An organic photochromic compound: (2S)-2'-ethoxy-1,3,3-trimethyl-6'-(piperi­din-1-yl)spiro­[indoline-2,3'-3'H-naphtho[2,1-b][1,4]oxazine]

In the course of our synthesis of hybrid photochromic compounds, the unexpected new organic photochromic title compound, C₂₉H₃₃N₃O₂, (I), was obtained. It is a deri­vative of the parent spiro­oxazine 1,3,3-trimethyl-6'-(piperi­din-1-yl)spiro­[indoline-2,3'-3'H-naphtho[2,1-b][1,4]oxazine], (II). The 2'-eth­oxy group gives (I) different photochromic properties from its parent spiro­oxazine (II).

S1. Comment

Organic photochromic compounds play an important role in various organic–inorganic hybrid photochromic systems. They are employed to implement the photochromic function. In such organic compounds interesting reversible chemical and physical conversions have also been observed, based on photoinduced ring opening and closing, cycloaddition, or electron- and energy-transfer processes (Raymo & Tomasulo, 2005; Shimizu et al., 2006; Aldoshin, 2008).

Spirooxazines are one of the well known families of organic photochromic molecules with fast photocoloring rates and high light-fatigue resistance. Over the past several decades, numerous types of spirooxazine derivatives have been characterized. It is certain that C—O bond cleavage in spirooxazines induced by UV irradiation or heating is the main reason for their photochromism, and the C═N bond in the oxazinic ring improves its durability (Clegg et al., 1991; Osano et al., 1991; Reboul et al., 1995; Pèpe et al., 1995; Malatesta et al., 1995; Sun et al., 1997; Liang et al., 1998; Chamontin et al., 1998; Guo et al., 2005), but there are still some details of the structure–property relationships needing further explanation. For example, it was assumed that the more planar the oxazinic ring, the less photochromatic the molecule (Reboul et al., 1995). However, investigation of the molecular geometry of spirooxazines by Chamontin et al. (1998) showed that there is no obvious correlation. Additional research on the influence of substituent groups in 2'-substituted spirooxazines is also baffling (Clegg et al., 1991; Liang et al., 1998; Uznanski et al., 2001).

In the title compound, (I), there are two equivalent spirooxazine molecules in the asymmetric unit (Fig. 1). The least-squares planes through the aromatic rings show that the two benzene rings [maximum deviations of 0.0024 (1) and 0.0062 (2) Å for which rings?, respectively] and two phenanthroline rings [maximum deviations of 0.0250 (2) and 0.0312 (2) Å for which rings?, respectively] both exhibit expected planar geometries, and the dihedral angles between the two types of plane are 108.1 (2) and 109.3 (2)°. Atoms C7 and N1 (or C36 and N4) attached to the benzene rings lie very close to the ring planes in the two molecules, with deviations of 0.062 (4) and 0.002 (4) Å [or 0.057 (4) and 0.011 (4) Å], respectively. Similarly, atoms N2 and O2 (or N5 and O4) are also approximately coplanar with the phenanthroline ring planes, with deviations of 0.072 (3) and 0.126 (2) Å [or 0.090 (3) and 0.050 (2) Å], respectively. The non-aromatic five- and six-membered rings around C_spiro are twisted and their conformations may be characterized as half-chair according to the method given by Cremer & Pople (1975). Furthermore, there are two substitutent groups in the molecule; the piperidine ring at the 6'-C site is in a chair conformation and the ethoxy group at the 2'-C site is approximately coplanar with C═N.

The oxazine rings (the key zone of the photochromism) suggest bond delocalization involving the C, N and O atoms, including the adjacent aromatic ring (Sun et al., 1997; Liang et al., 1998.). This is confirmed by the bond lengths involving the C, N and O atoms. For instance, the C1—N1 bond length is 1.395 (3) Å, which is between the values of 1.48 Å for a C—N single bond and 1.28 Å for a C═N double bond (Allen et al., 1987), indicating partial delocalization of the π-electron density over the indole ring. Similarly, the C19—O2 bond length is 1.370 (2) Å, which is between the values of 1.43 Å for a C—O single bond and 1.23 Å for a C═O double bond (Allen et al., 1987). The C10—N2 bond length is 1.408 (3) Å, indicating that atoms O2, N2 in the oxazine ring are conjugated with the π-electron system of the naphthalene ring. All of these delocalizations are beneficial to the stabilization of the open-ring form of the spirooxazine.

The distances of the C_spiro—O and C_spiro—N bonds are two key points in the structure of (I). The former cleaves upon photoexcitation to give an open form of the spirooxazine, and the latter has an influence on the stability of the open form. Here, the C_spiro—O bond lengths are 1.458 (2) and 1.466 (3) Å, respectively, for atoms C8 and C37, and the C_spiro—N bond lengths are 1.423 (3) and 1.434 (3) Å, respectively, for atoms C8 and C37. These bond lengths show no significant differences compared with other photochromic spirooxazines (Clegg et al., 1991; Osano et al., 1991; Reboul et al., 1995; Pèpe et al., 1995; Malatesta et al., 1995; Sun et al., 1997; Liang et al., 1998; Chamontin et al., 1998; Guo et al., 2005).

A characteristic of (I) is that there is an ethoxy group at the 2'-position. A similar ethoxy-substituted compound, 2'-ethoxy-1,3,3-trimethyl-5-nitrospiro[indoline-2,3'-naphtho[2,1- b][1,4]oxazine], was synthesized by Uznanski et al. (2001), but it displays no photochromic properties. Interestingly, this ethoxy substituent at the 2'-position (atoms C2 and C38) leads to an obvious change in (I) compared with the parent spirooxazine, (II). The parent shows no colour change under UV light or sunlight, but the substituted compound displays various photochromic conversions in different solvents under UV exposure.

The different photochromic properties found in compound (I) require further study of its structure–property relationships. Research on the mechanism of the ethoxy reaction at the 2'-position of spirooxazine is also in progress.

S2. Experimental

Lead(II) iodide (24 mg, 0.05 mmol), potassium iodide (17 mg, 0.1 mmol) and the parent spirooxazine, 1,3,3-trimethyl-6'-(piperidin-1-yl)spiro[indoline-2,3'-3'H-naphtho[2,1-b][1,4]oxazine] (21 mg, 0.05 mmol), were heated in a Teflon-lined stainless steel autoclave with ethanol (10 ml) at 393 K. Chunky pale-yellow crystals of (I) were obtained by slow evaporation of the reaction solution.

