(1R,6R,13R,18R)-(Z,Z)-1,18-Bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-3,16-dimethyl-ene-8,20-diaza-dispiro-[5.6.5.6]tetra-cosa-7,19-diene.

The crystal structure of the title compound, C(34)H(54)N(2)O(4), has been solved in order to prove the relative and absolute chirality of the newly-formed stereocentres which were established using an asymmetric Diels-Alder reaction at an earlier stage in the synthesis. This unprecedented stable dialdimine contains a 14-membered ring and was obtained as the minor diastereoisomer in the Diels-Alder reaction. The absolute stereochemistry of the stereocentres of the acetal functionality was known to be R based on the use of a chiral (R)-tris-ubstituted dienophile derived from enanti-opure (S)-glyceraldehyde. The assignment of the configuration in the dienophile and the title di-aldimine differs from (S)-glyceraldehyde due to a change in the priority order of the substituents. The crystal structure establishes the presence of six stereocentres all attributed to be R. The 14-membered ring contains two aldimine bonds [C-N = 1.258 (2) and 1.259 (2) Å]. It adopts a similar conformation to that proposed for trans-trans-cyclo-tetra-deca-1,8-dienes.

Related literature

For related structures, see: Allmann (1974 ▶); Dale (1966 ▶). For background to the spiro­lide family, see: Gill et al. (2003 ▶); Guéret & Brimble (2010 ▶); Hu et al. (1995 ▶, 2001 ▶). For the applications of Danishefsky’s diene, see: Asano et al. (2006 ▶); Danishefsky et al. (1990 ▶); Petrzilka & Grayson (1981 ▶).

Experimental

Crystal data

C34H54N2O4

M = 554.80

Triclinic,

a = 6.8710 (1) Å

b = 10.1701 (2) Å

c = 11.7947 (2) Å

α = 79.143 (1)°

β = 88.043 (1)°

γ = 83.855 (1)°

V = 804.71 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.07 mm−1

T = 93 K

0.36 × 0.19 × 0.1 mm

Data collection

Siemens SMART CCD diffractometer

19146 measured reflections

3824 independent reflections

3555 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.091

S = 0.92

3824 reflections

365 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Siemens, 1995 ▶); cell refinement: SAINT (Siemens, 1995 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023998/dn2578sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023998/dn2578Isup2.hkl

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

C34H54N2O4	Z = 1
Mr = 554.80	F(000) = 304
Triclinic, P1	Dx = 1.145 Mg m−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8710 (1) Å	Cell parameters from 6455 reflections
b = 10.1701 (2) Å	θ = 1.8–27.9°
c = 11.7947 (2) Å	µ = 0.07 mm−1
α = 79.143 (1)°	T = 93 K
β = 88.043 (1)°	Needle, colourless
γ = 83.855 (1)°	0.36 × 0.19 × 0.1 mm
V = 804.71 (2) Å3

Siemens SMART CCD diffractometer	3555 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
graphite	θmax = 27.9°, θmin = 1.8°
ω scans	h = −9→9
19146 measured reflections	k = −13→13
3824 independent reflections	l = −15→15

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H-atom parameters constrained
S = 0.92	w = 1/[σ2(Fo2) + (0.0645P)2 + 0.1019P] where P = (Fo2 + 2Fc2)/3
3824 reflections	(Δ/σ)max < 0.001
365 parameters	Δρmax = 0.28 e Å−3
3 restraints	Δρmin = −0.18 e Å−3

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. Three restraints for a floating origins were used.

