 (4)	C51—C46—C48	118.6 (5)
C21—C16—C15	114.7 (5)	C47—C46—C45	103.4 (4)
C17—C16—C15	103.0 (4)	C51—C46—C45	114.1 (4)
C18—C16—C15	101.6 (4)	C48—C46—C45	101.6 (4)
O1—C17—C12	128.8 (5)	O2—C47—C42	128.7 (5)
O1—C17—C16	125.3 (4)	O2—C47—C46	126.1 (4)
C12—C17—C16	105.9 (4)	C42—C47—C46	105.2 (4)
C19—C18—C20	107.9 (4)	C46—C48—C49	113.7 (4)
C19—C18—C13	113.1 (4)	C46—C48—C43	93.7 (4)
C20—C18—C13	114.2 (4)	C49—C48—C43	113.4 (4)
C19—C18—C16	113.2 (4)	C46—C48—C50	115.1 (4)
C20—C18—C16	113.7 (4)	C49—C48—C50	107.2 (5)
C13—C18—C16	94.5 (3)	C43—C48—C50	113.5 (4)
C18—C19—H191	109.5	C48—C49—H491	109.5
C18—C19—H192	109.5	C48—C49—H492	109.5
H191—C19—H192	109.5	H491—C49—H492	109.5
C18—C19—H193	109.5	C48—C49—H493	109.5
H191—C19—H193	109.5	H491—C49—H493	109.5
H192—C19—H193	109.5	H492—C49—H493	109.5
C18—C20—H201	109.5	C48—C50—H501	109.5
C18—C20—H202	109.5	C48—C50—H502	109.5
H201—C20—H202	109.5	H501—C50—H502	109.5
C18—C20—H203	109.5	C48—C50—H503	109.5
H201—C20—H203	109.5	H501—C50—H503	109.5
H202—C20—H203	109.5	H502—C50—H503	109.5
C16—C21—H211	109.5	C46—C51—H511	109.5
C16—C21—H212	109.5	C46—C51—H512	109.5
H211—C21—H212	109.5	H511—C51—H512	109.5
C16—C21—H213	109.5	C46—C51—H513	109.5
H211—C21—H213	109.5	H511—C51—H513	109.5
H212—C21—H213	109.5	H512—C51—H513	109.5
C11—N1—C1—C10	21.3 (7)	C41—N2—C31—C40	−24.4 (8)
C11—N1—C1—C2	−159.3 (4)	C41—N2—C31—C32	158.1 (5)
C10—C1—C2—C3	−174.3 (5)	C40—C31—C32—C37	−1.3 (7)
N1—C1—C2—C3	6.2 (7)	N2—C31—C32—C37	176.1 (5)
C10—C1—C2—C7	6.2 (7)	C40—C31—C32—C33	174.7 (5)
N1—C1—C2—C7	−173.2 (4)	N2—C31—C32—C33	−7.8 (8)
C1—C2—C3—C4	−177.2 (5)	C37—C32—C33—C34	−4.1 (7)
C7—C2—C3—C4	2.2 (7)	C31—C32—C33—C34	179.9 (5)
C2—C3—C4—C5	0.9 (8)	C32—C33—C34—C35	0.5 (8)
C3—C4—C5—C6	−2.8 (9)	C33—C34—C35—C36	1.8 (9)
C4—C5—C6—C7	1.5 (9)	C34—C35—C36—C37	−0.4 (9)
C5—C6—C7—C8	−176.0 (5)	C31—C32—C37—C38	1.2 (8)
C5—C6—C7—C2	1.7 (8)	C33—C32—C37—C38	−175.2 (5)
C3—C2—C7—C8	174.3 (5)	C31—C32—C37—C36	−178.5 (5)
C1—C2—C7—C8	−6.2 (7)	C33—C32—C37—C36	5.2 (7)
C3—C2—C7—C6	−3.5 (7)	C35—C36—C37—C32	−3.1 (8)
C1—C2—C7—C6	176.0 (4)	C35—C36—C37—C38	177.2 (6)
C6—C7—C8—C9	−179.8 (5)	C32—C37—C38—C39	−0.3 (8)
C2—C7—C8—C9	2.5 (8)	C36—C37—C38—C39	179.3 (5)
C7—C8—C9—C10	1.5 (8)	C37—C38—C39—C40	−0.4 (8)
N1—C1—C10—C9	177.1 (5)	N2—C31—C40—C39	−176.7 (5)
C2—C1—C10—C9	−2.4 (8)	C32—C31—C40—C39	0.7 (8)