Compound (I) dissolves in ethanol (EtOH), dimethylbenzene (C₈H₁₀), dichloromethane (CH₂Cl₂) and chloroform (CHCl₃), and appears colourless, yellow, pale green and colourless, respectively. After irradiation with UV light, these solutions change to aqua green, light blue, green and pale bluish–green, respectively. A pale-green solution is observed when (I) is dissolved in chloroform-d (CDCl₃) which turns purple when exposed to sunlight. However, no colour change was observed under UV light.

S3. Refinement

H atoms were added at calculated positions and refined using a riding model, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H. [Please check added text]

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I), viewed along the a direction.

(2S)-2'-ethoxy-1,3,3-trimethyl-6'-(piperidin-1-yl)spiro[indoline- 2,3'-3'H-naphtho[2,1-b][1,4]oxazine]

Crystal data

C29H33N3O2	Z = 4
Mr = 455.58	F(000) = 976
Triclinic, P1	Dx = 1.204 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 10.001 (2) Å	Cell parameters from 12969 reflections
b = 12.345 (3) Å	θ = 3.1–27.5°
c = 20.513 (4) Å	µ = 0.08 mm^−1
α = 88.49 (3)°	T = 296 K
β = 87.32 (3)°	Block, yellow
γ = 83.62 (3)°	0.43 × 0.37 × 0.28 mm
V = 2513.6 (9) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	11325 independent reflections
Radiation source: fine-focus sealed tube	5097 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 14.6306 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→15
Tmin = 0.968, Tmax = 0.979	l = −26→26
24807 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)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.189	w = 1/[σ^2(Fo^2) + (0.0846P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
11325 reflections	Δρmax = 0.21 e Å^−3
621 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0083 (12)

