1-Benzyl-5-(1-naphthyl­methyl­ene)piperidinespiro-3,3′-1′-methyl-4′-(1-naphthyl)pyrrolidinespiro-2′,3′′-indole-2′′,4-dione–diethyl ether (1/0.75)

The title compound, C₄₄H₃₇N₃O₂·0.75(C₂H₅)₂O, was synthesized by the intermolecular [3 + 2] cyclo­addition of the azomethine yl­ide, derived from isatin and sarcosine by a de­carboxyl­ative route, and 1-benzyl-3,5-bis-naphth-1-yl­methyl­ene-piperidin-4-one. In the mol­ecule, the two spiro junctions link a planar 2-ox­indole ring, a pyrrolidine ring in an envelope conformation and a piperidone in a boat conformation. Molecules are connected into chains along the a direction by O—H...N hydrogen bonds, with an O...N distance of 2.944 (3) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.062
• wR factor = 0.188
• Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_302  Alert C Anion/Solvent Disorder .........................      38.00 Perc.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Spiro compounds represent an important class of naturally occurring substances characterized by highly pronounced biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-dipolar cycloaddition reactions are important in the construction of spiro compounds (Caramella & Grunanger, 1984). The molecular structure of (I) is illustrated in Fig. 1. The two spiro junctions in the molecule consist of a 2-oxindole ring, a pyrrolidine ring and a piperidone ring. The pyrrolidine ring (N2/C7/C9/C10/C11) is in an envelope conformation; the atoms C7/C9/C10/C11 are almost planar with a mean deviation of 0.031 (3)%A and N2 is 0.594 (2) Å from this plane, forming the flap of the envelope. However, in the previously reported structure, 1"-benzyl-5"-benzylidene-1' -methyl-4'-phenyl-1H-indole-3-spiro-2'-pyrrolidine-3'-spiro-3"- piperidine-2(3H),3"-dione, it is the C atom of the —CH₂— group of the pyrrolidine which ring forms the flap of the envelope (Li et al., 2003) rather than the N atom of the —N—CH₃ group.

The dihedral angle between the C7/N2/C11 and C7//C9/C10/C11 least-squres planes is 137.3 (2)°. The dihedral angle between ther naphthalene plane (C17/C18/C19/C20/C21/C22/C23/C24/C25/C26) and C7/C9/C10/C11 plane is 108.4 (3)°. The 2-oxindole ring (C1/C2/C3/C4/C5/C6/C7/C8/N1) is nearly planar, with a mean deviation from the plane of 0.042 (3)%A and a dihedral angle between the 2-oxindole ring and the plane C7/C9/C10/C11 of 82.0 (2)°. The piperidone ring has a boat conformation, which is different from the chair conformation of piperidone ring in 1"-benzyl-5"-benzylidene-1'-methyl-4'- phenyl-1H-indole-3-spiro-2'-pyrrolidine-3'-spiro-3"-piperidine-2(3H),3" -dione (Li et al., 2003). Molecules are connected into chains along the a direction through O—H.·N hydrogen bonds. The O···N and H···N distances are 2.944 (3) and 2.11 Å, respectively, and the O—H.·N angle is 162°.

S2. Experimental

A mixture of 1-benzyl-3,5-bis-naphthalen-1-ylmethylene-piperidin-4-one (2 mmol), isatin (2 mmol) and sarcosine (2 mmol) were refluxed in methanol (80 ml) until the starting material had disappeared (as evidenced by TLC). After the reaction was complete, the solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ethylcetate 5:1) to give the title compound, (I). M.p. 439–440 K; IR (KBr): 3490(N—H), 1734.1, 1718.7 (C=O), 1614.5(C=C) cm⁻¹; ¹H NMR (CDCl₃, p.p.m.): 1.76 (d, J=12.9 Hz, 1H), 2.14 (s, 3H), 2.50 (dd, J=2.7, 14.7 Hz, 1H), 2.90 (d, J=13.5 Hz, 1H), 3.15 (d, J=14.7 Hz, 1H), 3.42–3.55 (m, 3H), 4.20 (dd, J=9.3, 10.8 Hz, 1H), 5.67 (dd, J=7.5, 9.9 Hz, 1H), 7.12 (s, 1H), 7.01–8.24 (m, 23H), 7.94 (bs, 1H). 20 mg of (I) was dissolved in 15 ml of a mixture of chloroform and ether and the solution was kept at room temperature for 15 days to undergo natural evaporation. This gave colorless single crystals of (I) suitable for X-ray analysis.

S3. Refinement

All H atoms were placed in calculated positions, with C—H distances ranging from 0.93 to 0.98 Å and and an N—H distance of 0.86 Å. They were included in the refinement in riding motion approximation, with U_iso = 1.2(1.5 for methyl) U_eq of the carrier atom. The 0.75 partial occupancy (3/4) solvent ether molecule is disordered over two sites, with occupancies of 0.5 and 0.25.

Computing details

Data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids. H atoms are omitted.
	Fig. 2. The crystal packing diagram of (I), viewed along the a axis, with dashed lines indicating hydrogen bonds. The disordered ether molecules are not shown.