C8—C9—C10—C1	−1.6 (8)	C38—C39—C40—C31	0.2 (9)
C1—N1—C11—C12	−155.0 (5)	C31—N2—C41—C42	159.3 (5)
N1—C11—C12—C17	−179.9 (5)	N2—C41—C42—C47	177.4 (5)
N1—C11—C12—C13	12.9 (9)	N2—C41—C42—C43	−7.6 (10)
C11—C12—C13—C14	94.2 (6)	C41—C42—C43—C44	112.2 (6)
C17—C12—C13—C14	−74.5 (4)	C47—C42—C43—C44	−72.2 (5)
C11—C12—C13—C18	−159.5 (5)	C41—C42—C43—C48	−140.7 (6)
C17—C12—C13—C18	31.8 (5)	C47—C42—C43—C48	34.8 (5)
C12—C13—C14—C15	67.9 (4)	C42—C43—C44—C45	70.0 (5)
C18—C13—C14—C15	−37.7 (4)	C48—C43—C44—C45	−35.9 (5)
C13—C14—C15—C16	3.6 (5)	C43—C44—C45—C46	1.1 (5)
C14—C15—C16—C21	162.2 (4)	C44—C45—C46—C47	−70.1 (5)
C14—C15—C16—C17	−71.8 (4)	C44—C45—C46—C51	163.3 (5)
C14—C15—C16—C18	31.4 (5)	C44—C45—C46—C48	34.5 (5)
C11—C12—C17—O1	10.6 (8)	C41—C42—C47—O2	−5.9 (9)
C13—C12—C17—O1	−179.2 (5)	C43—C42—C47—O2	177.8 (5)
C11—C12—C17—C16	−167.4 (5)	C41—C42—C47—C46	175.3 (5)
C13—C12—C17—C16	2.8 (5)	C43—C42—C47—C46	−0.9 (6)
C21—C16—C17—O1	15.9 (7)	C51—C46—C47—O2	17.8 (8)
C18—C16—C17—O1	145.8 (5)	C48—C46—C47—O2	147.4 (5)
C15—C16—C17—O1	−109.7 (5)	C45—C46—C47—O2	−107.8 (6)
C21—C16—C17—C12	−166.0 (4)	C51—C46—C47—C42	−163.4 (5)
C18—C16—C17—C12	−36.1 (5)	C48—C46—C47—C42	−33.8 (5)
C15—C16—C17—C12	68.4 (4)	C45—C46—C47—C42	71.0 (5)
C12—C13—C18—C19	65.7 (5)	C47—C46—C48—C49	−65.4 (5)
C14—C13—C18—C19	173.7 (4)	C51—C46—C48—C49	62.4 (6)
C12—C13—C18—C20	−170.4 (4)	C45—C46—C48—C49	−171.7 (4)
C14—C13—C18—C20	−62.4 (5)	C47—C46—C48—C43	52.2 (4)
C12—C13—C18—C16	−51.9 (4)	C51—C46—C48—C43	179.9 (5)
C14—C13—C18—C16	56.2 (4)	C45—C46—C48—C43	−54.2 (4)
C21—C16—C18—C19	62.3 (6)	C47—C46—C48—C50	170.3 (5)
C17—C16—C18—C19	−64.5 (4)	C51—C46—C48—C50	−61.9 (7)
C15—C16—C18—C19	−170.2 (4)	C45—C46—C48—C50	64.0 (6)
C21—C16—C18—C20	−61.2 (6)	C42—C43—C48—C46	−53.2 (4)
C17—C16—C18—C20	171.9 (4)	C44—C43—C48—C46	56.2 (4)
C15—C16—C18—C20	66.3 (5)	C42—C43—C48—C49	64.7 (5)
C21—C16—C18—C13	179.8 (5)	C44—C43—C48—C49	174.1 (4)
C17—C16—C18—C13	53.0 (4)	C42—C43—C48—C50	−172.7 (4)
C15—C16—C18—C13	−52.7 (4)	C44—C43—C48—C50	−63.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	1.03 (4)	1.93 (4)	2.909 (5)	157 (4)
N2—H2···O1	0.83 (5)	2.08 (5)	2.913 (5)	174 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	1.03 (4)	1.93 (4)	2.909 (5)	157 (4)
N2—H2⋯O1	0.83 (5)	2.08 (5)	2.913 (5)	174 (5)

Symmetry code: (i) .