	x	y	z	Uiso*/Ueq
C5	0.4859 (3)	−0.46661 (18)	0.09602 (16)	0.0179 (3)
H1A	0.6114	−0.4649	0.0558	0.021*
H1B	0.5112	−0.4882	0.1782	0.021*
C4	0.3776 (3)	−0.57809 (18)	0.06285 (17)	0.0213 (4)
H2A	0.3781	−0.5684	−0.0206	0.026*
H2B	0.4463	−0.6650	0.0942	0.026*
C3	0.1690 (3)	−0.57332 (19)	0.10718 (17)	0.0220 (4)
C2	0.0573 (3)	−0.43578 (19)	0.07628 (17)	0.0203 (4)
H4A	−0.0731	−0.4383	0.1103	0.024*
H4B	0.0441	−0.4122	−0.0069	0.024*
C1	0.1606 (3)	−0.32679 (18)	0.11917 (16)	0.0157 (3)
H5	0.0887	−0.2394	0.0889	0.019*
C6	0.3720 (3)	−0.32518 (17)	0.06741 (15)	0.0154 (3)
C19	0.4921 (3)	−0.22460 (17)	0.11200 (15)	0.0168 (3)
H7A	0.5030	−0.2515	0.1951	0.020*
H7B	0.6233	−0.2327	0.0793	0.020*
C18	0.4100 (3)	−0.07590 (18)	0.08484 (16)	0.0181 (4)
H8A	0.4276	−0.0419	0.0030	0.022*
H8B	0.2705	−0.0689	0.1019	0.022*
C17	0.5083 (3)	0.01164 (19)	0.15356 (16)	0.0217 (4)
H9A	0.4320	0.0988	0.1453	0.026*
H9B	0.5053	−0.0297	0.2346	0.026*
C16	0.7199 (3)	0.03345 (19)	0.11786 (16)	0.0204 (4)
H10A	0.7725	0.0862	0.1679	0.024*
H10B	0.7985	−0.0529	0.1267	0.024*
C14	0.8639 (3)	0.05893 (18)	−0.06562 (16)	0.0172 (3)
H11	0.9483	−0.0144	−0.0314	0.021*
C13	0.8986 (3)	0.11417 (17)	−0.19270 (15)	0.0158 (3)
C12	0.8646 (3)	−0.00132 (17)	−0.25696 (15)	0.0166 (3)
H13A	0.8760	0.0318	−0.3393	0.020*
H13B	0.9680	−0.0739	−0.2363	0.020*
C11	0.6682 (3)	−0.05878 (18)	−0.23246 (16)	0.0185 (4)
H14A	0.5636	0.0120	−0.2564	0.022*
H14B	0.6535	−0.0900	−0.1500	0.022*
C10	0.6486 (3)	−0.17543 (19)	−0.29504 (16)	0.0211 (4)
H15A	0.6386	−0.1407	−0.3773	0.025*
H15B	0.7658	−0.2383	−0.2827	0.025*
C9	0.4705 (3)	−0.25019 (19)	−0.25415 (16)	0.0200 (4)
H16A	0.3527	−0.1878	−0.2649	0.024*
H16B	0.4596	−0.3191	−0.2997	0.024*
C7	0.3587 (3)	−0.27786 (17)	−0.06275 (15)	0.0168 (3)
H17	0.2497	−0.2210	−0.0922	0.020*
C24	1.1175 (3)	0.13759 (19)	−0.20847 (16)	0.0186 (4)
H24A	1.1966	0.0552	−0.1758	0.022*
H24B	1.1485	0.1584	−0.2903	0.022*
C23	1.1716 (3)	0.2520 (2)	−0.15120 (18)	0.0228 (4)
H19A	1.1577	0.2268	−0.0680	0.027*