(I)

Crystal data

C44H37N3O2·0.75C4H10O	F(000) = 2956
Mr = 695.36	Dx = 1.127 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 909 reflections
a = 12.958 (3) Å	θ = 3.3–23.9°
b = 24.556 (5) Å	µ = 0.07 mm^−1
c = 25.753 (6) Å	T = 293 K
V = 8195 (3) Å^3	Plate, colorless
Z = 8	0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART-CCD diffractometer	3812 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.050
Graphite monochromator	θmax = 25.0°, θmin = 1.3°
ϕ and ω scans	h = −11→15
20973 measured reflections	k = −25→29
7092 independent reflections	l = −23→30

Refinement

Refinement on F^2	200 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.084P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.188	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.59 e Å^−3
7092 reflections	Δρmin = −0.16 e Å^−3
534 parameters

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)
N1	0.16261 (18)	0.20071 (10)	0.22102 (9)	0.0541 (6)
H1	0.1020	0.2030	0.2076	0.065*
N2	0.42783 (17)	0.20977 (9)	0.21698 (8)	0.0477 (6)
N3	0.29246 (17)	0.34608 (9)	0.33256 (8)	0.0467 (6)
O1	0.23842 (16)	0.27239 (9)	0.17882 (7)	0.0593 (5)
O2	0.47679 (14)	0.22641 (8)	0.34005 (6)	0.0499 (5)
C1	0.1926 (2)	0.16026 (11)	0.25612 (10)	0.0496 (7)
C2	0.1375 (3)	0.11465 (13)	0.27052 (13)	0.0651 (9)
H2	0.0700	0.1092	0.2594	0.078*
C3	0.1867 (3)	0.07742 (14)	0.30218 (14)	0.0748 (10)
H3	0.1516	0.0463	0.3128	0.090*
C4	0.2869 (3)	0.08549 (13)	0.31828 (12)	0.0683 (9)
H4	0.3187	0.0597	0.3394	0.082*
C5	0.3408 (2)	0.13149 (12)	0.30336 (10)	0.0559 (8)
H5	0.4088	0.1365	0.3139	0.067*
C6	0.2928 (2)	0.16989 (11)	0.27267 (9)	0.0449 (6)
C7	0.33345 (19)	0.22102 (11)	0.24649 (9)	0.0426 (6)
C8	0.2404 (2)	0.23591 (12)	0.21077 (10)	0.0463 (7)
C9	0.36363 (19)	0.27208 (11)	0.28045 (9)	0.0401 (6)
C10	0.4608 (2)	0.29667 (11)	0.25103 (9)	0.0446 (6)
H10	0.5213	0.2876	0.2722	0.054*
C11	0.4687 (2)	0.26246 (12)	0.20183 (10)	0.0548 (8)
H11A	0.4280	0.2783	0.1740	0.066*
H11B	0.5398	0.2594	0.1905	0.066*
C12	0.4151 (3)	0.17226 (14)	0.17385 (11)	0.0660 (9)
H12A	0.3846	0.1391	0.1861	0.099*
H12B	0.4813	0.1645	0.1588	0.099*
H12C	0.3711	0.1884	0.1481	0.099*
C13	0.27366 (19)	0.31197 (11)	0.28750 (10)	0.0440 (6)
H13A	0.2668	0.3345	0.2568	0.053*
H13B	0.2099	0.2919	0.2921	0.053*
C14	0.2684 (2)	0.31480 (12)	0.37912 (10)	0.0544 (8)
H14A	0.1949	0.3077	0.3806	0.065*
H14B	0.2874	0.3356	0.4097	0.065*
C15	0.3264 (2)	0.26205 (11)	0.37848 (9)	0.0455 (7)
C16	0.3967 (2)	0.25207 (11)	0.33406 (9)	0.0416 (6)
C17	0.4636 (2)	0.35759 (12)	0.24275 (10)	0.0510 (7)
C18	0.4109 (3)	0.38086 (14)	0.20213 (12)	0.0676 (9)
H18	0.3704	0.3588	0.1810	0.081*
C19	0.4161 (3)	0.43655 (17)	0.19150 (16)	0.0844 (11)
H19	0.3800	0.4509	0.1635	0.101*
C20	0.4735 (3)	0.46950 (16)	0.22186 (18)	0.0872 (12)
H20	0.4773	0.5065	0.2142	0.105*
C21	0.5276 (3)	0.44894 (15)	0.26476 (15)	0.0735 (10)
C22	0.5870 (4)	0.48356 (17)	0.2973 (2)	0.1026 (14)
H22	0.5911	0.5206	0.2898	0.123*
C23	0.6375 (4)	0.4634 (2)	0.3388 (2)	0.1105 (15)
H23	0.6751	0.4866	0.3601	0.133*
C24	0.6336 (3)	0.40747 (18)	0.35018 (17)	0.0892 (11)
H24	0.6691	0.3938	0.3788	0.107*
C25	0.5778 (2)	0.37305 (14)	0.31937 (12)	0.0645 (8)
H25	0.5758	0.3362	0.3275	0.077*
C26	0.5232 (2)	0.39215 (13)	0.27544 (12)	0.0569 (8)
C27	0.2329 (3)	0.39688 (13)	0.33008 (11)	0.0600 (8)
H27A	0.1598	0.3883	0.3305	0.072*
H27B	0.2480	0.4154	0.2977	0.072*
C28	0.2574 (3)	0.43425 (12)	0.37483 (11)	0.0594 (8)
