8β-Acet-oxy-14α-benzo-yloxy-N-ethyl-3α,10β,13β,15α-tetra-hydr-oxy-1α,6α,16β-trimeth-oxy-4β-(methoxy-methyl-ene)aconitane: aconifine from Aconitum karakolicum Rapaics.

The title compound, C(34)H(47)NO(12), is the norditerpenoid alkaloid aconifine isolated from the leaves and tubers of Aconitum karakolicum Rapaics. It has a lycoctonine carbon skeleton and contains four six-membered rings and two five-membered rings; its geometry is similar to that observed in other lycoctonine-type diterpenoid alkaloids. There are two intra-molecular O-H⋯O hydrogen bonds which close five- and seven-membered pseudo-rings, respectively. In the crystal, two inter-molecular O-H⋯O hydrogen bonds cross-link the mol-ecules into double chains along the a axis.

Related literature

For the isolation of aconifine, see: Sultankhodzhaev et al. (1973 ▶). For spectroscopic data and the chemical structure of aconifine, see: Sultankhodzhaev et al. (1980 ▶). For the neurocardiotoxic activity of aconifine, see: Dzhakhangirov et al. (1997 ▶). For the neurocardiotoxic activity of lycoctonine alkaloids, see: Dzhakhangirov et al. (1976 ▶). For general background to lycoctonine alkaloids and their structures, see: Joshi & Pelletier (1987 ▶).

Experimental

Crystal data

C34H47NO12

M = 661.73

Orthorhombic,

a = 12.0213 (3) Å

b = 15.4938 (6) Å

c = 17.1038 (4) Å

V = 3185.68 (16) Å3

Z = 4

Cu Kα radiation

μ = 0.87 mm−1

T = 100 K

0.40 × 0.30 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer

Absorption correction: multi-scan (CrysAlisPro; Oxford Diffraction, 2009 ▶) T min = 0.767, T max = 0.811

11111 measured reflections

6334 independent reflections

6050 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.098

S = 1.06

6334 reflections

451 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 2633 Friedel pairs

Flack parameter: 0.04 (10)

Data collection: CrysAlisPro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021436/zl2215sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021436/zl2215Isup2.hkl

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

C34H47NO12	Dx = 1.380 Mg m−3
Mr = 661.73	Melting point: 472(2) K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11111 reflections
a = 12.0213 (3) Å	θ = 3.7–75.5°
b = 15.4938 (6) Å	µ = 0.87 mm−1
c = 17.1038 (4) Å	T = 100 K
V = 3185.68 (16) Å3	Prizmatic, colourless
Z = 4	0.40 × 0.30 × 0.25 mm
F(000) = 1416

Oxford Diffraction Xcalibur Ruby diffractometer	6334 independent reflections
Radiation source: Enhance (Cu) X-ray Source	6050 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 10.2576 pixels mm-1	θmax = 75.6°, θmin = 3.9°
ω scans	h = −15→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −19→19
Tmin = 0.767, Tmax = 0.811	l = −21→21
11111 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.0771P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.36 e Å−3
6334 reflections	Δρmin = −0.22 e Å−3
451 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.00043 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2633 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.04 (10)

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.