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
O1	−0.46493 (18)	0.26659 (17)	0.51199 (8)	0.0832 (6)
O2	−0.12153 (15)	0.22614 (12)	0.45679 (6)	0.0552 (4)
O3	0.96570 (16)	0.09168 (15)	0.12882 (8)	0.0733 (5)
O4	0.61987 (14)	0.19400 (11)	0.11737 (6)	0.0500 (4)
N1	−0.2393 (2)	0.13182 (15)	0.53471 (9)	0.0619 (5)
N2	−0.35855 (19)	0.35948 (17)	0.43074 (9)	0.0622 (5)
N3	0.13034 (18)	0.40203 (15)	0.28729 (8)	0.0522 (5)
N4	0.73884 (19)	0.12827 (15)	0.20726 (8)	0.0540 (5)
N5	0.85784 (19)	0.16636 (16)	0.03974 (9)	0.0587 (5)
N6	0.36956 (18)	0.36184 (14)	−0.06043 (8)	0.0518 (4)
C1	−0.1434 (3)	0.1080 (2)	0.58175 (11)	0.0651 (7)
C2	−0.0940 (4)	0.0083 (2)	0.60732 (15)	0.0976 (10)
H2	−0.1240	−0.0554	0.5932	0.117*
C3	−0.0005 (5)	0.0042 (4)	0.65356 (19)	0.1321 (16)
H3	0.0327	−0.0628	0.6715	0.158*
C4	0.0454 (5)	0.0968 (4)	0.67407 (17)	0.1356 (16)
H4	0.1096	0.0920	0.7057	0.163*
C5	−0.0027 (4)	0.1996 (3)	0.64827 (14)	0.1045 (11)
H5	0.0292	0.2628	0.6619	0.125*
C6	−0.0990 (3)	0.2033 (2)	0.60205 (11)	0.0658 (7)
C7	−0.1743 (2)	0.29945 (18)	0.56764 (10)	0.0562 (6)
C8	−0.2258 (2)	0.23843 (18)	0.50900 (9)	0.0504 (5)
C9	−0.3529 (2)	0.2938 (2)	0.47950 (11)	0.0598 (6)
C10	−0.2353 (2)	0.37487 (18)	0.39774 (10)	0.0520 (5)
C11	−0.2287 (2)	0.45873 (17)	0.34926 (9)	0.0498 (5)
C12	−0.3420 (3)	0.5347 (2)	0.33662 (11)	0.0642 (6)
H12	−0.4240	0.5269	0.3585	0.077*
C13	−0.3330 (3)	0.6187 (2)	0.29307 (12)	0.0718 (7)
H13	−0.4084	0.6678	0.2855	0.086*
C14	−0.2103 (3)	0.6316 (2)	0.25946 (11)	0.0687 (7)
H14	−0.2042	0.6902	0.2304	0.082*
C15	−0.0999 (3)	0.55872 (19)	0.26914 (10)	0.0601 (6)
H15	−0.0194	0.5676	0.2461	0.072*
C16	−0.1057 (2)	0.46982 (17)	0.31366 (9)	0.0485 (5)
C17	0.0098 (2)	0.39240 (17)	0.32549 (9)	0.0477 (5)
C18	0.0000 (2)	0.31395 (17)	0.37342 (9)	0.0496 (5)
H18	0.0746	0.2646	0.3819	0.060*
C19	−0.1206 (2)	0.30703 (17)	0.40980 (9)	0.0483 (5)
C20	0.1244 (3)	0.3605 (2)	0.22117 (10)	0.0652 (7)
H20A	0.0406	0.3904	0.2024	0.078*
H20B	0.1264	0.2818	0.2233	0.078*
C21	0.2418 (3)	0.3915 (3)	0.17813 (12)	0.0838 (8)
H21A	0.2350	0.4702	0.1725	0.101*
H21B	0.2387	0.3602	0.1354	0.101*
C22	0.3750 (3)	0.3509 (3)	0.20808 (13)	0.0849 (8)
H22A	0.3883	0.2719	0.2076	0.102*
H22B	0.4485	0.3784	0.1824	0.102*
C23	0.3755 (3)	0.3888 (2)	0.27728 (12)	0.0738 (7)
H23A	0.3747	0.4674	0.2771	0.089*
H23B	0.4573	0.3569	0.2971	0.089*
C24	0.2547 (2)	0.3567 (2)	0.31708 (11)	0.0639 (6)
H24A	0.2584	0.2778	0.3197	0.077*
H24B	0.2562	0.3833	0.3611	0.077*
C25	−0.2742 (3)	0.0474 (2)	0.49213 (14)	0.0940 (10)
H25A	−0.1947	0.0167	0.4682	0.141*
H25B	−0.3393	0.0787	0.4621	0.141*
H25C	−0.3114	−0.0088	0.5180	0.141*
C26	−0.0890 (3)	0.3903 (2)	0.54633 (13)	0.0764 (7)
H26A	−0.0573	0.4219	0.5842	0.115*
H26B	−0.1426	0.4453	0.5221	0.115*
H26C	−0.0135	0.3608	0.5193	0.115*
C27	−0.2918 (3)	0.3474 (2)	0.61226 (12)	0.0768 (8)
H27A	−0.3464	0.2909	0.6260	0.115*
H27B	−0.3454	0.4036	0.5889	0.115*
H27C	−0.2575	0.3777	0.6499	0.115*
C28	−0.7002 (3)	0.2667 (3)	0.52684 (19)	0.1236 (13)
H28A	−0.6898	0.1894	0.5202	0.185*
H28B	−0.7863	0.2976	0.5123	0.185*
H28C	−0.6945	0.2805	0.5724	0.185*
C29	−0.5926 (3)	0.3166 (3)	0.48935 (16)	0.1131 (12)
H29A	−0.5985	0.3043	0.4431	0.136*
H29B	−0.6015	0.3946	0.4961	0.136*
C30	0.6423 (2)	0.07325 (19)	0.24151 (10)	0.0583 (6)
C31	0.5927 (3)	0.0879 (3)	0.30506 (12)	0.0854 (9)
H31	0.6224	0.1403	0.3310	0.103*
C32	0.4980 (4)	0.0225 (3)	0.32870 (17)	0.1165 (12)
H32	0.4632	0.0310	0.3713	0.140*
C33	0.4534 (4)	−0.0551 (3)	0.29081 (19)	0.1205 (13)
H33	0.3894	−0.0984	0.3080	0.145*
C34	0.5039 (3)	−0.0694 (2)	0.22627 (15)	0.0920 (9)
H34	0.4736	−0.1214	0.2003	0.110*
C35	0.5987 (2)	−0.00513 (19)	0.20246 (11)	0.0596 (6)
C36	0.6755 (2)	−0.00388 (17)	0.13711 (10)	0.0529 (5)