C29	0.1801 (3)	0.45802 (15)	0.40362 (14)	0.0807 (10)
H29	0.1116	0.4508	0.3954	0.097*
C30	0.2028 (5)	0.49227 (19)	0.44436 (18)	0.1080 (15)
H30	0.1497	0.5080	0.4635	0.130*
C31	0.3041 (5)	0.50332 (17)	0.45688 (16)	0.1045 (15)
H31	0.3196	0.5262	0.4846	0.125*
C32	0.3818 (4)	0.48035 (16)	0.42812 (16)	0.0946 (12)
H32	0.4503	0.4879	0.4361	0.113*
C33	0.3587 (3)	0.44609 (14)	0.38744 (13)	0.0743 (9)
H33	0.4120	0.4307	0.3682	0.089*
C34	0.3155 (2)	0.22317 (13)	0.41379 (9)	0.0559 (8)
H34	0.3523	0.1912	0.4084	0.067*
C35	0.2503 (3)	0.22580 (13)	0.46112 (10)	0.0615 (8)
C36	0.2760 (3)	0.26089 (17)	0.49995 (12)	0.0858 (11)
H36	0.3302	0.2852	0.4951	0.103*
C37	0.2221 (4)	0.2609 (2)	0.54705 (14)	0.1089 (15)
H37	0.2421	0.2844	0.5735	0.131*
C38	0.1425 (4)	0.2275 (2)	0.55427 (13)	0.1015 (14)
H38	0.1075	0.2282	0.5858	0.122*
C39	0.1102 (3)	0.19131 (16)	0.51520 (12)	0.0750 (10)
C40	0.0262 (3)	0.1553 (2)	0.52138 (18)	0.0977 (14)
H40	−0.0094	0.1547	0.5527	0.117*
C41	−0.0033 (3)	0.1218 (2)	0.4829 (2)	0.1038 (15)
H41	−0.0603	0.0994	0.4876	0.125*
C42	0.0502 (3)	0.12041 (17)	0.43635 (16)	0.0885 (11)
H42	0.0299	0.0965	0.4103	0.106*
C43	0.1329 (3)	0.15416 (14)	0.42875 (13)	0.0703 (9)
H43	0.1682	0.1531	0.3973	0.084*
C44	0.1654 (2)	0.19039 (13)	0.46772 (10)	0.0576 (8)
O3	0.5465 (11)	0.1139 (7)	0.4767 (6)	0.241 (5)	0.50
C45	0.4665 (13)	0.1589 (6)	0.5541 (5)	0.188 (6)	0.50
H45A	0.5114	0.1450	0.5806	0.282*	0.50
H45B	0.3996	0.1659	0.5687	0.282*	0.50
H45C	0.4945	0.1921	0.5404	0.282*	0.50
C46	0.4567 (14)	0.1169 (8)	0.5103 (7)	0.214 (7)	0.50
H46A	0.4450	0.0813	0.5256	0.257*	0.50
H46B	0.3968	0.1258	0.4894	0.257*	0.50
C47	0.5411 (13)	0.0926 (10)	0.4258 (6)	0.223 (7)	0.50
H47A	0.4964	0.1162	0.4056	0.268*	0.50
H47B	0.5080	0.0573	0.4277	0.268*	0.50
C48	0.6436 (17)	0.0858 (11)	0.3955 (8)	0.266 (10)	0.50
H48A	0.6478	0.1130	0.3688	0.400*	0.50
H48B	0.6458	0.0502	0.3800	0.400*	0.50
H48C	0.7008	0.0898	0.4189	0.400*	0.50
O3'	0.4931 (18)	0.1034 (10)	0.4781 (8)	0.203 (7)	0.25
C45'	0.3834 (16)	0.1240 (9)	0.5544 (7)	0.134 (7)	0.25
H45D	0.3582	0.1543	0.5742	0.201*	0.25
H45E	0.4076	0.0961	0.5775	0.201*	0.25
H45F	0.3286	0.1097	0.5333	0.201*	0.25
C46'	0.473 (2)	0.1430 (10)	0.5192 (10)	0.154 (8)	0.25
H46C	0.4557	0.1778	0.5038	0.184*	0.25
H46D	0.5348	0.1478	0.5400	0.184*	0.25
C47'	0.576 (2)	0.1143 (12)	0.4425 (12)	0.181 (9)	0.25
H47C	0.6378	0.1218	0.4623	0.217*	0.25
H47D	0.5590	0.1470	0.4231	0.217*	0.25
C48'	0.599 (3)	0.0686 (16)	0.4039 (14)	0.235 (15)	0.25
H48D	0.5844	0.0808	0.3693	0.352*	0.25
H48E	0.5573	0.0375	0.4119	0.352*	0.25
H48F	0.6708	0.0588	0.4064	0.352*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0374 (13)	0.0555 (16)	0.0694 (14)	−0.0004 (12)	−0.0121 (12)	−0.0035 (12)
N2	0.0416 (13)	0.0561 (15)	0.0453 (11)	0.0021 (11)	0.0060 (10)	−0.0049 (11)
N3	0.0469 (13)	0.0462 (14)	0.0471 (11)	0.0039 (11)	0.0027 (10)	0.0009 (10)
O1	0.0619 (13)	0.0632 (14)	0.0529 (10)	0.0055 (11)	−0.0108 (10)	0.0074 (10)
O2	0.0372 (10)	0.0650 (13)	0.0477 (10)	0.0050 (10)	−0.0017 (9)	0.0064 (9)
C1	0.0439 (16)	0.0453 (17)	0.0596 (16)	0.0011 (14)	0.0029 (14)	−0.0056 (14)
C2	0.0552 (19)	0.054 (2)	0.086 (2)	−0.0068 (16)	0.0061 (18)	−0.0064 (17)
C3	0.088 (3)	0.050 (2)	0.087 (2)	−0.0133 (19)	0.015 (2)	0.0005 (18)
C4	0.090 (3)	0.0453 (19)	0.0692 (19)	0.0049 (19)	0.0014 (19)	0.0094 (15)
C5	0.0606 (19)	0.0511 (19)	0.0559 (16)	0.0039 (16)	−0.0033 (15)	0.0037 (14)
C6	0.0450 (16)	0.0444 (16)	0.0454 (13)	0.0021 (13)	0.0014 (13)	−0.0002 (12)