	x	y	z	Uiso*/Ueq
O1	0.66866 (9)	−0.16533 (7)	−0.10572 (6)	0.0176 (2)
O2	1.04961 (9)	−0.13201 (8)	−0.02826 (7)	0.0209 (2)
O3	0.98504 (9)	−0.08240 (8)	0.16387 (7)	0.0217 (2)
O4	0.82173 (10)	0.09161 (8)	0.13342 (7)	0.0232 (2)
O5	0.55172 (11)	0.23615 (8)	0.08471 (7)	0.0251 (3)
O6	0.53676 (9)	0.10653 (7)	0.14475 (6)	0.0171 (2)
O7	0.58835 (9)	−0.18623 (7)	0.09376 (6)	0.0175 (2)
O8	0.29051 (9)	−0.12191 (8)	−0.00458 (6)	0.0183 (2)
O9	0.33324 (9)	0.00330 (7)	0.12982 (6)	0.0162 (2)
O10	0.38215 (10)	−0.02601 (8)	0.25398 (6)	0.0234 (2)
O11	0.50108 (10)	0.13929 (8)	−0.04816 (7)	0.0213 (2)
O12	0.26888 (9)	0.04325 (8)	−0.02596 (7)	0.0210 (2)
N	0.79454 (11)	0.02206 (9)	−0.06929 (8)	0.0169 (3)
C1	0.73828 (12)	−0.16204 (9)	−0.03752 (8)	0.0145 (3)
H1A	0.7261	−0.2152	−0.0076	0.017*
C2	0.85921 (13)	−0.16088 (10)	−0.06393 (9)	0.0170 (3)
H2A	0.8792	−0.2176	−0.0834	0.020*
H2B	0.8673	−0.1202	−0.1066	0.020*
C3	0.93799 (12)	−0.13616 (10)	0.00116 (9)	0.0163 (3)
H3A	0.9347	−0.1807	0.0418	0.020*
C4	0.90603 (12)	−0.04888 (9)	0.03803 (9)	0.0157 (3)
C5	0.79025 (12)	−0.06011 (9)	0.07794 (8)	0.0143 (3)
H5A	0.7935	−0.1039	0.1192	0.017*
C6	0.74394 (13)	0.02751 (10)	0.11062 (9)	0.0170 (3)
H6A	0.6966	0.0146	0.1558	0.020*
C7	0.66856 (12)	0.06323 (9)	0.04426 (8)	0.0155 (3)
H7A	0.6874	0.1233	0.0320	0.019*
C8	0.54779 (12)	0.05540 (9)	0.07171 (8)	0.0147 (3)
C9	0.52897 (12)	−0.03713 (10)	0.10283 (8)	0.0140 (3)
H9A	0.5578	−0.0423	0.1562	0.017*
C10	0.58311 (13)	−0.10691 (9)	0.04910 (8)	0.0143 (3)
C11	0.70101 (12)	−0.08482 (10)	0.01411 (8)	0.0137 (3)
C12	0.49078 (12)	−0.12252 (10)	−0.01330 (8)	0.0147 (3)
H12A	0.5152	−0.1018	−0.0640	0.018*
H12B	0.4746	−0.1837	−0.0175	0.018*
C13	0.38627 (12)	−0.07295 (10)	0.01320 (8)	0.0156 (3)
C14	0.40634 (12)	−0.06253 (9)	0.10058 (8)	0.0151 (3)
H14A	0.3941	−0.1172	0.1281	0.018*
C15	0.45606 (12)	0.08664 (10)	0.01258 (8)	0.0157 (3)
H15A	0.4053	0.1236	0.0424	0.019*
C16	0.38277 (13)	0.01688 (10)	−0.02702 (8)	0.0167 (3)
H16A	0.4066	0.0104	−0.0815	0.020*
C17	0.69192 (12)	0.00319 (9)	−0.02677 (9)	0.0149 (3)
H17A	0.6284	0.0035	−0.0627	0.018*