C37	0.7264 (2)	0.11151 (17)	0.13898 (10)	0.0489 (5)
C38	0.8527 (2)	0.12677 (18)	0.09753 (11)	0.0544 (5)
C39	0.7340 (2)	0.20795 (17)	0.01361 (10)	0.0491 (5)
C40	0.7298 (2)	0.24092 (17)	−0.05351 (10)	0.0498 (5)
C41	0.8436 (3)	0.2246 (2)	−0.09657 (11)	0.0656 (6)
H41	0.9254	0.1946	−0.0806	0.079*
C42	0.8360 (3)	0.2520 (2)	−0.16136 (13)	0.0778 (8)
H42	0.9123	0.2404	−0.1891	0.093*
C43	0.7154 (3)	0.2969 (2)	−0.18592 (12)	0.0755 (8)
H43	0.7111	0.3145	−0.2302	0.091*
C44	0.6022 (3)	0.31594 (19)	−0.14589 (10)	0.0636 (6)
H44	0.5220	0.3465	−0.1632	0.076*
C45	0.6062 (2)	0.28950 (17)	−0.07812 (9)	0.0493 (5)
C46	0.4900 (2)	0.30835 (16)	−0.03475 (10)	0.0476 (5)
C47	0.4976 (2)	0.27300 (16)	0.02907 (9)	0.0466 (5)
H47	0.4217	0.2826	0.0572	0.056*
C48	0.6189 (2)	0.22256 (16)	0.05197 (9)	0.0448 (5)
C49	0.3752 (3)	0.48055 (18)	−0.06930 (12)	0.0652 (7)
H49A	0.4601	0.4937	−0.0912	0.078*
H49B	0.3702	0.5144	−0.0270	0.078*
C50	0.2604 (3)	0.5308 (2)	−0.10905 (13)	0.0789 (8)
H50A	0.2693	0.5012	−0.1526	0.095*
H50B	0.2635	0.6089	−0.1130	0.095*
C51	0.1272 (3)	0.5077 (2)	−0.07715 (15)	0.0893 (9)
H51A	0.0548	0.5345	−0.1053	0.107*
H51B	0.1127	0.5456	−0.0362	0.107*
C52	0.1251 (3)	0.3860 (2)	−0.06459 (13)	0.0747 (7)
H52A	0.0424	0.3729	−0.0406	0.090*
H52B	0.1277	0.3491	−0.1059	0.090*
C53	0.2450 (2)	0.3408 (2)	−0.02582 (11)	0.0627 (6)
H53A	0.2393	0.3745	0.0165	0.075*
H53B	0.2437	0.2629	−0.0189	0.075*
C54	0.7740 (3)	0.2317 (2)	0.23008 (12)	0.0726 (7)
H54A	0.6956	0.2843	0.2309	0.109*
H54B	0.8425	0.2574	0.2011	0.109*
H54C	0.8071	0.2218	0.2732	0.109*
C55	0.5897 (3)	−0.0187 (2)	0.07882 (11)	0.0699 (7)
H55A	0.5600	−0.0901	0.0812	0.105*
H55B	0.6425	−0.0108	0.0390	0.105*
H55C	0.5129	0.0354	0.0796	0.105*
C56	0.7943 (3)	−0.09406 (19)	0.13666 (13)	0.0754 (7)
H56A	0.8484	−0.0860	0.1733	0.113*
H56B	0.8480	−0.0885	0.0969	0.113*
H56C	0.7607	−0.1640	0.1394	0.113*
C57	1.2024 (3)	0.0625 (3)	0.13793 (18)	0.1083 (11)
H57A	1.1890	0.1022	0.1777	0.162*
H57B	1.2880	0.0745	0.1175	0.162*
H57C	1.2007	−0.0139	0.1475	0.162*
C58	1.0931 (3)	0.1008 (3)	0.09305 (16)	0.0970 (10)
H58A	1.0997	0.1758	0.0793	0.116*
H58B	1.1001	0.0561	0.0546	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0484 (11)	0.1201 (16)	0.0791 (11)	−0.0088 (10)	0.0012 (9)	0.0250 (11)
O2	0.0576 (10)	0.0588 (9)	0.0464 (8)	0.0013 (8)	0.0048 (7)	0.0073 (7)
O3	0.0453 (10)	0.0896 (13)	0.0830 (11)	0.0006 (9)	−0.0082 (8)	0.0097 (10)
O4	0.0508 (9)	0.0523 (8)	0.0441 (7)	0.0064 (7)	−0.0029 (6)	0.0043 (6)
N1	0.0703 (14)	0.0544 (11)	0.0613 (11)	−0.0111 (10)	−0.0006 (10)	0.0066 (9)
N2	0.0478 (12)	0.0833 (14)	0.0529 (10)	0.0007 (10)	−0.0004 (9)	0.0117 (10)
N3	0.0486 (11)	0.0623 (11)	0.0452 (9)	−0.0046 (9)	0.0009 (8)	−0.0038 (8)
N4	0.0563 (12)	0.0595 (11)	0.0468 (9)	−0.0061 (9)	−0.0114 (8)	0.0003 (9)
N5	0.0490 (12)	0.0640 (12)	0.0613 (11)	−0.0015 (9)	−0.0010 (9)	0.0069 (10)
N6	0.0539 (12)	0.0493 (10)	0.0525 (10)	−0.0055 (9)	−0.0098 (9)	0.0049 (8)
C1	0.0772 (18)	0.0611 (15)	0.0522 (13)	0.0066 (13)	0.0084 (12)	0.0095 (11)
C2	0.128 (3)	0.0710 (19)	0.0847 (19)	0.0202 (19)	0.001 (2)	0.0238 (16)
C3	0.178 (4)	0.109 (3)	0.093 (3)	0.058 (3)	−0.016 (3)	0.021 (2)
C4	0.155 (4)	0.152 (4)	0.086 (2)	0.065 (3)	−0.054 (2)	0.002 (3)
C5	0.119 (3)	0.115 (3)	0.0737 (17)	0.034 (2)	−0.0394 (19)	−0.0195 (18)
C6	0.0739 (18)	0.0695 (16)	0.0490 (12)	0.0163 (13)	−0.0060 (12)	−0.0004 (12)
C7	0.0601 (15)	0.0575 (14)	0.0488 (12)	0.0036 (12)	−0.0018 (11)	−0.0028 (10)
C8	0.0478 (14)	0.0578 (13)	0.0441 (11)	−0.0030 (11)	0.0036 (10)	0.0062 (10)
C9	0.0445 (14)	0.0795 (17)	0.0546 (13)	−0.0070 (12)	0.0028 (11)	0.0042 (12)
C10	0.0462 (14)	0.0633 (14)	0.0447 (11)	0.0013 (11)	−0.0007 (10)	0.0010 (10)