C7	0.0362 (14)	0.0509 (17)	0.0409 (12)	0.0034 (13)	0.0020 (11)	0.0031 (12)
C8	0.0480 (17)	0.0474 (17)	0.0435 (13)	0.0044 (14)	−0.0044 (13)	−0.0051 (14)
C9	0.0339 (13)	0.0448 (16)	0.0417 (12)	0.0000 (12)	0.0014 (11)	0.0033 (12)
C10	0.0363 (14)	0.0519 (17)	0.0456 (13)	−0.0015 (13)	0.0016 (12)	0.0066 (12)
C11	0.0483 (17)	0.066 (2)	0.0499 (14)	−0.0033 (16)	0.0078 (13)	0.0077 (14)
C12	0.063 (2)	0.077 (2)	0.0581 (16)	0.0133 (17)	0.0064 (15)	−0.0157 (16)
C13	0.0359 (15)	0.0471 (17)	0.0491 (13)	0.0022 (12)	0.0013 (12)	0.0009 (12)
C14	0.0576 (19)	0.0568 (19)	0.0488 (14)	0.0062 (15)	0.0052 (14)	−0.0018 (13)
C15	0.0420 (15)	0.0528 (18)	0.0419 (13)	0.0009 (13)	0.0002 (12)	0.0004 (13)
C16	0.0361 (14)	0.0447 (16)	0.0439 (13)	−0.0034 (13)	−0.0003 (12)	0.0009 (11)
C17	0.0412 (15)	0.0548 (18)	0.0571 (15)	−0.0002 (14)	0.0084 (14)	0.0101 (14)
C18	0.063 (2)	0.069 (2)	0.0707 (19)	0.0002 (18)	0.0024 (17)	0.0196 (17)
C19	0.086 (3)	0.074 (3)	0.094 (3)	0.010 (2)	0.007 (2)	0.031 (2)
C20	0.091 (3)	0.050 (2)	0.120 (3)	0.008 (2)	0.026 (3)	0.024 (2)
C21	0.062 (2)	0.054 (2)	0.105 (3)	−0.0011 (18)	0.019 (2)	0.004 (2)
C22	0.086 (3)	0.060 (3)	0.161 (4)	−0.013 (2)	0.008 (3)	−0.015 (3)
C23	0.082 (3)	0.090 (4)	0.160 (4)	−0.017 (3)	−0.012 (3)	−0.040 (3)
C24	0.068 (2)	0.086 (3)	0.113 (3)	0.000 (2)	−0.015 (2)	−0.023 (2)
C25	0.0476 (18)	0.061 (2)	0.085 (2)	−0.0028 (16)	−0.0043 (17)	−0.0078 (17)
C26	0.0421 (16)	0.056 (2)	0.0726 (18)	−0.0025 (15)	0.0117 (15)	−0.0005 (16)
C27	0.062 (2)	0.0547 (19)	0.0629 (17)	0.0141 (16)	−0.0014 (15)	−0.0001 (15)
C28	0.075 (2)	0.0409 (17)	0.0628 (17)	0.0096 (16)	0.0040 (18)	0.0044 (14)
C29	0.091 (3)	0.064 (2)	0.087 (2)	0.008 (2)	0.017 (2)	−0.011 (2)
C30	0.143 (5)	0.080 (3)	0.100 (3)	0.007 (3)	0.043 (3)	−0.022 (2)
C31	0.167 (5)	0.065 (3)	0.082 (3)	−0.008 (3)	0.009 (3)	−0.017 (2)
C32	0.115 (4)	0.068 (3)	0.100 (3)	−0.009 (2)	−0.017 (3)	−0.002 (2)
C33	0.084 (3)	0.061 (2)	0.078 (2)	0.0043 (19)	−0.003 (2)	−0.0108 (18)
C34	0.066 (2)	0.0583 (19)	0.0437 (14)	0.0060 (16)	0.0072 (14)	0.0001 (14)
C35	0.078 (2)	0.064 (2)	0.0432 (15)	0.0110 (18)	0.0105 (15)	0.0070 (15)
C36	0.109 (3)	0.093 (3)	0.0549 (18)	−0.010 (2)	0.011 (2)	−0.0065 (19)
C37	0.140 (4)	0.133 (4)	0.053 (2)	−0.011 (3)	0.016 (2)	−0.019 (2)
C38	0.113 (4)	0.144 (4)	0.0480 (19)	0.016 (3)	0.026 (2)	−0.002 (2)
C39	0.070 (2)	0.100 (3)	0.0545 (18)	0.018 (2)	0.0167 (17)	0.0228 (19)
C40	0.069 (3)	0.140 (4)	0.084 (3)	0.013 (3)	0.024 (2)	0.042 (3)
C41	0.071 (3)	0.126 (4)	0.115 (3)	−0.007 (3)	0.005 (3)	0.059 (3)
C42	0.088 (3)	0.084 (3)	0.093 (3)	−0.007 (2)	−0.012 (2)	0.027 (2)
C43	0.079 (2)	0.067 (2)	0.0650 (18)	0.007 (2)	0.0057 (18)	0.0227 (18)
C44	0.063 (2)	0.065 (2)	0.0441 (15)	0.0120 (17)	0.0062 (14)	0.0147 (15)
O3	0.238 (7)	0.240 (7)	0.247 (7)	−0.004 (5)	−0.006 (5)	0.001 (5)
C45	0.189 (7)	0.191 (7)	0.185 (7)	0.015 (5)	−0.013 (5)	0.007 (5)
C46	0.212 (8)	0.213 (8)	0.217 (8)	0.001 (5)	−0.012 (5)	0.004 (5)
C47	0.226 (8)	0.221 (8)	0.223 (8)	−0.008 (5)	−0.002 (5)	0.004 (5)
C48	0.272 (11)	0.253 (11)	0.274 (11)	−0.004 (5)	−0.004 (5)	−0.005 (5)
O3'	0.202 (8)	0.202 (8)	0.205 (8)	−0.002 (5)	0.004 (5)	−0.005 (5)
C45'	0.136 (8)	0.136 (8)	0.131 (8)	0.004 (5)	−0.002 (5)	0.009 (5)
C46'	0.156 (9)	0.154 (9)	0.151 (9)	0.012 (5)	−0.005 (5)	−0.007 (5)
C47'	0.183 (10)	0.181 (10)	0.179 (10)	−0.003 (5)	0.001 (5)	−0.001 (5)
C48'	0.234 (16)	0.233 (16)	0.237 (16)	0.001 (5)	0.002 (5)	−0.007 (5)