C18	0.99741 (13)	−0.02636 (10)	0.09801 (9)	0.0177 (3)
H18A	1.0703	−0.0340	0.0747	0.021*
H18B	0.9902	0.0333	0.1143	0.021*
C19	0.89793 (13)	0.02424 (10)	−0.02277 (9)	0.0181 (3)
H19A	0.9025	0.0793	0.0041	0.022*
H19B	0.9610	0.0203	−0.0579	0.022*
C20	0.78363 (14)	0.09877 (11)	−0.11883 (10)	0.0221 (3)
H20A	0.7980	0.1499	−0.0878	0.026*
H20B	0.7080	0.1024	−0.1384	0.026*
C21	0.86362 (17)	0.09632 (14)	−0.18710 (11)	0.0345 (4)
H21A	0.8541	0.0433	−0.2153	0.052*
H21B	0.9386	0.1000	−0.1681	0.052*
H21C	0.8489	0.1442	−0.2213	0.052*
C22	0.65941 (14)	−0.24944 (10)	−0.13754 (9)	0.0204 (3)
H22A	0.7274	−0.2644	−0.1636	0.031*
H22B	0.5991	−0.2510	−0.1743	0.031*
H22C	0.6454	−0.2900	−0.0963	0.031*
C23	1.06760 (15)	−0.06738 (12)	0.22176 (10)	0.0264 (4)
H23A	1.0660	−0.0078	0.2371	0.040*
H23B	1.1396	−0.0811	0.2009	0.040*
H23C	1.0530	−0.1031	0.2665	0.040*
C24	0.84230 (16)	0.09095 (14)	0.21572 (11)	0.0320 (4)
H24A	0.7750	0.1051	0.2431	0.048*
H24B	0.8987	0.1327	0.2280	0.048*
H24C	0.8670	0.0346	0.2313	0.048*
C25	0.54687 (13)	0.19314 (10)	0.14337 (10)	0.0206 (3)
C26	0.55057 (18)	0.22808 (12)	0.22522 (11)	0.0316 (4)
H26A	0.6043	0.1964	0.2552	0.047*
H26B	0.4786	0.2223	0.2489	0.047*
H26C	0.5711	0.2879	0.2239	0.047*
C27	0.33426 (13)	0.01855 (10)	0.20752 (9)	0.0170 (3)
C28	0.26739 (12)	0.09676 (10)	0.22593 (9)	0.0170 (3)
C29	0.26246 (13)	0.12388 (11)	0.30387 (9)	0.0198 (3)
H29	0.3007	0.0937	0.3424	0.024*
C30	0.19980 (14)	0.19638 (11)	0.32318 (9)	0.0223 (3)
H30	0.1962	0.2147	0.3749	0.027*
C31	0.14270 (14)	0.24149 (10)	0.26579 (10)	0.0227 (3)
H31	0.1015	0.2902	0.2790	0.027*
C32	0.14703 (14)	0.21384 (11)	0.18828 (10)	0.0221 (3)
H32	0.1080	0.2437	0.1500	0.027*
C33	0.20932 (13)	0.14203 (11)	0.16821 (9)	0.0195 (3)
H33	0.2125	0.1239	0.1164	0.023*
C34	0.24229 (16)	0.10857 (13)	−0.08130 (11)	0.0303 (4)
H34A	0.2836	0.1600	−0.0694	0.045*
H34B	0.1641	0.1208	−0.0790	0.045*
H34C	0.2613	0.0890	−0.1329	0.045*
H2	1.061 (2)	−0.1796 (17)	−0.0539 (15)	0.032 (6)*
H7	0.640 (2)	−0.1782 (18)	0.1299 (17)	0.040 (7)*
H8	0.237 (2)	−0.0881 (15)	−0.0020 (13)	0.023 (5)*
H11	0.519 (2)	0.1832 (19)	−0.0238 (17)	0.041 (7)*