H19B	1.3070	0.2674	−0.1692	0.027*
C22	1.0408 (3)	0.37918 (19)	−0.19363 (17)	0.0215 (4)
C21	0.8255 (3)	0.36185 (18)	−0.17768 (16)	0.0192 (4)
H21A	0.7500	0.4456	−0.2108	0.023*
H21B	0.7945	0.3424	−0.0958	0.023*
C20	0.7648 (3)	0.24717 (17)	−0.23484 (15)	0.0161 (3)
H22	0.6311	0.2313	−0.2085	0.019*
C25	0.0869 (4)	−0.6775 (2)	0.1672 (2)	0.0326 (5)
H23A	0.1591	−0.7612	0.1848	0.039*
H23B	−0.0430	−0.6667	0.1917	0.039*
C26	0.1524 (3)	−0.34631 (18)	0.25092 (15)	0.0177 (3)
H24	0.2561	−0.4151	0.2841	0.021*
C27	−0.0430 (3)	−0.3762 (2)	0.30981 (17)	0.0253 (4)
H25A	−0.1517	−0.3269	0.2644	0.030*
H25B	−0.0578	−0.4716	0.3225	0.030*
C28	0.0987 (3)	−0.2278 (2)	0.39969 (16)	0.0252 (4)
C29	−0.0117 (5)	−0.0934 (3)	0.4064 (2)	0.0448 (7)
H27A	−0.0607	−0.0939	0.4837	0.067*
H27B	−0.1193	−0.0765	0.3540	0.067*
H27C	0.0743	−0.0240	0.3858	0.067*
C30	0.2597 (4)	−0.2692 (3)	0.4873 (2)	0.0409 (6)
H28A	0.3296	−0.3527	0.4758	0.061*
H28B	0.2036	−0.2803	0.5637	0.061*
H28C	0.3482	−0.2009	0.4780	0.061*
C31	1.1091 (3)	0.4943 (2)	−0.2410 (2)	0.0293 (4)
H29A	1.2434	0.4991	−0.2492	0.035*
H29B	1.0228	0.5704	−0.2660	0.035*
C32	0.7610 (3)	0.28862 (18)	−0.36663 (16)	0.0186 (4)
H30	0.8924	0.2709	−0.3990	0.022*
C33	0.6765 (3)	0.4318 (2)	−0.41643 (17)	0.0232 (4)
H31A	0.5655	0.4606	−0.3708	0.028*
H31B	0.7745	0.4945	−0.4207	0.028*
C34	0.5546 (3)	0.28908 (19)	−0.52033 (16)	0.0232 (4)
C36	0.3332 (3)	0.2966 (2)	−0.5167 (2)	0.0309 (5)
H33A	0.2833	0.3430	−0.4564	0.046*
H33B	0.2935	0.2072	−0.5020	0.046*
H33C	0.2825	0.3443	−0.5895	0.046*
C35	0.6449 (4)	0.2274 (2)	−0.61933 (19)	0.0352 (5)
H34A	0.6040	0.1391	−0.6145	0.053*
H34B	0.7850	0.2209	−0.6152	0.053*
H34C	0.6031	0.2829	−0.6912	0.053*
N15	0.7312 (2)	0.10360 (16)	−0.00257 (14)	0.0188 (3)
N8	0.4889 (2)	−0.31236 (15)	−0.13220 (13)	0.0183 (3)
O1	−0.0310 (2)	−0.33110 (17)	0.41672 (13)	0.0323 (4)
O2	0.1763 (2)	−0.22053 (14)	0.28513 (11)	0.0225 (3)
O3	0.6256 (2)	0.21281 (14)	−0.41259 (12)	0.0250 (3)
O4	0.6178 (2)	0.42036 (14)	−0.52929 (12)	0.0261 (3)