Geometric parameters (Å, º)

N1—C8	1.354 (4)	C27—H27A	0.9700
N1—C1	1.398 (3)	C27—H27B	0.9700
N1—H1	0.8600	C28—C29	1.376 (5)
N2—C12	1.452 (3)	C28—C33	1.383 (5)
N2—C11	1.451 (4)	C29—C30	1.376 (6)
N2—C7	1.466 (3)	C29—H29	0.9300
N3—C13	1.452 (3)	C30—C31	1.379 (7)
N3—C14	1.458 (3)	C30—H30	0.9300
N3—C27	1.468 (4)	C31—C32	1.371 (6)
O1—C8	1.217 (3)	C31—H31	0.9300
O2—C16	1.223 (3)	C32—C33	1.377 (5)
C1—C2	1.380 (4)	C32—H32	0.9300
C1—C6	1.387 (4)	C33—H33	0.9300
C2—C3	1.381 (5)	C34—C35	1.485 (4)
C2—H2	0.9300	C34—H34	0.9300
C3—C4	1.378 (5)	C35—C36	1.362 (5)
C3—H3	0.9300	C35—C44	1.412 (5)
C4—C5	1.382 (4)	C36—C37	1.400 (5)
C4—H4	0.9300	C36—H36	0.9300
C5—C6	1.379 (4)	C37—C38	1.330 (6)
C5—H5	0.9300	C37—H37	0.9300
C6—C7	1.519 (4)	C38—C39	1.407 (6)
C7—C8	1.560 (4)	C38—H38	0.9300
C7—C9	1.578 (4)	C39—C40	1.412 (6)
C9—C16	1.527 (3)	C39—C44	1.417 (4)
C9—C13	1.533 (4)	C40—C41	1.342 (6)
C9—C10	1.589 (3)	C40—H40	0.9300
C10—C17	1.512 (4)	C41—C42	1.386 (6)
C10—C11	1.524 (4)	C41—H41	0.9300
C10—H10	0.9800	C42—C43	1.369 (5)
C11—H11A	0.9700	C42—H42	0.9300
C11—H11B	0.9700	C43—C44	1.406 (5)
C12—H12A	0.9600	C43—H43	0.9300
C12—H12B	0.9600	O3—C47	1.414 (9)
C12—H12C	0.9600	O3—C46	1.451 (9)
C13—H13A	0.9700	C45—C46	1.534 (9)
C13—H13B	0.9700	C45—H45A	0.9600
C14—C15	1.497 (4)	C45—H45B	0.9600
C14—H14A	0.9700	C45—H45C	0.9600
C14—H14B	0.9700	C46—H46A	0.9700
C15—C34	1.326 (4)	C46—H46B	0.9700
C15—C16	1.483 (3)	C47—C48	1.550 (9)
C17—C18	1.374 (4)	C47—H47A	0.9700
C17—C26	1.423 (4)	C47—H47B	0.9700
C18—C19	1.396 (5)	C48—H48A	0.9600
C18—H18	0.9300	C48—H48B	0.9600
C19—C20	1.349 (5)	C48—H48C	0.9600
C19—H19	0.9300	O3'—C47'	1.436 (10)
C20—C21	1.403 (5)	O3'—C46'	1.459 (10)
C20—H20	0.9300	C45'—C46'	1.546 (10)
C21—C22	1.419 (6)	C45'—H45D	0.9600
C21—C26	1.423 (5)	C45'—H45E	0.9600
C22—C23	1.350 (6)	C45'—H45F	0.9600
C22—H22	0.9300	C46'—H46C	0.9700
C23—C24	1.404 (6)	C46'—H46D	0.9700
C23—H23	0.9300	C47'—C48'	1.530 (10)
C24—C25	1.366 (5)	C47'—H47C	0.9700
C24—H24	0.9300	C47'—H47D	0.9700
C25—C26	1.415 (4)	C48'—H48D	0.9600
C25—H25	0.9300	C48'—H48E	0.9600
C27—C28	1.507 (4)	C48'—H48F	0.9600
C8—N1—C1	111.9 (2)	N3—C27—C28	111.9 (2)
C8—N1—H1	124.1	N3—C27—H27A	109.2
C1—N1—H1	124.1	C28—C27—H27A	109.2
C12—N2—C11	113.6 (2)	N3—C27—H27B	109.2
C12—N2—C7	114.9 (2)	C28—C27—H27B	109.2
C11—N2—C7	106.0 (2)	H27A—C27—H27B	107.9
C13—N3—C14	108.5 (2)	C29—C28—C33	118.4 (3)
C13—N3—C27	111.5 (2)	C29—C28—C27	121.1 (3)
C14—N3—C27	111.8 (2)	C33—C28—C27	120.5 (3)
