A new photochromic tetra­hydro­indolizine

The title compound, di­methyl 10b'-(4-fluoro­styryl)-8',9'-di­methoxy-4-nitro-5',6'-di­hydrospiro­[9H-fluorene-9,1'(10b'H)-pyrrolo­[2,1-a]­iso­quinoline]-2',3'-di­carboxyl­ate, C₃₈H₃₁FN₂O₈, is a new photochromic tetra­hydro­indolizine. One of the C-C bonds at the spiro C atom is very long [1.630 (2) Å], thus explaining the photochromic behaviour.

S1. Comment

Photochromism, one of the most noticeable phenomena of photochemistry, which involves light-induced reversible transformation of a molecule between two states with different distinguishable absorption spectra, has attracted increasing interest in recent years. Amongst the many known photochromic systems, photochromic tetrahydroindolizines (THIs; Dürr et al., 1983) have received particular attention owing to their remarkable photofatigue resistence and the range of photochromic properties that they possess (Tan et al., 2001).

We report here the structue of the title compound, (I) (Fig. 1) (Tan et al., 2001). The photochromic properties of (I) have been studied by laser flash photolysis [308 nm; the maximum full width at middle height (fwmh) is 20 ns (Jian et al., 1991)], which shows that there are three transients.

All the THI regions [i.e. the fluorene, ester and dihydroisoquinoline groups, denoted A, B and C (Dürr et al., 1983)] are clearly present. The molecule comprises seven rings, denoted D, E, F, G, H, I and J (see scheme). The dihedral angles between these planes are 80.11 (14) (D/E; plane through C2, C3 and C4), 42.31 (16) [E (plane through C2, C3 and C4)/F (plane through C1, C5, C10 and C11), 79.48 (14) [E (plane through C2, C3 and C4)/H], 40.52 (7) (H/I), 37.72 (7) (H/J) and 2.85 (3)° (I/J).

The bonds and dihedral angles of the C3—C2—C1—N1 fragment show clearly that the dihydroisoquinoline region is not planar, the C1/N1/C12 and N1/C12/C11 planes making angles of, respectively, 11.56 (13)° below and 47.76 (13)° above the C1/C5/C10/C11 plane. The vertical distances between atom N1 and the C1/C5/C10/C11 plane, and between atom C12 and the C1/C5/C10/C11 plane, are 0.096 (3) and 0.600 (3) Å, respectively. The pyrroline ring is also not planar, the plane through atoms C1, N1 and C4 being 11.56 (13)° above, and the plane through N1, sp³-hybridized C1 and C2 being 21.91 (10)° above the C2/C3/C4 plane. The vertical distances between atom N1 and the C2/C3/C4 plane, and between atom C1 and the C2/C3/C4 plane, are 0.168 (4) and 0.449 (5) Å, respectively. Atoms N1, C3 and C4 all exhibit planar coordination.

The bond lengths (Table 1) in the non-aromatic portion of the molecule show clear evidence of bond fixation, most of the single- and double-bond distances being typical of their types (Dorweiler et al., 1985). However, the C1—C2 bond is significantly longer than a typical single bond between four-connected C atoms. This lengthening may be due to the spiro-concatenation on C2. This effect is also shown by a MINDO/3 calculation in the spiro-azanonatriene system ((Dorweiler et al., 1988). This long bond is relatively weak and is easily cleaved by UV light, leading to ring opening (Dorweiler et al., 1988).

The C2—C23 and C2—C34 bonds are ca 0.06 Å longer than the corrsponding bonds in the unsubstituted fluorene molecule (Burns & Hall, 1954). They are, however, in good agreement with those in bisfluorene systems (Neupert-Laes & Dobler, 1981). The C23—C2—C34 angle is almost identical to those found in bisfluorenes and spiro-linked systems (Ege et al., 1981).