	U11	U22	U33	U12	U13	U23
C5	0.0147 (8)	0.0156 (8)	0.0226 (9)	−0.0016 (7)	−0.0016 (7)	−0.0012 (7)
C4	0.0204 (9)	0.0150 (8)	0.0286 (10)	−0.0041 (7)	0.0015 (7)	−0.0036 (7)
C3	0.0213 (10)	0.0216 (9)	0.0257 (10)	−0.0065 (7)	−0.0005 (8)	−0.0081 (7)
C2	0.0145 (8)	0.0245 (9)	0.0235 (9)	−0.0059 (7)	−0.0016 (7)	−0.0066 (7)
C1	0.0120 (8)	0.0160 (7)	0.0190 (8)	−0.0015 (6)	−0.0016 (6)	−0.0026 (6)
C6	0.0138 (8)	0.0144 (8)	0.0181 (8)	−0.0028 (6)	−0.0007 (6)	−0.0023 (6)
C19	0.0152 (8)	0.0162 (8)	0.0191 (8)	−0.0026 (7)	−0.0017 (7)	−0.0029 (7)
C18	0.0173 (9)	0.0176 (8)	0.0189 (8)	−0.0023 (7)	0.0006 (7)	−0.0022 (7)
C17	0.0286 (10)	0.0175 (9)	0.0202 (9)	−0.0065 (7)	0.0057 (8)	−0.0050 (7)
C16	0.0259 (10)	0.0197 (8)	0.0172 (8)	−0.0076 (7)	0.0013 (7)	−0.0048 (7)
C14	0.0165 (9)	0.0162 (8)	0.0196 (8)	−0.0024 (7)	−0.0028 (7)	−0.0044 (7)
C13	0.0152 (9)	0.0155 (8)	0.0177 (8)	−0.0030 (6)	0.0009 (7)	−0.0049 (6)
C12	0.0167 (8)	0.0153 (8)	0.0179 (8)	−0.0023 (7)	0.0021 (7)	−0.0036 (6)
C11	0.0191 (9)	0.0166 (8)	0.0206 (8)	−0.0039 (7)	0.0023 (7)	−0.0046 (7)
C10	0.0237 (9)	0.0220 (9)	0.0198 (8)	−0.0078 (7)	0.0043 (7)	−0.0075 (7)
C9	0.0239 (9)	0.0202 (8)	0.0182 (8)	−0.0075 (7)	0.0004 (7)	−0.0064 (7)
C7	0.0163 (9)	0.0141 (8)	0.0199 (8)	−0.0021 (7)	−0.0027 (7)	−0.0020 (6)
C24	0.0131 (8)	0.0202 (9)	0.0230 (9)	−0.0020 (7)	0.0022 (7)	−0.0052 (7)
C23	0.0162 (9)	0.0232 (9)	0.0301 (10)	−0.0050 (7)	0.0022 (8)	−0.0068 (8)
C22	0.0226 (10)	0.0216 (9)	0.0226 (9)	−0.0061 (8)	0.0028 (7)	−0.0087 (7)
C21	0.0209 (9)	0.0147 (8)	0.0223 (9)	−0.0023 (7)	0.0024 (7)	−0.0046 (7)
C20	0.0145 (8)	0.0156 (8)	0.0180 (8)	−0.0030 (6)	0.0024 (6)	−0.0022 (6)
C25	0.0293 (11)	0.0237 (10)	0.0451 (13)	−0.0077 (8)	0.0085 (10)	−0.0061 (9)
C26	0.0191 (9)	0.0159 (8)	0.0176 (8)	−0.0039 (7)	−0.0003 (7)	−0.0008 (6)
C27	0.0243 (10)	0.0339 (11)	0.0185 (9)	−0.0090 (8)	0.0015 (8)	−0.0040 (8)
C28	0.0303 (11)	0.0298 (10)	0.0159 (8)	−0.0079 (8)	0.0021 (8)	−0.0032 (7)
C29	0.0646 (18)	0.0409 (13)	0.0276 (11)	0.0057 (12)	0.0111 (11)	−0.0115 (10)
C30	0.0420 (14)	0.0545 (15)	0.0261 (11)	−0.0148 (12)	−0.0092 (10)	0.0001 (10)
C31	0.0250 (10)	0.0236 (10)	0.0409 (12)	−0.0096 (8)	0.0057 (9)	−0.0073 (9)
C32	0.0189 (9)	0.0162 (8)	0.0205 (8)	−0.0044 (7)	0.0006 (7)	−0.0015 (6)
C33	0.0249 (10)	0.0201 (9)	0.0234 (9)	−0.0025 (8)	−0.0019 (8)	−0.0008 (7)
C34	0.0277 (10)	0.0212 (9)	0.0186 (9)	−0.0031 (8)	−0.0005 (8)	0.0025 (7)
C36	0.0266 (11)	0.0340 (11)	0.0306 (11)	−0.0048 (9)	−0.0026 (9)	−0.0005 (9)
C35	0.0470 (14)	0.0316 (11)	0.0243 (10)	0.0027 (10)	0.0038 (10)	−0.0028 (9)
N15	0.0205 (8)	0.0176 (7)	0.0186 (7)	−0.0051 (6)	0.0020 (6)	−0.0026 (6)
N8	0.0202 (8)	0.0151 (7)	0.0209 (7)	−0.0064 (6)	0.0011 (6)	−0.0044 (6)
O1	0.0334 (9)	0.0466 (10)	0.0200 (7)	−0.0171 (7)	0.0064 (6)	−0.0085 (7)
O2	0.0295 (8)	0.0223 (6)	0.0174 (6)	−0.0072 (6)	0.0051 (5)	−0.0067 (5)
O3	0.0331 (8)	0.0200 (6)	0.0213 (7)	−0.0086 (6)	−0.0082 (6)	0.0024 (5)
O4	0.0322 (8)	0.0218 (7)	0.0220 (7)	−0.0065 (6)	−0.0028 (6)	0.0039 (5)