C2—C1—C6	122.8 (3)	C30—C29—C28	121.0 (4)
C2—C1—N1	127.3 (3)	C30—C29—H29	119.5
C6—C1—N1	109.8 (2)	C28—C29—H29	119.5
C3—C2—C1	117.2 (3)	C29—C30—C31	120.1 (4)
C3—C2—H2	121.4	C29—C30—H30	119.9
C1—C2—H2	121.4	C31—C30—H30	119.9
C4—C3—C2	121.2 (3)	C32—C31—C30	119.5 (4)
C4—C3—H3	119.4	C32—C31—H31	120.3
C2—C3—H3	119.4	C30—C31—H31	120.3
C3—C4—C5	120.7 (3)	C31—C32—C33	120.2 (4)
C3—C4—H4	119.7	C31—C32—H32	119.9
C5—C4—H4	119.7	C33—C32—H32	119.9
C6—C5—C4	119.4 (3)	C32—C33—C28	120.9 (4)
C6—C5—H5	120.3	C32—C33—H33	119.6
C4—C5—H5	120.3	C28—C33—H33	119.6
C5—C6—C1	118.8 (3)	C15—C34—C35	126.3 (3)
C5—C6—C7	131.6 (3)	C15—C34—H34	116.8
C1—C6—C7	109.2 (2)	C35—C34—H34	116.9
N2—C7—C6	111.3 (2)	C36—C35—C44	119.5 (3)
N2—C7—C8	112.53 (19)	C36—C35—C34	119.4 (3)
C6—C7—C8	100.8 (2)	C44—C35—C34	121.0 (3)
N2—C7—C9	103.32 (19)	C35—C36—C37	120.9 (4)
C6—C7—C9	119.78 (19)	C35—C36—H36	119.5
C8—C7—C9	109.4 (2)	C37—C36—H36	119.5
O1—C8—N1	125.9 (3)	C38—C37—C36	120.6 (4)
O1—C8—C7	126.0 (3)	C38—C37—H37	119.7
N1—C8—C7	108.1 (2)	C36—C37—H37	119.7
C16—C9—C13	108.2 (2)	C37—C38—C39	121.3 (3)
C16—C9—C7	108.4 (2)	C37—C38—H38	119.3
C13—C9—C7	112.6 (2)	C39—C38—H38	119.3
C16—C9—C10	109.3 (2)	C38—C39—C40	123.0 (4)
C13—C9—C10	114.6 (2)	C38—C39—C44	118.5 (4)
C7—C9—C10	103.53 (18)	C40—C39—C44	118.5 (4)
C17—C10—C11	115.3 (2)	C41—C40—C39	121.4 (4)
C17—C10—C9	117.5 (2)	C41—C40—H40	119.3
C11—C10—C9	103.9 (2)	C39—C40—H40	119.3
C17—C10—H10	106.5	C40—C41—C42	120.7 (4)
C11—C10—H10	106.5	C40—C41—H41	119.6
C9—C10—H10	106.5	C42—C41—H41	119.6
N2—C11—C10	104.1 (2)	C43—C42—C41	120.0 (4)
N2—C11—H11A	110.9	C43—C42—H42	120.0
C10—C11—H11A	110.9	C41—C42—H42	120.0
N2—C11—H11B	110.9	C42—C43—C44	121.0 (3)
C10—C11—H11B	110.9	C42—C43—H43	119.5
H11A—C11—H11B	109.0	C44—C43—H43	119.5
N2—C12—H12A	109.5	C43—C44—C35	122.5 (3)
N2—C12—H12B	109.5	C43—C44—C39	118.4 (3)
H12A—C12—H12B	109.5	C35—C44—C39	119.1 (3)
N2—C12—H12C	109.5	C47—O3—C46	122.1 (10)
H12A—C12—H12C	109.5	C46—C45—H45A	109.5
H12B—C12—H12C	109.5	C46—C45—H45B	109.5
N3—C13—C9	109.6 (2)	H45A—C45—H45B	109.5
N3—C13—H13A	109.8	C46—C45—H45C	109.5
C9—C13—H13A	109.8	H45A—C45—H45C	109.5
N3—C13—H13B	109.8	H45B—C45—H45C	109.5
C9—C13—H13B	109.8	O3—C46—C45	113.9 (9)
H13A—C13—H13B	108.2	O3—C46—H46A	108.8
N3—C14—C15	109.9 (2)	C45—C46—H46A	108.8
N3—C14—H14A	109.7	O3—C46—H46B	108.8
C15—C14—H14A	109.7	C45—C46—H46B	108.8
N3—C14—H14B	109.7	H46A—C46—H46B	107.7
C15—C14—H14B	109.7	O3—C47—C48	117.7 (10)