S2. Experimental

The title compound, (I), was synthesized as described by Tan et al. (2001). Recrystallization from dichloromethane–ether solution gave yellow prisms of (I) (m.p. 448–450 K).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 10% probability level.

dimethyl 10b'-(4-fluorostyryl)-8',9'-dimethoxy-4-nitro-5',6'-dihydro-spiro[9H- fluorene-9,1'(10b'H)-pyrrolo[2,1-a]isoquinoline]-2',3'-dicarboxylate

Crystal data

C38H31FN2O8	F(000) = 1384
Mr = 662.65	Dx = 1.351 Mg m^−3
MONOCLINIC, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6208 reflections
a = 12.2895 (16) Å	θ = 2.3–26.8°
b = 20.015 (3) Å	µ = 0.10 mm^−1
c = 13.4042 (18) Å	T = 298 K
β = 98.739 (2)°	Prism, yellow
V = 3258.8 (8) Å^3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	6400 independent reflections
Radiation source: fine-focus sealed tube	4837 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→10
Tmin = 0.962, Tmax = 0.981	k = −24→24
14831 measured reflections	l = −16→16

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)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0831P)^2 + 0.2767P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.014
6400 reflections	Δρmax = 0.48 e Å^−3
447 parameters	Δρmin = −0.25 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: 0.0088 (9)