C11	0.0505 (14)	0.0567 (13)	0.0408 (10)	0.0017 (11)	−0.0060 (10)	−0.0006 (10)
C12	0.0584 (16)	0.0734 (16)	0.0576 (13)	0.0081 (13)	−0.0064 (11)	0.0027 (12)
C13	0.0737 (19)	0.0733 (17)	0.0637 (14)	0.0153 (14)	−0.0126 (14)	0.0062 (13)
C14	0.084 (2)	0.0581 (15)	0.0604 (14)	0.0037 (14)	−0.0082 (14)	0.0137 (12)
C15	0.0708 (17)	0.0609 (14)	0.0485 (12)	−0.0068 (13)	−0.0038 (11)	0.0034 (11)
C16	0.0529 (14)	0.0522 (12)	0.0399 (10)	−0.0013 (11)	−0.0043 (10)	−0.0037 (9)
C17	0.0469 (13)	0.0546 (13)	0.0413 (10)	−0.0039 (10)	0.0016 (9)	−0.0055 (10)
C18	0.0468 (13)	0.0545 (13)	0.0450 (11)	0.0041 (10)	0.0018 (9)	−0.0014 (10)
C19	0.0517 (14)	0.0532 (12)	0.0387 (10)	−0.0014 (11)	0.0003 (9)	0.0005 (9)
C20	0.0675 (17)	0.0813 (17)	0.0466 (12)	−0.0083 (14)	0.0033 (11)	−0.0091 (12)
C21	0.081 (2)	0.114 (2)	0.0558 (14)	−0.0159 (18)	0.0189 (14)	−0.0075 (15)
C22	0.069 (2)	0.103 (2)	0.0810 (18)	−0.0086 (17)	0.0224 (15)	−0.0100 (16)
C23	0.0519 (16)	0.0862 (18)	0.0823 (17)	−0.0064 (14)	0.0049 (13)	−0.0041 (14)
C24	0.0512 (15)	0.0788 (17)	0.0608 (13)	−0.0039 (13)	0.0004 (11)	−0.0010 (12)
C25	0.114 (3)	0.0750 (19)	0.098 (2)	−0.0331 (18)	−0.0037 (18)	−0.0063 (16)
C26	0.081 (2)	0.0745 (17)	0.0765 (16)	−0.0165 (15)	−0.0079 (14)	−0.0076 (14)
C27	0.085 (2)	0.0783 (17)	0.0607 (14)	0.0141 (15)	0.0108 (13)	−0.0053 (13)
C28	0.059 (2)	0.150 (3)	0.163 (3)	−0.024 (2)	0.012 (2)	−0.014 (3)
C29	0.0481 (19)	0.176 (4)	0.111 (2)	−0.005 (2)	−0.0067 (17)	0.037 (2)
C30	0.0600 (15)	0.0642 (15)	0.0486 (12)	0.0005 (12)	−0.0034 (11)	0.0101 (11)
C31	0.099 (2)	0.098 (2)	0.0564 (15)	−0.0031 (19)	0.0030 (15)	0.0060 (15)
C32	0.139 (3)	0.131 (3)	0.077 (2)	−0.021 (3)	0.032 (2)	0.013 (2)
C33	0.122 (3)	0.126 (3)	0.113 (3)	−0.039 (3)	0.044 (2)	0.028 (2)
C34	0.095 (2)	0.082 (2)	0.100 (2)	−0.0272 (18)	0.0146 (18)	0.0104 (17)
C35	0.0602 (16)	0.0566 (14)	0.0616 (13)	−0.0085 (12)	0.0026 (11)	0.0091 (11)
C36	0.0550 (14)	0.0477 (12)	0.0554 (12)	−0.0025 (11)	−0.0051 (10)	0.0001 (10)
C37	0.0416 (13)	0.0512 (12)	0.0522 (12)	0.0034 (10)	−0.0056 (10)	0.0001 (10)
C38	0.0424 (14)	0.0561 (13)	0.0637 (14)	−0.0007 (11)	−0.0072 (11)	0.0038 (11)
C39	0.0461 (13)	0.0501 (12)	0.0506 (11)	−0.0048 (10)	−0.0002 (10)	0.0022 (10)
C40	0.0530 (14)	0.0476 (12)	0.0492 (11)	−0.0104 (10)	0.0045 (10)	−0.0004 (10)
C41	0.0614 (16)	0.0699 (16)	0.0648 (14)	−0.0094 (13)	0.0108 (12)	0.0007 (12)
C42	0.081 (2)	0.0866 (19)	0.0640 (16)	−0.0141 (16)	0.0204 (14)	0.0014 (14)
C43	0.094 (2)	0.0827 (18)	0.0500 (13)	−0.0187 (17)	0.0100 (14)	0.0040 (13)
C44	0.0768 (18)	0.0636 (15)	0.0516 (13)	−0.0132 (13)	−0.0055 (12)	0.0039 (11)
C45	0.0579 (15)	0.0480 (12)	0.0440 (11)	−0.0143 (11)	−0.0024 (10)	0.0008 (9)
C46	0.0525 (14)	0.0419 (11)	0.0497 (11)	−0.0075 (10)	−0.0101 (10)	−0.0019 (9)
C47	0.0456 (13)	0.0473 (12)	0.0465 (11)	−0.0021 (10)	−0.0025 (9)	−0.0018 (9)
C48	0.0495 (13)	0.0433 (11)	0.0411 (10)	−0.0033 (10)	−0.0010 (9)	0.0013 (9)
C49	0.0817 (19)	0.0480 (13)	0.0668 (14)	−0.0044 (12)	−0.0223 (13)	0.0023 (11)
C50	0.101 (2)	0.0534 (15)	0.0818 (17)	0.0051 (15)	−0.0364 (17)	0.0022 (13)
C51	0.086 (2)	0.089 (2)	0.0883 (19)	0.0254 (17)	−0.0342 (17)	−0.0114 (16)
C52	0.0598 (17)	0.091 (2)	0.0715 (15)	0.0065 (14)	−0.0145 (13)	−0.0079 (14)
C53	0.0560 (16)	0.0730 (16)	0.0581 (13)	−0.0018 (13)	−0.0032 (11)	−0.0007 (12)
C54	0.084 (2)	0.0733 (17)	0.0638 (14)	−0.0155 (14)	−0.0198 (13)	−0.0072 (13)
C55	0.0764 (18)	0.0634 (15)	0.0728 (15)	−0.0155 (13)	−0.0122 (13)	−0.0067 (13)
C56	0.079 (2)	0.0543 (14)	0.0881 (17)	0.0134 (13)	−0.0059 (15)	−0.0032 (13)
C57	0.0529 (19)	0.111 (3)	0.160 (3)	0.0051 (17)	−0.0222 (19)	−0.015 (2)
C58	0.0433 (17)	0.130 (3)	0.115 (2)	−0.0036 (17)	0.0046 (16)	0.010 (2)