	U11	U22	U33	U12	U13	U23
O1	0.0172 (5)	0.0198 (5)	0.0158 (5)	0.0027 (4)	−0.0020 (4)	−0.0033 (4)
O2	0.0136 (5)	0.0231 (6)	0.0259 (5)	0.0012 (4)	0.0028 (4)	−0.0038 (5)
O3	0.0188 (5)	0.0242 (6)	0.0221 (5)	−0.0053 (5)	−0.0068 (4)	0.0021 (5)
O4	0.0197 (6)	0.0220 (5)	0.0280 (6)	−0.0039 (5)	−0.0034 (4)	−0.0074 (5)
O5	0.0278 (6)	0.0180 (5)	0.0294 (6)	−0.0022 (5)	0.0028 (5)	−0.0010 (5)
O6	0.0167 (5)	0.0162 (5)	0.0183 (5)	−0.0002 (4)	0.0021 (4)	−0.0033 (4)
O7	0.0168 (5)	0.0162 (5)	0.0196 (5)	−0.0005 (4)	−0.0001 (4)	0.0022 (4)
O8	0.0109 (5)	0.0204 (5)	0.0237 (5)	−0.0001 (5)	−0.0016 (4)	−0.0030 (4)
O9	0.0136 (5)	0.0195 (5)	0.0155 (5)	0.0026 (4)	0.0018 (4)	−0.0008 (4)
O10	0.0243 (6)	0.0280 (6)	0.0180 (5)	0.0066 (5)	0.0015 (4)	0.0020 (5)
O11	0.0229 (6)	0.0199 (5)	0.0210 (5)	0.0006 (5)	0.0027 (4)	0.0060 (5)
O12	0.0165 (5)	0.0228 (6)	0.0238 (5)	0.0051 (4)	−0.0029 (4)	0.0014 (5)
N	0.0148 (6)	0.0172 (6)	0.0188 (6)	0.0009 (5)	0.0032 (5)	0.0030 (5)
C1	0.0131 (7)	0.0155 (6)	0.0148 (6)	0.0004 (5)	−0.0011 (5)	−0.0012 (5)
C2	0.0146 (7)	0.0193 (7)	0.0171 (6)	0.0023 (6)	0.0007 (5)	−0.0032 (5)
C3	0.0115 (6)	0.0177 (7)	0.0197 (7)	0.0005 (5)	0.0006 (5)	−0.0006 (6)
C4	0.0112 (6)	0.0161 (7)	0.0199 (6)	−0.0009 (6)	0.0005 (5)	−0.0006 (5)
C5	0.0116 (6)	0.0149 (6)	0.0163 (6)	−0.0017 (5)	0.0005 (5)	−0.0002 (5)
C6	0.0134 (7)	0.0175 (7)	0.0201 (7)	−0.0005 (6)	0.0007 (5)	−0.0019 (5)
C7	0.0139 (7)	0.0149 (6)	0.0178 (6)	−0.0017 (5)	0.0012 (5)	−0.0004 (5)
C8	0.0144 (6)	0.0135 (6)	0.0163 (6)	−0.0002 (5)	−0.0002 (5)	−0.0019 (5)
C9	0.0128 (7)	0.0152 (6)	0.0140 (6)	−0.0012 (5)	0.0011 (5)	0.0001 (5)
C10	0.0136 (7)	0.0138 (6)	0.0153 (6)	−0.0004 (5)	0.0010 (5)	0.0006 (5)
C11	0.0106 (6)	0.0154 (6)	0.0152 (6)	0.0004 (5)	0.0006 (5)	−0.0001 (5)
C12	0.0113 (6)	0.0162 (7)	0.0167 (6)	0.0001 (5)	−0.0005 (5)	−0.0023 (5)
C13	0.0129 (6)	0.0170 (7)	0.0170 (6)	−0.0009 (6)	−0.0001 (5)	−0.0011 (5)
C14	0.0137 (7)	0.0149 (6)	0.0166 (6)	0.0005 (5)	0.0012 (5)	0.0015 (5)
C15	0.0153 (6)	0.0146 (6)	0.0173 (6)	0.0018 (6)	0.0015 (5)	0.0032 (5)
C16	0.0165 (7)	0.0184 (7)	0.0151 (6)	0.0032 (6)	−0.0005 (5)	−0.0008 (5)
C17	0.0124 (6)	0.0150 (6)	0.0173 (6)	0.0004 (5)	0.0010 (5)	−0.0006 (5)
C18	0.0138 (6)	0.0175 (7)	0.0217 (7)	−0.0024 (6)	−0.0002 (5)	−0.0017 (6)
C19	0.0146 (7)	0.0172 (7)	0.0225 (7)	−0.0010 (6)	0.0034 (6)	0.0022 (6)
C20	0.0224 (8)	0.0220 (8)	0.0217 (7)	0.0003 (6)	0.0033 (6)	0.0056 (6)
C21	0.0328 (10)	0.0407 (11)	0.0299 (9)	0.0001 (8)	0.0118 (8)	0.0116 (8)
C22	0.0215 (7)	0.0204 (7)	0.0194 (7)	−0.0025 (6)	−0.0008 (6)	−0.0023 (6)
C23	0.0236 (8)	0.0293 (9)	0.0263 (8)	−0.0067 (7)	−0.0086 (6)	0.0000 (7)
C24	0.0226 (8)	0.0441 (11)	0.0294 (9)	−0.0014 (8)	−0.0025 (6)	−0.0159 (8)
C25	0.0158 (7)	0.0168 (7)	0.0291 (8)	−0.0004 (6)	0.0020 (6)	−0.0034 (6)
C26	0.0426 (11)	0.0229 (8)	0.0293 (9)	0.0017 (8)	0.0006 (8)	−0.0095 (7)
C27	0.0155 (7)	0.0184 (7)	0.0171 (7)	−0.0026 (6)	0.0027 (5)	0.0007 (5)
C28	0.0131 (7)	0.0190 (7)	0.0190 (6)	−0.0017 (6)	0.0030 (5)	−0.0006 (6)
C29	0.0194 (7)	0.0213 (7)	0.0188 (7)	0.0001 (6)	0.0010 (5)	−0.0006 (6)
C30	0.0205 (8)	0.0246 (8)	0.0216 (7)	−0.0034 (7)	0.0036 (6)	−0.0048 (6)
C31	0.0217 (7)	0.0179 (7)	0.0287 (8)	0.0011 (6)	0.0053 (6)	−0.0042 (6)
C32	0.0207 (8)	0.0212 (8)	0.0245 (8)	0.0014 (6)	−0.0016 (6)	0.0024 (6)
C33	0.0192 (7)	0.0215 (7)	0.0178 (6)	−0.0017 (6)	0.0024 (5)	−0.0001 (6)
C34	0.0267 (9)	0.0285 (9)	0.0358 (9)	0.0051 (7)	−0.0108 (7)	0.0074 (8)