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
F1	0.3715 (2)	−0.07142 (10)	0.38067 (19)	0.1560 (10)
N1	0.13174 (11)	0.27379 (8)	0.61325 (11)	0.0395 (4)
N2	0.17940 (16)	0.54469 (10)	0.72109 (15)	0.0642 (5)
O1	0.45098 (10)	0.44908 (6)	0.41767 (10)	0.0453 (3)
O2	0.27302 (11)	0.51678 (7)	0.35152 (10)	0.0543 (4)
O3	0.20694 (17)	0.60217 (9)	0.7099 (2)	0.1072 (8)
O4	0.08452 (15)	0.52841 (10)	0.72176 (17)	0.0975 (7)
O5	0.32026 (11)	0.29583 (8)	0.93543 (10)	0.0566 (4)
O6	0.15590 (11)	0.24502 (8)	0.91979 (9)	0.0563 (4)
O7	−0.04992 (12)	0.28166 (8)	0.76151 (14)	0.0683 (5)
O8	−0.00211 (9)	0.17923 (6)	0.71812 (10)	0.0450 (3)
C1	0.24502 (13)	0.28762 (8)	0.59700 (12)	0.0339 (4)
C2	0.30456 (12)	0.30471 (8)	0.71124 (12)	0.0319 (4)
C3	0.22253 (13)	0.27437 (8)	0.77303 (12)	0.0335 (4)
C4	0.12617 (13)	0.26350 (8)	0.71161 (12)	0.0344 (4)
C5	0.24632 (13)	0.34658 (8)	0.52512 (12)	0.0334 (4)
C6	0.34786 (13)	0.36864 (9)	0.50196 (12)	0.0355 (4)
H6	0.4113	0.3448	0.5263	0.043*
C7	0.35580 (14)	0.42469 (9)	0.44402 (13)	0.0371 (4)
C8	0.25929 (15)	0.46056 (9)	0.40716 (13)	0.0410 (4)
C9	0.16005 (14)	0.43762 (10)	0.42719 (14)	0.0431 (4)
H9	0.0964	0.4609	0.4014	0.052*
C10	0.15113 (13)	0.38022 (9)	0.48527 (13)	0.0378 (4)
C11	0.03847 (14)	0.35631 (10)	0.50146 (15)	0.0470 (5)
H11A	0.0134	0.3825	0.5544	0.056*
H11B	−0.0133	0.3627	0.4400	0.056*
C12	0.04175 (14)	0.28339 (10)	0.53044 (14)	0.0440 (4)
H12A	−0.0275	0.2704	0.5512	0.053*
H12B	0.0533	0.2561	0.4732	0.053*
C13	0.55041 (15)	0.41623 (10)	0.45945 (16)	0.0500 (5)
H13A	0.5550	0.4140	0.5315	0.075*
H13B	0.6122	0.4408	0.4426	0.075*
H13C	0.5509	0.3718	0.4324	0.075*
C14	0.1883 (2)	0.56543 (12)	0.3465 (2)	0.0779 (8)
H14A	0.1218	0.5479	0.3086	0.117*
H14B	0.2100	0.6049	0.3140	0.117*
H14C	0.1757	0.5764	0.4135	0.117*
C15	0.29176 (15)	0.22565 (9)	0.55389 (13)	0.0395 (4)
H15	0.3591	0.2298	0.5308	0.047*
C16	0.24431 (17)	0.16624 (9)	0.54662 (14)	0.0472 (5)
H16	0.1787	0.1629	0.5729	0.057*
C17	0.28167 (19)	0.10508 (10)	0.50260 (15)	0.0549 (5)
C18	0.2213 (2)	0.04692 (12)	0.50706 (19)	0.0752 (7)
H18	0.1584	0.0482	0.5377	0.090*
C19	0.2514 (3)	−0.01269 (14)	0.4675 (3)	0.0998 (10)
H19	0.2109	−0.0514	0.4728	0.120*
C20	0.3413 (4)	−0.01327 (15)	0.4210 (3)	0.1013 (11)
C21	0.4042 (3)	0.04191 (16)	0.4146 (2)	0.0947 (9)
H21	0.4668	0.0395	0.3834	0.114*
C22	0.3745 (2)	0.10199 (13)	0.45488 (19)	0.0722 (7)
H22	0.4166	0.1401	0.4500	0.087*
C23	0.42494 (13)	0.28281 (8)	0.73462 (12)	0.0326 (4)