Geometric parameters (Å, º)

O1—C9	1.347 (3)	C26—H26A	0.9600
O1—C29	1.446 (3)	C26—H26B	0.9600
O2—C19	1.370 (2)	C26—H26C	0.9600
O2—C8	1.458 (2)	C27—H27A	0.9600
O3—C38	1.349 (3)	C27—H27B	0.9600
O3—C58	1.454 (3)	C27—H27C	0.9600
O4—C48	1.378 (2)	C28—C29	1.474 (4)
O4—C37	1.466 (2)	C28—H28A	0.9600
N1—C1	1.395 (3)	C28—H28B	0.9600
N1—C8	1.423 (3)	C28—H28C	0.9600
N1—C25	1.459 (3)	C29—H29A	0.9700
N2—C9	1.270 (3)	C29—H29B	0.9700
N2—C10	1.408 (3)	C30—C31	1.382 (3)
N3—C17	1.421 (3)	C30—C35	1.391 (3)
N3—C24	1.460 (3)	C31—C32	1.375 (4)
N3—C20	1.468 (3)	C31—H31	0.9300
N4—C30	1.394 (3)	C32—C33	1.374 (5)
N4—C37	1.434 (2)	C32—H32	0.9300
N4—C54	1.457 (3)	C33—C34	1.403 (4)
N5—C38	1.271 (3)	C33—H33	0.9300
N5—C39	1.411 (3)	C34—C35	1.368 (3)
N6—C46	1.424 (3)	C34—H34	0.9300
N6—C53	1.450 (3)	C35—C36	1.514 (3)
N6—C49	1.479 (3)	C36—C55	1.530 (3)
C1—C2	1.375 (4)	C36—C56	1.535 (3)
C1—C6	1.384 (3)	C36—C37	1.568 (3)
C2—C3	1.358 (5)	C37—C38	1.516 (3)
C2—H2	0.9300	C39—C48	1.361 (3)
C3—C4	1.362 (5)	C39—C40	1.426 (3)
C3—H3	0.9300	C40—C41	1.408 (3)
C4—C5	1.405 (5)	C40—C45	1.421 (3)
C4—H4	0.9300	C41—C42	1.366 (3)
C5—C6	1.379 (4)	C41—H41	0.9300
C5—H5	0.9300	C42—C43	1.382 (4)
C6—C7	1.510 (3)	C42—H42	0.9300
C7—C26	1.525 (3)	C43—C44	1.369 (4)
C7—C27	1.531 (3)	C43—H43	0.9300
C7—C8	1.573 (3)	C44—C45	1.421 (3)
C8—C9	1.518 (3)	C44—H44	0.9300
C10—C19	1.371 (3)	C45—C46	1.432 (3)
C10—C11	1.421 (3)	C46—C47	1.372 (3)
C11—C12	1.417 (3)	C47—C48	1.397 (3)
C11—C16	1.418 (3)	C47—H47	0.9300
C12—C13	1.358 (3)	C49—C50	1.507 (3)
C12—H12	0.9300	C49—H49A	0.9700
C13—C14	1.401 (4)	C49—H49B	0.9700
C13—H13	0.9300	C50—C51	1.509 (4)
C14—C15	1.364 (3)	C50—H50A	0.9700
C14—H14	0.9300	C50—H50B	0.9700
C15—C16	1.413 (3)	C51—C52	1.520 (4)
C15—H15	0.9300	C51—H51A	0.9700
C16—C17	1.441 (3)	C51—H51B	0.9700
C17—C18	1.370 (3)	C52—C53	1.516 (3)
C18—C19	1.398 (3)	C52—H52A	0.9700
C18—H18	0.9300	C52—H52B	0.9700
C20—C21	1.513 (3)	C53—H53A	0.9700
C20—H20A	0.9700	C53—H53B	0.9700
C20—H20B	0.9700	C54—H54A	0.9600
C21—C22	1.521 (4)	C54—H54B	0.9600
C21—H21A	0.9700	C54—H54C	0.9600
C21—H21B	0.9700	C55—H55A	0.9600
C22—C23	1.507 (3)	C55—H55B	0.9600
C22—H22A	0.9700	C55—H55C	0.9600
C22—H22B	0.9700	C56—H56A	0.9600
C23—C24	1.510 (3)	C56—H56B	0.9600
C23—H23A	0.9700	C56—H56C	0.9600
C23—H23B	0.9700	C57—C58	1.491 (4)
C24—H24A	0.9700	C57—H57A	0.9600
C24—H24B	0.9700	C57—H57B	0.9600
C25—H25A	0.9600	C57—H57C	0.9600
C25—H25B	0.9600	C58—H58A	0.9700
C25—H25C	0.9600	C58—H58B	0.9700
C9—O1—C29	117.0 (2)	C29—C28—H28C	109.5
C19—O2—C8	117.89 (16)	H28A—C28—H28C	109.5
C38—O3—C58	116.7 (2)	H28B—C28—H28C	109.5
C48—O4—C37	118.00 (15)	O1—C29—C28	107.7 (3)
C1—N1—C8	107.94 (18)	O1—C29—H29A	110.2
C1—N1—C25	120.9 (2)	C28—C29—H29A	110.2
C8—N1—C25	120.01 (19)	O1—C29—H29B	110.2
C9—N2—C10	116.4 (2)	C28—C29—H29B	110.2
C17—N3—C24	115.64 (17)	H29A—C29—H29B	108.5
C17—N3—C20	112.34 (16)	C31—C30—C35	121.4 (2)
C24—N3—C20	110.51 (18)	C31—C30—N4	128.3 (2)
C30—N4—C37	107.82 (16)	C35—C30—N4	110.22 (18)
C30—N4—C54	120.69 (19)	C32—C31—C30	117.9 (3)
C37—N4—C54	120.64 (18)	C32—C31—H31	121.1
C38—N5—C39	116.60 (19)	C30—C31—H31	121.1
C46—N6—C53	116.00 (17)	C33—C32—C31	121.5 (3)
C46—N6—C49	112.02 (16)	C33—C32—H32	119.2
C53—N6—C49	110.25 (19)	C31—C32—H32	119.2
C2—C1—C6	121.1 (3)	C32—C33—C34	120.3 (3)
C2—C1—N1	129.0 (3)	C32—C33—H33	119.8
C6—C1—N1	109.9 (2)	C34—C33—H33	119.8
C3—C2—C1	119.0 (3)	C35—C34—C33	118.5 (3)
C3—C2—H2	120.5	C35—C34—H34	120.8
C1—C2—H2	120.5	C33—C34—H34	120.8
C2—C3—C4	121.0 (3)	C34—C35—C30	120.3 (2)
C2—C3—H3	119.5	C34—C35—C36	131.0 (2)
C4—C3—H3	119.5	C30—C35—C36	108.67 (19)
C3—C4—C5	121.1 (3)	C35—C36—C55	114.0 (2)
C3—C4—H4	119.5	C35—C36—C56	109.58 (19)
C5—C4—H4	119.5	C55—C36—C56	108.69 (18)
C6—C5—C4	117.6 (3)	C35—C36—C37	99.76 (16)
C6—C5—H5	121.2	C55—C36—C37	113.74 (18)
C4—C5—H5	121.2	C56—C36—C37	110.82 (19)
C5—C6—C1	120.2 (3)	N4—C37—O4	106.32 (16)
C5—C6—C7	130.5 (3)	N4—C37—C38	113.99 (17)
C1—C6—C7	109.3 (2)	O4—C37—C38	107.41 (17)
C6—C7—C26	114.9 (2)	N4—C37—C36	103.63 (17)
C6—C7—C27	109.22 (19)	O4—C37—C36	109.08 (16)
C26—C7—C27	108.7 (2)	C38—C37—C36	115.97 (17)
C6—C7—C8	99.07 (17)	N5—C38—O3	121.5 (2)
C26—C7—C8	113.56 (18)	N5—C38—C37	126.5 (2)