O1—C22	1.4167 (18)	C10—C11	1.5762 (19)
O1—C1	1.4365 (17)	C11—C17	1.536 (2)
O2—C3	1.4346 (17)	C12—C13	1.5406 (19)
O2—H2	0.87 (3)	C12—H12A	0.9700
O3—C23	1.4211 (19)	C12—H12B	0.9700
O3—C18	1.4301 (19)	C13—C14	1.5225 (19)
O4—C6	1.4187 (19)	C13—C16	1.553 (2)
O4—C24	1.429 (2)	C14—H14A	0.9800
O5—C25	1.206 (2)	C15—C16	1.550 (2)
O6—C25	1.3476 (19)	C15—H15A	0.9800
O6—C8	1.4852 (17)	C16—H16A	0.9800
O7—C10	1.4484 (17)	C17—H17A	0.9800
O7—H7	0.89 (3)	C18—H18A	0.9700
O8—C13	1.4118 (18)	C18—H18B	0.9700
O8—H8	0.83 (3)	C19—H19A	0.9700
O9—C27	1.3500 (17)	C19—H19B	0.9700
O9—C14	1.4362 (18)	C20—C21	1.513 (2)
O10—C27	1.200 (2)	C20—H20A	0.9700
O11—C15	1.4275 (18)	C20—H20B	0.9700
O11—H11	0.83 (3)	C21—H21A	0.9600
O12—C34	1.422 (2)	C21—H21B	0.9600
O12—C16	1.4289 (18)	C21—H21C	0.9600
N—C17	1.4615 (18)	C22—H22A	0.9600
N—C20	1.466 (2)	C22—H22B	0.9600
N—C19	1.476 (2)	C22—H22C	0.9600
C1—C2	1.522 (2)	C23—H23A	0.9600
C1—C11	1.553 (2)	C23—H23B	0.9600
C1—H1A	0.9800	C23—H23C	0.9600
C2—C3	1.511 (2)	C24—H24A	0.9600
C2—H2A	0.9700	C24—H24B	0.9600
C2—H2B	0.9700	C24—H24C	0.9600
C3—C4	1.541 (2)	C25—C26	1.502 (2)
C3—H3A	0.9800	C26—H26A	0.9600
C4—C19	1.541 (2)	C26—H26B	0.9600
C4—C18	1.543 (2)	C26—H26C	0.9600
C4—C5	1.5599 (19)	C27—C28	1.488 (2)
C5—C6	1.570 (2)	C28—C33	1.398 (2)
C5—C11	1.5778 (19)	C28—C29	1.399 (2)
C5—H5A	0.9800	C29—C30	1.392 (2)
C6—C7	1.554 (2)	C29—H29	0.9300
C6—H6A	0.9800	C30—C31	1.387 (3)
C7—C8	1.531 (2)	C30—H30	0.9300
C7—C17	1.5557 (19)	C31—C32	1.394 (2)
C7—H7A	0.9800	C31—H31	0.9300
C8—C9	1.546 (2)	C32—C33	1.384 (2)
C8—C15	1.573 (2)	C32—H32	0.9300
C9—C14	1.526 (2)	C33—H33	0.9300
C9—C10	1.561 (2)	C34—H34A	0.9600
C9—H9A	0.9800	C34—H34B	0.9600
C10—C12	1.5588 (19)	C34—H34C	0.9600
C22—O1—C1	112.97 (11)	O11—C15—C16	107.21 (12)
C3—O2—H2	107.0 (17)	O11—C15—C8	112.21 (12)
C23—O3—C18	112.14 (12)	C16—C15—C8	117.71 (12)
C6—O4—C24	112.32 (14)	O11—C15—H15A	106.3