H14A—C14—H14B	108.2	O3—C47—H47A	107.9
C34—C15—C16	118.4 (3)	C48—C47—H47A	107.9
C34—C15—C14	124.2 (2)	O3—C47—H47B	107.9
C16—C15—C14	117.4 (2)	C48—C47—H47B	107.9
O2—C16—C15	120.6 (2)	H47A—C47—H47B	107.2
O2—C16—C9	121.2 (2)	C47—C48—H48A	109.5
C15—C16—C9	118.1 (2)	C47—C48—H48B	109.5
C18—C17—C26	118.2 (3)	H48A—C48—H48B	109.5
C18—C17—C10	120.5 (3)	C47—C48—H48C	109.5
C26—C17—C10	121.3 (2)	H48A—C48—H48C	109.5
C17—C18—C19	122.2 (4)	H48B—C48—H48C	109.5
C17—C18—H18	118.9	C47'—O3'—C46'	118.2 (11)
C19—C18—H18	118.9	C46'—C45'—H45D	109.5
C20—C19—C18	120.0 (4)	C46'—C45'—H45E	109.5
C20—C19—H19	120.0	H45D—C45'—H45E	109.5
C18—C19—H19	120.0	C46'—C45'—H45F	109.5
C19—C20—C21	121.1 (3)	H45D—C45'—H45F	109.5
C19—C20—H20	119.5	H45E—C45'—H45F	109.5
C21—C20—H20	119.5	O3'—C46'—C45'	111.0 (10)
C20—C21—C22	121.3 (4)	O3'—C46'—H46C	109.4
C20—C21—C26	119.0 (3)	C45'—C46'—H46C	109.4
C22—C21—C26	119.7 (4)	O3'—C46'—H46D	109.4
C23—C22—C21	120.7 (4)	C45'—C46'—H46D	109.4
C23—C22—H22	119.7	H46C—C46'—H46D	108.0
C21—C22—H22	119.7	O3'—C47'—C48'	115.2 (11)
C22—C23—C24	120.5 (4)	O3'—C47'—H47C	108.5
C22—C23—H23	119.8	C48'—C47'—H47C	108.5
C24—C23—H23	119.8	O3'—C47'—H47D	108.5
C25—C24—C23	120.2 (4)	C48'—C47'—H47D	108.5
C25—C24—H24	119.9	H47C—C47'—H47D	107.5
C23—C24—H24	119.9	C47'—C48'—H48D	109.5
C24—C25—C26	121.6 (3)	C47'—C48'—H48E	109.5
C24—C25—H25	119.2	H48D—C48'—H48E	109.5
C26—C25—H25	119.2	C47'—C48'—H48F	109.5
C25—C26—C17	123.2 (3)	H48D—C48'—H48F	109.5
C25—C26—C21	117.3 (3)	H48E—C48'—H48F	109.5
C17—C26—C21	119.5 (3)
C8—N1—C1—C2	−172.0 (3)	C7—C9—C16—C15	−108.0 (2)
C8—N1—C1—C6	3.4 (3)	C10—C9—C16—C15	139.9 (2)
C6—C1—C2—C3	−0.9 (4)	C11—C10—C17—C18	41.1 (4)
N1—C1—C2—C3	173.9 (3)	C9—C10—C17—C18	−81.9 (3)
C1—C2—C3—C4	−0.5 (5)	C11—C10—C17—C26	−136.7 (3)
C2—C3—C4—C5	0.5 (5)	C9—C10—C17—C26	100.2 (3)
C3—C4—C5—C6	0.9 (5)	C26—C17—C18—C19	1.5 (4)
C4—C5—C6—C1	−2.2 (4)	C10—C17—C18—C19	−176.4 (3)
C4—C5—C6—C7	−173.8 (3)	C17—C18—C19—C20	−0.7 (5)
C2—C1—C6—C5	2.2 (4)	C18—C19—C20—C21	−0.8 (6)
N1—C1—C6—C5	−173.4 (2)	C19—C20—C21—C22	−179.1 (4)
C2—C1—C6—C7	175.6 (3)	C19—C20—C21—C26	1.3 (5)
N1—C1—C6—C7	0.0 (3)	C20—C21—C22—C23	179.0 (4)
C12—N2—C7—C6	63.5 (3)	C26—C21—C22—C23	−1.4 (6)
C11—N2—C7—C6	−170.1 (2)	C21—C22—C23—C24	1.1 (7)
C12—N2—C7—C8	−48.8 (3)	C22—C23—C24—C25	−0.6 (6)
C11—N2—C7—C8	77.6 (3)	C23—C24—C25—C26	0.3 (5)
C12—N2—C7—C9	−166.7 (2)	C24—C25—C26—C17	−179.4 (3)
C11—N2—C7—C9	−40.3 (2)	C24—C25—C26—C21	−0.6 (4)