C27—C7—C8	111.1 (2)	O3—C38—C37	112.06 (19)
N1—C8—O2	106.47 (17)	C48—C39—N5	121.26 (18)
N1—C8—C9	113.74 (19)	C48—C39—C40	118.9 (2)
O2—C8—C9	107.43 (16)	N5—C39—C40	119.71 (19)
N1—C8—C7	103.95 (16)	C41—C40—C45	118.8 (2)
O2—C8—C7	109.84 (17)	C41—C40—C39	122.0 (2)
C9—C8—C7	115.08 (18)	C45—C40—C39	119.13 (19)
N2—C9—O1	121.7 (2)	C42—C41—C40	121.2 (3)
N2—C9—C8	126.4 (2)	C42—C41—H41	119.4
O1—C9—C8	111.9 (2)	C40—C41—H41	119.4
C19—C10—N2	120.9 (2)	C41—C42—C43	120.3 (2)
C19—C10—C11	118.7 (2)	C41—C42—H42	119.8
N2—C10—C11	120.4 (2)	C43—C42—H42	119.8
C12—C11—C16	118.5 (2)	C44—C43—C42	120.8 (2)
C12—C11—C10	121.4 (2)	C44—C43—H43	119.6
C16—C11—C10	120.0 (2)	C42—C43—H43	119.6
C13—C12—C11	121.2 (2)	C43—C44—C45	120.7 (2)
C13—C12—H12	119.4	C43—C44—H44	119.7
C11—C12—H12	119.4	C45—C44—H44	119.7
C12—C13—C14	120.2 (2)	C44—C45—C40	118.2 (2)
C12—C13—H13	119.9	C44—C45—C46	122.2 (2)
C14—C13—H13	119.9	C40—C45—C46	119.56 (18)
C15—C14—C13	120.3 (2)	C47—C46—N6	122.62 (19)
C15—C14—H14	119.9	C47—C46—C45	119.33 (19)
C13—C14—H14	119.9	N6—C46—C45	118.04 (18)
C14—C15—C16	121.1 (2)	C46—C47—C48	120.24 (19)
C14—C15—H15	119.5	C46—C47—H47	119.9
C16—C15—H15	119.5	C48—C47—H47	119.9
C15—C16—C11	118.6 (2)	C39—C48—O4	120.56 (18)
C15—C16—C17	122.2 (2)	C39—C48—C47	122.66 (19)
C11—C16—C17	119.10 (19)	O4—C48—C47	116.64 (18)
C18—C17—N3	122.8 (2)	N6—C49—C50	110.58 (19)
C18—C17—C16	119.01 (19)	N6—C49—H49A	109.5
N3—C17—C16	118.23 (19)	C50—C49—H49A	109.5
C17—C18—C19	121.0 (2)	N6—C49—H49B	109.5
C17—C18—H18	119.5	C50—C49—H49B	109.5
C19—C18—H18	119.5	H49A—C49—H49B	108.1
O2—C19—C10	120.78 (19)	C49—C50—C51	110.5 (2)
O2—C19—C18	117.15 (19)	C49—C50—H50A	109.6
C10—C19—C18	122.0 (2)	C51—C50—H50A	109.6
N3—C20—C21	110.79 (19)	C49—C50—H50B	109.6
N3—C20—H20A	109.5	C51—C50—H50B	109.6
C21—C20—H20A	109.5	H50A—C50—H50B	108.1
N3—C20—H20B	109.5	C50—C51—C52	110.5 (2)
C21—C20—H20B	109.5	C50—C51—H51A	109.6
H20A—C20—H20B	108.1	C52—C51—H51A	109.6
C20—C21—C22	110.8 (2)	C50—C51—H51B	109.6
C20—C21—H21A	109.5	C52—C51—H51B	109.6
C22—C21—H21A	109.5	H51A—C51—H51B	108.1
C20—C21—H21B	109.5	C53—C52—C51	110.3 (2)
C22—C21—H21B	109.5	C53—C52—H52A	109.6
H21A—C21—H21B	108.1	C51—C52—H52A	109.6
C23—C22—C21	110.2 (2)	C53—C52—H52B	109.6
C23—C22—H22A	109.6	C51—C52—H52B	109.6
C21—C22—H22A	109.6	H52A—C52—H52B	108.1
C23—C22—H22B	109.6	N6—C53—C52	110.36 (19)
C21—C22—H22B	109.6	N6—C53—H53A	109.6
H22A—C22—H22B	108.1	C52—C53—H53A	109.6
C22—C23—C24	111.1 (2)	N6—C53—H53B	109.6
C22—C23—H23A	109.4	C52—C53—H53B	109.6
C24—C23—H23A	109.4	H53A—C53—H53B	108.1
C22—C23—H23B	109.4	N4—C54—H54A	109.5
C24—C23—H23B	109.4	N4—C54—H54B	109.5
H23A—C23—H23B	108.0	H54A—C54—H54B	109.5
N3—C24—C23	110.4 (2)	N4—C54—H54C	109.5
N3—C24—H24A	109.6	H54A—C54—H54C	109.5
C23—C24—H24A	109.6	H54B—C54—H54C	109.5
N3—C24—H24B	109.6	C36—C55—H55A	109.5
C23—C24—H24B	109.6	C36—C55—H55B	109.5
H24A—C24—H24B	108.1	H55A—C55—H55B	109.5
N1—C25—H25A	109.5	C36—C55—H55C	109.5
N1—C25—H25B	109.5	H55A—C55—H55C	109.5
H25A—C25—H25B	109.5	H55B—C55—H55C	109.5
N1—C25—H25C	109.5	C36—C56—H56A	109.5
H25A—C25—H25C	109.5	C36—C56—H56B	109.5
H25B—C25—H25C	109.5	H56A—C56—H56B	109.5
C7—C26—H26A	109.5	C36—C56—H56C	109.5
C7—C26—H26B	109.5	H56A—C56—H56C	109.5
H26A—C26—H26B	109.5	H56B—C56—H56C	109.5
C7—C26—H26C	109.5	C58—C57—H57A	109.5
H26A—C26—H26C	109.5	C58—C57—H57B	109.5
H26B—C26—H26C	109.5	H57A—C57—H57B	109.5
C7—C27—H27A	109.5	C58—C57—H57C	109.5
C7—C27—H27B	109.5	H57A—C57—H57C	109.5
H27A—C27—H27B	109.5	H57B—C57—H57C	109.5
C7—C27—H27C	109.5	O3—C58—C57	107.2 (3)
H27A—C27—H27C	109.5	O3—C58—H58A	110.3
H27B—C27—H27C	109.5	C57—C58—H58A	110.3
C29—C28—H28A	109.5	O3—C58—H58B	110.3
C29—C28—H28B	109.5	C57—C58—H58B	110.3
H28A—C28—H28B	109.5	H58A—C58—H58B	108.5
C8—N1—C1—C2	−161.3 (3)	C37—N4—C30—C31	−161.7 (2)
C25—N1—C1—C2	−17.6 (4)	C54—N4—C30—C31	−17.3 (4)
C8—N1—C1—C6	18.7 (3)	C37—N4—C30—C35	19.2 (3)
C25—N1—C1—C6	162.4 (2)	C54—N4—C30—C35	163.6 (2)
C6—C1—C2—C3	0.4 (5)	C35—C30—C31—C32	−0.2 (4)
N1—C1—C2—C3	−179.5 (3)	N4—C30—C31—C32	−179.3 (3)
C1—C2—C3—C4	−0.8 (6)	C30—C31—C32—C33	0.0 (6)
C2—C3—C4—C5	0.2 (7)	C31—C32—C33—C34	−0.2 (6)
C3—C4—C5—C6	0.7 (6)	C32—C33—C34—C35	0.5 (6)
C4—C5—C6—C1	−1.1 (5)	C33—C34—C35—C30	−0.7 (5)