C5—C4	1.536 (3)	C24—C23	1.535 (3)
C5—C6	1.546 (2)	C24—H24A	0.9700
C5—H1A	0.9700	C24—H24B	0.9700
C5—H1B	0.9700	C23—C22	1.506 (3)
C4—C3	1.507 (3)	C23—H19A	0.9700
C4—H2A	0.9700	C23—H19B	0.9700
C4—H2B	0.9700	C22—C31	1.326 (3)
C3—C25	1.327 (3)	C22—C21	1.509 (3)
C3—C2	1.509 (3)	C21—C20	1.552 (2)
C2—C1	1.547 (2)	C21—H21A	0.9700
C2—H4A	0.9700	C21—H21B	0.9700
C2—H4B	0.9700	C20—C32	1.532 (3)
C1—C26	1.529 (2)	C20—H22	0.9800
C1—C6	1.557 (2)	C25—H23A	0.9300
C1—H5	0.9800	C25—H23B	0.9300
C6—C7	1.523 (2)	C26—O2	1.439 (2)
C6—C19	1.554 (2)	C26—C27	1.523 (3)
C19—C18	1.535 (2)	C26—H24	0.9800
C19—H7A	0.9700	C27—O1	1.428 (2)
C19—H7B	0.9700	C27—H25A	0.9700
C18—C17	1.531 (3)	C27—H25B	0.9700
C18—H8A	0.9700	C28—O2	1.427 (2)
C18—H8B	0.9700	C28—O1	1.430 (3)
C17—C16	1.527 (3)	C28—C29	1.505 (3)
C17—H9A	0.9700	C28—C30	1.511 (3)
C17—H9B	0.9700	C29—H27A	0.9600
C16—N15	1.468 (2)	C29—H27B	0.9600
C16—H10A	0.9700	C29—H27C	0.9600
C16—H10B	0.9700	C30—H28A	0.9600
C14—N15	1.258 (2)	C30—H28B	0.9600
C14—C13	1.518 (2)	C30—H28C	0.9600
C14—H11	0.9300	C31—H29A	0.9300
C13—C24	1.547 (3)	C31—H29B	0.9300
C13—C12	1.554 (2)	C32—O3	1.449 (2)
C13—C20	1.560 (2)	C32—C33	1.524 (3)
C12—C11	1.525 (3)	C32—H30	0.9800
C12—H13A	0.9700	C33—O4	1.433 (2)
C12—H13B	0.9700	C33—H31A	0.9700
C11—C10	1.530 (2)	C33—H31B	0.9700
C11—H14A	0.9700	C34—O4	1.432 (2)
C11—H14B	0.9700	C34—O3	1.430 (2)
C10—C9	1.526 (3)	C34—C36	1.514 (3)
C10—H15A	0.9700	C34—C35	1.512 (3)
C10—H15B	0.9700	C36—H33A	0.9600
C9—N8	1.462 (2)	C36—H33B	0.9600
C9—H16A	0.9700	C36—H33C	0.9600
C9—H16B	0.9700	C35—H34A	0.9600
C7—N8	1.259 (2)	C35—H34B	0.9600
C7—H17	0.9300	C35—H34C	0.9600
C4—C5—C6	113.61 (15)	C23—C24—H24B	109.0
C4—C5—H1A	108.8	C13—C24—H24B	109.0
C6—C5—H1A	108.8	H24A—C24—H24B	107.8
C4—C5—H1B	108.8	C22—C23—C24	110.26 (16)
C6—C5—H1B	108.8	C22—C23—H19A	109.6
H1A—C5—H1B	107.7	C24—C23—H19A	109.6