C24	0.47051 (15)	0.21956 (9)	0.73820 (13)	0.0410 (4)
H24	0.4260	0.1820	0.7251	0.049*
C25	0.58436 (15)	0.21315 (10)	0.76187 (14)	0.0459 (5)
H25	0.6159	0.1708	0.7641	0.055*
C26	0.65137 (15)	0.26837 (11)	0.78215 (14)	0.0474 (5)
H26	0.7272	0.2629	0.7975	0.057*
C27	0.60647 (14)	0.33151 (10)	0.77980 (13)	0.0423 (4)
H27	0.6513	0.3688	0.7940	0.051*
C28	0.49324 (13)	0.33857 (8)	0.75588 (12)	0.0345 (4)
C29	0.42580 (13)	0.39880 (8)	0.75151 (12)	0.0341 (4)
C30	0.45536 (15)	0.46548 (9)	0.76487 (14)	0.0443 (4)
H30	0.5290	0.4776	0.7803	0.053*
C31	0.37401 (16)	0.51340 (10)	0.75497 (15)	0.0475 (5)
H31	0.3919	0.5585	0.7620	0.057*
C32	0.26501 (15)	0.49335 (9)	0.73431 (14)	0.0433 (4)
C33	0.23293 (14)	0.42697 (9)	0.72277 (13)	0.0385 (4)
H33	0.1590	0.4149	0.7113	0.046*
C34	0.31515 (13)	0.37985 (8)	0.72904 (12)	0.0329 (4)
C35	0.24083 (14)	0.27307 (9)	0.88194 (13)	0.0384 (4)
C36	0.1594 (2)	0.25083 (14)	1.02722 (15)	0.0713 (7)
H36A	0.2230	0.2279	1.0611	0.107*
H36B	0.0942	0.2313	1.0462	0.107*
H36C	0.1633	0.2971	1.0460	0.107*
C37	0.01561 (14)	0.24369 (9)	0.73665 (13)	0.0370 (4)
C38	−0.11209 (16)	0.15487 (11)	0.72289 (19)	0.0618 (6)
H38A	−0.1339	0.1680	0.7859	0.093*
H38B	−0.1129	0.1070	0.7179	0.093*
H38C	−0.1624	0.1734	0.6681	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.222 (3)	0.0742 (13)	0.166 (2)	0.0406 (14)	0.0133 (18)	−0.0555 (13)
N1	0.0308 (7)	0.0492 (9)	0.0380 (8)	−0.0096 (6)	0.0040 (6)	0.0005 (7)
N2	0.0622 (13)	0.0468 (12)	0.0804 (13)	0.0162 (9)	0.0002 (10)	−0.0093 (9)
O1	0.0377 (7)	0.0439 (7)	0.0566 (8)	−0.0011 (5)	0.0144 (6)	0.0108 (6)
O2	0.0497 (8)	0.0468 (8)	0.0672 (9)	0.0060 (6)	0.0115 (7)	0.0215 (7)
O3	0.0975 (15)	0.0374 (10)	0.185 (2)	0.0203 (9)	0.0159 (14)	−0.0024 (12)
O4	0.0506 (11)	0.0768 (13)	0.159 (2)	0.0209 (9)	−0.0023 (11)	−0.0079 (12)
O5	0.0427 (8)	0.0807 (11)	0.0438 (7)	−0.0139 (7)	−0.0019 (6)	0.0032 (7)
O6	0.0626 (9)	0.0714 (10)	0.0371 (7)	−0.0304 (7)	0.0149 (6)	−0.0031 (6)
O7	0.0495 (9)	0.0566 (10)	0.1054 (13)	−0.0024 (7)	0.0332 (8)	−0.0174 (9)
O8	0.0348 (7)	0.0372 (7)	0.0637 (8)	−0.0081 (5)	0.0091 (6)	0.0017 (6)
C1	0.0283 (8)	0.0379 (10)	0.0355 (8)	−0.0059 (7)	0.0053 (6)	−0.0009 (7)
C2	0.0283 (8)	0.0318 (9)	0.0357 (8)	−0.0020 (7)	0.0049 (6)	0.0013 (7)
C3	0.0311 (8)	0.0319 (9)	0.0379 (9)	−0.0033 (7)	0.0065 (7)	0.0005 (7)
C4	0.0351 (9)	0.0294 (9)	0.0398 (9)	−0.0030 (7)	0.0092 (7)	−0.0001 (7)
C5	0.0335 (9)	0.0345 (9)	0.0320 (8)	−0.0015 (7)	0.0047 (6)	−0.0025 (7)