C4—C5—C6—C7	177.0 (3)	C33—C34—C35—C36	177.2 (3)
C2—C1—C6—C5	0.6 (4)	C31—C30—C35—C34	0.6 (4)
N1—C1—C6—C5	−179.5 (2)	N4—C30—C35—C34	179.8 (2)
C2—C1—C6—C7	−177.9 (2)	C31—C30—C35—C36	−177.8 (2)
N1—C1—C6—C7	2.0 (3)	N4—C30—C35—C36	1.5 (3)
C5—C6—C7—C26	41.2 (4)	C34—C35—C36—C55	41.3 (4)
C1—C6—C7—C26	−140.6 (2)	C30—C35—C36—C55	−140.6 (2)
C5—C6—C7—C27	−81.2 (4)	C34—C35—C36—C56	−80.8 (3)
C1—C6—C7—C27	97.0 (2)	C30—C35—C36—C56	97.3 (2)
C5—C6—C7—C8	162.5 (3)	C34—C35—C36—C37	162.9 (3)
C1—C6—C7—C8	−19.2 (2)	C30—C35—C36—C37	−19.0 (2)
C1—N1—C8—O2	85.60 (19)	C30—N4—C37—O4	84.3 (2)
C25—N1—C8—O2	−58.5 (3)	C54—N4—C37—O4	−60.1 (2)
C1—N1—C8—C9	−156.29 (18)	C30—N4—C37—C38	−157.53 (19)
C25—N1—C8—C9	59.6 (3)	C54—N4—C37—C38	58.0 (3)
C1—N1—C8—C7	−30.4 (2)	C30—N4—C37—C36	−30.6 (2)
C25—N1—C8—C7	−174.5 (2)	C54—N4—C37—C36	−175.0 (2)
C19—O2—C8—N1	157.65 (16)	C48—O4—C37—N4	157.23 (16)
C19—O2—C8—C9	35.4 (2)	C48—O4—C37—C38	34.8 (2)
C19—O2—C8—C7	−90.4 (2)	C48—O4—C37—C36	−91.6 (2)
C6—C7—C8—N1	29.3 (2)	C35—C36—C37—N4	29.3 (2)
C26—C7—C8—N1	151.6 (2)	C55—C36—C37—N4	151.12 (19)
C27—C7—C8—N1	−85.5 (2)	C56—C36—C37—N4	−86.1 (2)
C6—C7—C8—O2	−84.3 (2)	C35—C36—C37—O4	−83.59 (19)
C26—C7—C8—O2	38.0 (2)	C55—C36—C37—O4	38.2 (2)
C27—C7—C8—O2	160.95 (18)	C56—C36—C37—O4	160.99 (17)
C6—C7—C8—C9	154.36 (19)	C35—C36—C37—C38	155.04 (18)
C26—C7—C8—C9	−83.3 (2)	C55—C36—C37—C38	−83.2 (2)
C27—C7—C8—C9	39.6 (2)	C56—C36—C37—C38	39.6 (2)
C10—N2—C9—O1	−175.2 (2)	C39—N5—C38—O3	−175.41 (19)
C10—N2—C9—C8	5.7 (3)	C39—N5—C38—C37	5.3 (3)
C29—O1—C9—N2	−0.7 (4)	C58—O3—C38—N5	−0.4 (3)
C29—O1—C9—C8	178.5 (2)	C58—O3—C38—C37	179.0 (2)
N1—C8—C9—N2	−146.3 (2)	N4—C37—C38—N5	−144.9 (2)
O2—C8—C9—N2	−28.7 (3)	O4—C37—C38—N5	−27.4 (3)
C7—C8—C9—N2	93.9 (3)	C36—C37—C38—N5	94.8 (3)
N1—C8—C9—O1	34.5 (3)	N4—C37—C38—O3	35.7 (3)
O2—C8—C9—O1	152.09 (18)	O4—C37—C38—O3	153.25 (17)
C7—C8—C9—O1	−85.3 (2)	C36—C37—C38—O3	−84.5 (2)
C9—N2—C10—C19	12.3 (3)	C38—N5—C39—C48	11.3 (3)
C9—N2—C10—C11	−170.2 (2)	C38—N5—C39—C40	−172.09 (19)
C19—C10—C11—C12	−176.99 (19)	C48—C39—C40—C41	−177.59 (19)
N2—C10—C11—C12	5.5 (3)	N5—C39—C40—C41	5.7 (3)
C19—C10—C11—C16	1.1 (3)	C48—C39—C40—C45	1.0 (3)
N2—C10—C11—C16	−176.46 (17)	N5—C39—C40—C45	−175.77 (18)
C16—C11—C12—C13	−2.2 (3)	C45—C40—C41—C42	−1.7 (3)
C10—C11—C12—C13	175.9 (2)	C39—C40—C41—C42	176.8 (2)
C11—C12—C13—C14	0.2 (3)	C40—C41—C42—C43	0.2 (4)
C12—C13—C14—C15	1.4 (4)	C41—C42—C43—C44	0.8 (4)
C13—C14—C15—C16	−0.9 (3)	C42—C43—C44—C45	−0.2 (4)
C14—C15—C16—C11	−1.1 (3)	C43—C44—C45—C40	−1.3 (3)
C14—C15—C16—C17	−179.15 (19)	C43—C44—C45—C46	179.9 (2)
C12—C11—C16—C15	2.6 (3)	C41—C40—C45—C44	2.2 (3)
C10—C11—C16—C15	−175.50 (18)	C39—C40—C45—C44	−176.41 (18)
C12—C11—C16—C17	−179.29 (17)	C41—C40—C45—C46	−178.97 (18)
C10—C11—C16—C17	2.6 (3)	C39—C40—C45—C46	2.4 (3)
C24—N3—C17—C18	−24.0 (3)	C53—N6—C46—C47	−23.2 (3)
C20—N3—C17—C18	104.1 (2)	C49—N6—C46—C47	104.6 (2)
C24—N3—C17—C16	154.97 (18)	C53—N6—C46—C45	155.63 (17)
C20—N3—C17—C16	−76.9 (2)	C49—N6—C46—C45	−76.6 (2)
C15—C16—C17—C18	174.30 (18)	C44—C45—C46—C47	174.77 (19)
C11—C16—C17—C18	−3.7 (3)	C40—C45—C46—C47	−4.0 (3)
C15—C16—C17—N3	−4.7 (3)	C44—C45—C46—N6	−4.1 (3)
C11—C16—C17—N3	177.25 (16)	C40—C45—C46—N6	177.08 (17)
N3—C17—C18—C19	−179.81 (16)	N6—C46—C47—C48	−178.95 (17)
C16—C17—C18—C19	1.2 (3)	C45—C46—C47—C48	2.2 (3)
C8—O2—C19—C10	−23.0 (3)	N5—C39—C48—O4	−1.8 (3)
C8—O2—C19—C18	159.57 (17)	C40—C39—C48—O4	−178.51 (17)
N2—C10—C19—O2	−3.5 (3)	N5—C39—C48—C47	173.78 (18)
C11—C10—C19—O2	178.95 (17)	C40—C39—C48—C47	−2.9 (3)
N2—C10—C19—C18	173.80 (17)	C37—O4—C48—C39	−23.7 (2)
C11—C10—C19—C18	−3.7 (3)	C37—O4—C48—C47	160.42 (16)
C17—C18—C19—O2	−179.98 (17)	C46—C47—C48—C39	1.3 (3)
C17—C18—C19—C10	2.6 (3)	C46—C47—C48—O4	177.08 (17)
C17—N3—C20—C21	169.1 (2)	C46—N6—C49—C50	168.2 (2)
C24—N3—C20—C21	−60.1 (3)	C53—N6—C49—C50	−61.0 (2)
N3—C20—C21—C22	56.2 (3)	N6—C49—C50—C51	57.0 (3)
C20—C21—C22—C23	−53.0 (3)	C49—C50—C51—C52	−53.9 (3)
C21—C22—C23—C24	53.8 (3)	C50—C51—C52—C53	54.1 (3)
C17—N3—C24—C23	−170.32 (17)	C46—N6—C53—C52	−170.09 (18)
C20—N3—C24—C23	60.7 (2)	C49—N6—C53—C52	61.3 (2)
C22—C23—C24—N3	−57.9 (3)	C51—C52—C53—N6	−58.0 (3)
C9—O1—C29—C28	174.0 (2)	C38—O3—C58—C57	177.4 (2)