C3—C4—C5	112.00 (16)	C22—C23—H19B	109.6
C3—C4—H2A	109.2	C24—C23—H19B	109.6
C5—C4—H2A	109.2	H19A—C23—H19B	108.1
C3—C4—H2B	109.2	C31—C22—C23	122.99 (19)
C5—C4—H2B	109.2	C31—C22—C21	123.65 (19)
H2A—C4—H2B	107.9	C23—C22—C21	113.35 (16)
C25—C3—C4	124.92 (19)	C22—C21—C20	112.61 (15)
C25—C3—C2	121.83 (19)	C22—C21—H21A	109.1
C4—C3—C2	113.25 (16)	C20—C21—H21A	109.1
C3—C2—C1	111.92 (15)	C22—C21—H21B	109.1
C3—C2—H4A	109.2	C20—C21—H21B	109.1
C1—C2—H4A	109.2	H21A—C21—H21B	107.8
C3—C2—H4B	109.2	C32—C20—C21	111.26 (15)
C1—C2—H4B	109.2	C32—C20—C13	113.04 (14)
H4A—C2—H4B	107.9	C21—C20—C13	110.28 (14)
C26—C1—C2	110.97 (15)	C32—C20—H22	107.3
C26—C1—C6	113.77 (14)	C21—C20—H22	107.3
C2—C1—C6	109.36 (14)	C13—C20—H22	107.3
C26—C1—H5	107.5	C3—C25—H23A	120.0
C2—C1—H5	107.5	C3—C25—H23B	120.0
C6—C1—H5	107.5	H23A—C25—H23B	120.0
C7—C6—C5	110.47 (14)	O2—C26—C27	100.21 (15)
C7—C6—C19	105.98 (14)	O2—C26—C1	109.10 (14)
C5—C6—C19	108.03 (14)	C27—C26—C1	117.03 (15)
C7—C6—C1	108.50 (14)	O2—C26—H24	110.0
C5—C6—C1	110.72 (14)	C27—C26—H24	110.0
C19—C6—C1	113.04 (14)	C1—C26—H24	110.0
C18—C19—C6	116.21 (14)	O1—C27—C26	102.98 (16)
C18—C19—H7A	108.2	O1—C27—H25A	111.2
C6—C19—H7A	108.2	C26—C27—H25A	111.2
C18—C19—H7B	108.2	O1—C27—H25B	111.2
C6—C19—H7B	108.2	C26—C27—H25B	111.2
H7A—C19—H7B	107.4	H25A—C27—H25B	109.1
C17—C18—C19	112.92 (15)	O2—C28—O1	106.40 (15)
C17—C18—H8A	109.0	O2—C28—C29	107.56 (17)
C19—C18—H8A	109.0	O1—C28—C29	110.7 (2)
C17—C18—H8B	109.0	O2—C28—C30	110.74 (19)
C19—C18—H8B	109.0	O1—C28—C30	107.89 (18)
H8A—C18—H8B	107.8	C29—C28—C30	113.4 (2)
C16—C17—C18	114.97 (15)	C28—C29—H27A	109.5
C16—C17—H9A	108.5	C28—C29—H27B	109.5
C18—C17—H9A	108.5	H27A—C29—H27B	109.5
C16—C17—H9B	108.5	C28—C29—H27C	109.5
C18—C17—H9B	108.5	H27A—C29—H27C	109.5
H9A—C17—H9B	107.5	H27B—C29—H27C	109.5
N15—C16—C17	110.75 (16)	C28—C30—H28A	109.5