C5—C6—C7—N2	49.9 (4)	C18—C17—C26—C25	177.9 (3)
C1—C6—C7—N2	−122.3 (2)	C10—C17—C26—C25	−4.2 (4)
C5—C6—C7—C8	169.5 (3)	C18—C17—C26—C21	−1.0 (4)
C1—C6—C7—C8	−2.7 (3)	C10—C17—C26—C21	177.0 (3)
C5—C6—C7—C9	−70.6 (4)	C20—C21—C26—C25	−179.3 (3)
C1—C6—C7—C9	117.2 (2)	C22—C21—C26—C25	1.1 (4)
C1—N1—C8—O1	174.1 (2)	C20—C21—C26—C17	−0.4 (4)
C1—N1—C8—C7	−5.2 (3)	C22—C21—C26—C17	−180.0 (3)
N2—C7—C8—O1	−55.9 (3)	C13—N3—C27—C28	−176.1 (2)
C6—C7—C8—O1	−174.5 (2)	C14—N3—C27—C28	62.2 (3)
C9—C7—C8—O1	58.4 (3)	N3—C27—C28—C29	−131.5 (3)
N2—C7—C8—N1	123.4 (2)	N3—C27—C28—C33	49.4 (4)
C6—C7—C8—N1	4.7 (3)	C33—C28—C29—C30	−0.7 (5)
C9—C7—C8—N1	−122.4 (2)	C27—C28—C29—C30	−179.8 (3)
N2—C7—C9—C16	−96.3 (2)	C28—C29—C30—C31	0.1 (6)
C6—C7—C9—C16	28.2 (3)	C29—C30—C31—C32	0.6 (7)
C8—C7—C9—C16	143.7 (2)	C30—C31—C32—C33	−0.7 (6)
N2—C7—C9—C13	144.1 (2)	C31—C32—C33—C28	0.0 (6)
C6—C7—C9—C13	−91.5 (3)	C29—C28—C33—C32	0.7 (5)
C8—C7—C9—C13	24.0 (3)	C27—C28—C33—C32	179.7 (3)
N2—C7—C9—C10	19.7 (2)	C16—C15—C34—C35	179.1 (3)
C6—C7—C9—C10	144.2 (2)	C14—C15—C34—C35	−3.8 (5)
C8—C7—C9—C10	−100.3 (2)	C15—C34—C35—C36	−67.5 (4)
C16—C9—C10—C17	−110.0 (3)	C15—C34—C35—C44	116.1 (4)
C13—C9—C10—C17	11.6 (3)	C44—C35—C36—C37	2.5 (6)
C7—C9—C10—C17	134.7 (2)	C34—C35—C36—C37	−174.0 (4)
C16—C9—C10—C11	121.3 (2)	C35—C36—C37—C38	−1.9 (7)
C13—C9—C10—C11	−117.1 (2)	C36—C37—C38—C39	0.2 (7)
C7—C9—C10—C11	6.0 (3)	C37—C38—C39—C40	179.9 (4)
C12—N2—C11—C10	172.3 (2)	C37—C38—C39—C44	0.8 (6)
C7—N2—C11—C10	45.1 (3)	C38—C39—C40—C41	179.0 (4)
C17—C10—C11—N2	−160.2 (2)	C44—C39—C40—C41	−1.9 (6)
C9—C10—C11—N2	−30.1 (3)	C39—C40—C41—C42	2.1 (7)
C14—N3—C13—C9	−78.1 (3)	C40—C41—C42—C43	−1.3 (6)
C27—N3—C13—C9	158.3 (2)	C41—C42—C43—C44	0.3 (5)
C16—C9—C13—N3	39.7 (3)	C42—C43—C44—C35	−179.9 (3)
C7—C9—C13—N3	159.41 (19)	C42—C43—C44—C39	−0.1 (5)
C10—C9—C13—N3	−82.6 (2)	C36—C35—C44—C43	178.3 (3)
C13—N3—C14—C15	53.4 (3)	C34—C35—C44—C43	−5.3 (5)
C27—N3—C14—C15	176.8 (2)	C36—C35—C44—C39	−1.4 (5)
N3—C14—C15—C34	−175.3 (3)	C34—C35—C44—C39	175.0 (3)
N3—C14—C15—C16	1.9 (3)	C38—C39—C44—C43	−180.0 (3)
C34—C15—C16—O2	−36.5 (4)	C40—C39—C44—C43	0.9 (5)
C14—C15—C16—O2	146.2 (3)	C38—C39—C44—C35	−0.2 (5)
C34—C15—C16—C9	140.4 (3)	C40—C39—C44—C35	−179.4 (3)
C14—C15—C16—C9	−36.9 (3)	C47—O3—C46—C45	−158.3 (18)
C13—C9—C16—O2	−168.7 (2)	C46—O3—C47—C48	−173.7 (19)
C7—C9—C16—O2	68.9 (3)	C47'—O3'—C46'—C45'	−179 (3)
C10—C9—C16—O2	−43.3 (3)	C46'—O3'—C47'—C48'	174 (3)
C13—C9—C16—C15	14.4 (3)