C6	0.0332 (9)	0.0367 (10)	0.0371 (9)	0.0028 (7)	0.0073 (7)	0.0014 (7)
C7	0.0374 (9)	0.0381 (10)	0.0370 (9)	−0.0023 (7)	0.0102 (7)	−0.0026 (7)
C8	0.0447 (10)	0.0383 (10)	0.0396 (9)	0.0010 (8)	0.0049 (7)	0.0050 (8)
C9	0.0351 (9)	0.0460 (11)	0.0461 (10)	0.0047 (8)	−0.0003 (7)	0.0045 (8)
C10	0.0335 (9)	0.0426 (10)	0.0368 (9)	−0.0015 (7)	0.0042 (7)	−0.0017 (8)
C11	0.0321 (9)	0.0579 (13)	0.0499 (11)	−0.0006 (8)	0.0026 (8)	0.0042 (9)
C12	0.0323 (9)	0.0570 (12)	0.0412 (10)	−0.0114 (8)	0.0005 (7)	−0.0004 (9)
C13	0.0380 (10)	0.0506 (12)	0.0634 (12)	0.0005 (9)	0.0143 (9)	0.0066 (10)
C14	0.0654 (15)	0.0572 (15)	0.113 (2)	0.0159 (12)	0.0206 (14)	0.0364 (14)
C15	0.0411 (10)	0.0393 (10)	0.0377 (9)	−0.0022 (8)	0.0049 (7)	0.0003 (7)
C16	0.0550 (12)	0.0421 (11)	0.0438 (10)	−0.0064 (9)	0.0053 (8)	−0.0012 (8)
C17	0.0762 (15)	0.0406 (11)	0.0442 (11)	0.0010 (10)	−0.0030 (10)	−0.0032 (9)
C18	0.108 (2)	0.0493 (14)	0.0666 (15)	−0.0164 (13)	0.0086 (14)	−0.0101 (11)
C19	0.153 (3)	0.0460 (16)	0.095 (2)	−0.0113 (18)	0.002 (2)	−0.0190 (15)
C20	0.151 (3)	0.0527 (18)	0.093 (2)	0.0250 (19)	−0.003 (2)	−0.0270 (16)
C21	0.109 (2)	0.078 (2)	0.097 (2)	0.0287 (18)	0.0148 (17)	−0.0215 (17)
C22	0.0835 (17)	0.0547 (15)	0.0780 (16)	0.0092 (12)	0.0106 (13)	−0.0112 (12)
C23	0.0305 (8)	0.0351 (9)	0.0322 (8)	0.0006 (7)	0.0046 (6)	0.0029 (7)
C24	0.0435 (10)	0.0371 (10)	0.0422 (10)	0.0017 (8)	0.0057 (8)	0.0054 (8)
C25	0.0466 (11)	0.0480 (11)	0.0440 (10)	0.0173 (9)	0.0095 (8)	0.0055 (8)
C26	0.0337 (9)	0.0649 (14)	0.0434 (10)	0.0098 (9)	0.0048 (8)	−0.0010 (9)
C27	0.0293 (9)	0.0544 (12)	0.0432 (10)	−0.0026 (8)	0.0061 (7)	−0.0043 (8)
C28	0.0312 (8)	0.0389 (10)	0.0338 (8)	−0.0014 (7)	0.0064 (6)	−0.0004 (7)
C29	0.0329 (8)	0.0350 (9)	0.0345 (8)	−0.0039 (7)	0.0052 (7)	−0.0007 (7)
C30	0.0389 (10)	0.0390 (10)	0.0543 (11)	−0.0091 (8)	0.0048 (8)	−0.0042 (8)
C31	0.0540 (12)	0.0326 (10)	0.0561 (11)	−0.0059 (8)	0.0086 (9)	−0.0058 (8)
C32	0.0473 (11)	0.0362 (10)	0.0452 (10)	0.0081 (8)	0.0033 (8)	−0.0045 (8)
C33	0.0321 (9)	0.0411 (10)	0.0411 (9)	0.0011 (7)	0.0018 (7)	−0.0037 (8)
C34	0.0321 (8)	0.0349 (9)	0.0317 (8)	−0.0032 (7)	0.0046 (6)	0.0000 (7)
C35	0.0388 (9)	0.0380 (10)	0.0388 (9)	−0.0024 (8)	0.0075 (8)	0.0026 (7)
C36	0.0868 (17)	0.0893 (19)	0.0418 (11)	−0.0339 (14)	0.0229 (11)	−0.0056 (11)
C37	0.0339 (9)	0.0383 (10)	0.0392 (9)	−0.0029 (8)	0.0074 (7)	−0.0002 (7)
C38	0.0374 (11)	0.0574 (14)	0.0897 (16)	−0.0150 (9)	0.0065 (10)	0.0161 (12)