N15—C16—H10A	109.5	C28—C30—H28B	109.5
C17—C16—H10A	109.5	H28A—C30—H28B	109.5
N15—C16—H10B	109.5	C28—C30—H28C	109.5
C17—C16—H10B	109.5	H28A—C30—H28C	109.5
H10A—C16—H10B	108.1	H28B—C30—H28C	109.5
N15—C14—C13	125.76 (16)	C22—C31—H29A	120.0
N15—C14—H11	117.1	C22—C31—H29B	120.0
C13—C14—H11	117.1	H29A—C31—H29B	120.0
C14—C13—C24	107.37 (14)	O3—C32—C33	100.30 (15)
C14—C13—C12	105.58 (14)	O3—C32—C20	109.32 (15)
C24—C13—C12	107.31 (14)	C33—C32—C20	117.28 (15)
C14—C13—C20	111.65 (14)	O3—C32—H30	109.8
C24—C13—C20	110.94 (14)	C33—C32—H30	109.8
C12—C13—C20	113.61 (14)	C20—C32—H30	109.8
C11—C12—C13	115.48 (15)	O4—C33—C32	102.53 (15)
C11—C12—H13A	108.4	O4—C33—H31A	111.3
C13—C12—H13A	108.4	C32—C33—H31A	111.3
C11—C12—H13B	108.4	O4—C33—H31B	111.3
C13—C12—H13B	108.4	C32—C33—H31B	111.3
H13A—C12—H13B	107.5	H31A—C33—H31B	109.2
C12—C11—C10	112.45 (15)	O4—C34—O3	106.23 (15)
C12—C11—H14A	109.1	O4—C34—C36	110.57 (17)
C10—C11—H14A	109.1	O3—C34—C36	108.03 (16)
C12—C11—H14B	109.1	O4—C34—C35	108.48 (17)
C10—C11—H14B	109.1	O3—C34—C35	110.33 (17)
H14A—C11—H14B	107.8	C36—C34—C35	112.99 (19)
C9—C10—C11	112.78 (16)	C34—C36—H33A	109.5
C9—C10—H15A	109.0	C34—C36—H33B	109.5
C11—C10—H15A	109.0	H33A—C36—H33B	109.5
C9—C10—H15B	109.0	C34—C36—H33C	109.5
C11—C10—H15B	109.0	H33A—C36—H33C	109.5
H15A—C10—H15B	107.8	H33B—C36—H33C	109.5
N8—C9—C10	110.21 (15)	C34—C35—H34A	109.5
N8—C9—H16A	109.6	C34—C35—H34B	109.5
C10—C9—H16A	109.6	H34A—C35—H34B	109.5
N8—C9—H16B	109.6	C34—C35—H34C	109.5
C10—C9—H16B	109.6	H34A—C35—H34C	109.5
H16A—C9—H16B	108.1	H34B—C35—H34C	109.5
N8—C7—C6	122.82 (16)	C14—N15—C16	117.19 (16)
N8—C7—H17	118.6	C7—N8—C9	118.06 (16)
C6—C7—H17	118.6	C27—O1—C28	107.81 (15)
C23—C24—C13	113.04 (15)	C28—O2—C26	107.24 (14)
C23—C24—H24A	109.0	C34—O3—C32	108.65 (14)
C13—C24—H24A	109.0	C34—O4—C33	107.11 (14)