Geometric parameters (Å, º)

F1—C20	1.359 (3)	C14—H14A	0.9600
N1—C1	1.468 (2)	C14—H14B	0.9600
N1—C4	1.347 (2)	C14—H14C	0.9600
N1—C12	1.456 (2)	C15—C16	1.321 (2)
N2—O4	1.212 (2)	C15—H15	0.9300
N2—O3	1.215 (3)	C16—C17	1.463 (3)
N2—C32	1.462 (2)	C16—H16	0.9300
O1—C7	1.363 (2)	C17—C18	1.387 (3)
O1—C13	1.425 (2)	C17—C22	1.391 (3)
O2—C8	1.375 (2)	C18—C19	1.379 (4)
O2—C14	1.420 (3)	C18—H18	0.9300
O5—C35	1.209 (2)	C19—C20	1.348 (5)
O6—C35	1.350 (2)	C19—H19	0.9300
O6—C36	1.439 (2)	C20—C21	1.358 (5)
O7—C37	1.191 (2)	C21—C22	1.390 (4)
O8—C37	1.326 (2)	C21—H21	0.9300
O8—C38	1.447 (2)	C22—H22	0.9300
C1—C2	1.630 (2)	C23—C24	1.382 (2)
C1—C5	1.525 (2)	C23—C28	1.400 (2)
C1—C15	1.518 (2)	C24—C25	1.393 (3)
C2—C3	1.525 (2)	C24—H24	0.9300
C2—C23	1.529 (2)	C25—C26	1.380 (3)
C2—C34	1.525 (2)	C25—H25	0.9300
C3—C4	1.353 (2)	C26—C27	1.377 (3)
C3—C35	1.443 (2)	C26—H26	0.9300
C4—C37	1.501 (2)	C27—C28	1.387 (2)
C5—C10	1.385 (2)	C27—H27	0.9300
C5—C6	1.402 (2)	C28—C29	1.459 (2)
C6—C7	1.376 (2)	C29—C30	1.388 (2)
C6—H6	0.9300	C29—C34	1.400 (2)
C7—C8	1.410 (2)	C30—C31	1.377 (3)
C8—C9	1.367 (3)	C30—H30	0.9300
C9—C10	1.401 (3)	C31—C32	1.385 (3)
C9—H9	0.9300	C31—H31	0.9300
C10—C11	1.511 (2)	C32—C33	1.388 (3)
C11—C12	1.509 (3)	C33—C34	1.375 (2)
C11—H11A	0.9700	C33—H33	0.9300
C11—H11B	0.9700	C36—H36A	0.9600
C12—H12A	0.9700	C36—H36B	0.9600
C12—H12B	0.9700	C36—H36C	0.9600
C13—H13A	0.9600	C38—H38A	0.9600
C13—H13B	0.9600	C38—H38B	0.9600
C13—H13C	0.9600	C38—H38C	0.9600
C4—N1—C12	128.39 (14)	C15—C16—H16	115.8
C4—N1—C1	111.39 (13)	C17—C16—H16	115.8
C12—N1—C1	119.33 (14)	C18—C17—C22	117.6 (2)
O4—N2—O3	122.8 (2)	C18—C17—C16	118.8 (2)
O4—N2—C32	119.05 (19)	C22—C17—C16	123.5 (2)
O3—N2—C32	118.1 (2)	C19—C18—C17	122.2 (3)
C7—O1—C13	116.83 (14)	C19—C18—H18	118.9
C8—O2—C14	115.95 (15)	C17—C18—H18	118.9
C35—O6—C36	115.81 (15)	C20—C19—C18	118.2 (3)
C37—O8—C38	116.59 (15)	C20—C19—H19	120.9
N1—C1—C15	108.95 (13)	C18—C19—H19	120.9
N1—C1—C5	109.93 (13)	C19—C20—F1	118.9 (4)
C15—C1—C5	110.55 (13)	C19—C20—C21	122.5 (3)
N1—C1—C2	101.58 (12)	F1—C20—C21	118.6 (4)
C15—C1—C2	112.79 (13)	C20—C21—C22	119.5 (3)
C5—C1—C2	112.63 (13)	C20—C21—H21	120.3
C1—C2—C3	100.79 (12)	C22—C21—H21	120.3
C1—C2—C23	114.50 (13)	C21—C22—C17	120.0 (3)
C1—C2—C34	111.68 (13)	C21—C22—H22	120.0
C3—C2—C23	118.26 (13)	C17—C22—H22	120.0
C3—C2—C34	110.82 (13)	C24—C23—C28	119.73 (15)
C23—C2—C34	101.17 (12)	C24—C23—C2	130.09 (15)
C4—C3—C35	126.87 (15)	C28—C23—C2	110.17 (14)
C4—C3—C2	108.86 (14)	C23—C24—C25	118.69 (17)
C35—C3—C2	122.85 (14)	C23—C24—H24	120.7
N1—C4—C3	113.65 (14)	C25—C24—H24	120.7
N1—C4—C37	116.21 (14)	C26—C25—C24	121.31 (17)
C3—C4—C37	130.13 (16)	C26—C25—H25	119.3
C10—C5—C6	119.31 (15)	C24—C25—H25	119.3
C10—C5—C1	122.05 (15)	C27—C26—C25	120.34 (17)
C6—C5—C1	118.60 (14)	C27—C26—H26	119.8
C7—C6—C5	121.56 (15)	C25—C26—H26	119.8
C7—C6—H6	119.2	C26—C27—C28	118.90 (18)
C5—C6—H6	119.2	C26—C27—H27	120.6
O1—C7—C6	125.13 (15)	C28—C27—H27	120.6
O1—C7—C8	115.87 (15)	C27—C28—C23	121.03 (16)
C6—C7—C8	119.00 (15)	C27—C28—C29	129.60 (16)
C9—C8—O2	124.62 (16)	C23—C28—C29	109.34 (14)
C9—C8—C7	119.22 (16)	C30—C29—C34	121.00 (16)
O2—C8—C7	116.16 (15)	C30—C29—C28	130.80 (16)
C8—C9—C10	122.12 (16)	C34—C29—C28	108.19 (14)
C8—C9—H9	118.9	C31—C30—C29	119.04 (17)
C10—C9—H9	118.9	C31—C30—H30	120.5
C5—C10—C9	118.70 (15)	C29—C30—H30	120.5
C5—C10—C11	121.96 (16)	C30—C31—C32	118.90 (17)
C9—C10—C11	119.34 (15)	C30—C31—H31	120.6
C12—C11—C10	110.72 (15)	C32—C31—H31	120.6
C12—C11—H11A	109.5	C31—C32—C33	123.32 (17)
C10—C11—H11A	109.5	C31—C32—N2	118.48 (17)
C12—C11—H11B	109.5	C33—C32—N2	118.18 (17)
C10—C11—H11B	109.5	C34—C33—C32	117.13 (16)
H11A—C11—H11B	108.1	C34—C33—H33	121.4
N1—C12—C11	108.14 (14)	C32—C33—H33	121.4
N1—C12—H12A	110.1	C33—C34—C29	120.54 (16)
C11—C12—H12A	110.1	C33—C34—C2	128.47 (15)
N1—C12—H12B	110.1	C29—C34—C2	110.97 (14)
C11—C12—H12B	110.1	O5—C35—O6	122.31 (16)
H12A—C12—H12B	108.4	O5—C35—C3	125.50 (16)
O1—C13—H13A	109.5	O6—C35—C3	112.15 (14)
O1—C13—H13B	109.5	O6—C36—H36A	109.5
H13A—C13—H13B	109.5	O6—C36—H36B	109.5
O1—C13—H13C	109.5	H36A—C36—H36B	109.5
H13A—C13—H13C	109.5	O6—C36—H36C	109.5
H13B—C13—H13C	109.5	H36A—C36—H36C	109.5
O2—C14—H14A	109.5	H36B—C36—H36C	109.5
O2—C14—H14B	109.5	O7—C37—O8	125.07 (16)
H14A—C14—H14B	109.5	O7—C37—C4	124.57 (17)
O2—C14—H14C	109.5	O8—C37—C4	110.09 (14)
H14A—C14—H14C	109.5	O8—C38—H38A	109.5
H14B—C14—H14C	109.5	O8—C38—H38B	109.5
C16—C15—C1	125.11 (17)	H38A—C38—H38B	109.5
C16—C15—H15	117.4	O8—C38—H38C	109.5
C1—C15—H15	117.4	H38A—C38—H38C	109.5
C15—C16—C17	128.4 (2)	H38B—C38—H38C	109.5