C25—O6—C8	120.55 (12)	C16—C15—H15A	106.3
C10—O7—H7	106.2 (18)	C8—C15—H15A	106.3
C13—O8—H8	106.3 (16)	O12—C16—C15	109.86 (12)
C27—O9—C14	117.48 (12)	O12—C16—C13	106.06 (12)
C15—O11—H11	102 (2)	C15—C16—C13	114.58 (12)
C34—O12—C16	114.23 (13)	O12—C16—H16A	108.7
C17—N—C20	111.98 (12)	C15—C16—H16A	108.7
C17—N—C19	116.56 (12)	C13—C16—H16A	108.7
C20—N—C19	111.61 (12)	N—C17—C11	110.11 (11)
O1—C1—C2	108.40 (11)	N—C17—C7	114.92 (12)
O1—C1—C11	108.72 (11)	C11—C17—C7	100.84 (11)
C2—C1—C11	115.78 (12)	N—C17—H17A	110.2
O1—C1—H1A	107.9	C11—C17—H17A	110.2
C2—C1—H1A	107.9	C7—C17—H17A	110.2
C11—C1—H1A	107.9	O3—C18—C4	108.21 (12)
C3—C2—C1	112.51 (12)	O3—C18—H18A	110.1
C3—C2—H2A	109.1	C4—C18—H18A	110.1
C1—C2—H2A	109.1	O3—C18—H18B	110.1
C3—C2—H2B	109.1	C4—C18—H18B	110.1
C1—C2—H2B	109.1	H18A—C18—H18B	108.4
H2A—C2—H2B	107.8	N—C19—C4	113.58 (12)
O2—C3—C2	109.83 (12)	N—C19—H19A	108.8
O2—C3—C4	109.72 (12)	C4—C19—H19A	108.8
C2—C3—C4	111.57 (12)	N—C19—H19B	108.8
O2—C3—H3A	108.6	C4—C19—H19B	108.8
C2—C3—H3A	108.6	H19A—C19—H19B	107.7
C4—C3—H3A	108.6	N—C20—C21	111.65 (15)
C3—C4—C19	112.64 (12)	N—C20—H20A	109.3
C3—C4—C18	107.04 (12)	C21—C20—H20A	109.3
C19—C4—C18	109.11 (12)	N—C20—H20B	109.3
C3—C4—C5	107.68 (11)	C21—C20—H20B	109.3
C19—C4—C5	108.72 (12)	H20A—C20—H20B	108.0
C18—C4—C5	111.68 (12)	C20—C21—H21A	109.5
C4—C5—C6	112.07 (12)	C20—C21—H21B	109.5
C4—C5—C11	109.32 (11)	H21A—C21—H21B	109.5
C6—C5—C11	102.42 (11)	C20—C21—H21C	109.5
C4—C5—H5A	110.9	H21A—C21—H21C	109.5
C6—C5—H5A	110.9	H21B—C21—H21C	109.5
C11—C5—H5A	110.9	O1—C22—H22A	109.5
O4—C6—C7	109.63 (12)	O1—C22—H22B	109.5
O4—C6—C5	117.99 (12)	H22A—C22—H22B	109.5
C7—C6—C5	104.75 (12)	O1—C22—H22C	109.5
O4—C6—H6A	108.0	H22A—C22—H22C	109.5
C7—C6—H6A	108.0	H22B—C22—H22C	109.5
C5—C6—H6A	108.0	O3—C23—H23A	109.5
C8—C7—C6	107.51 (11)	O3—C23—H23B	109.5
C8—C7—C17	111.31 (12)	H23A—C23—H23B	109.5
C6—C7—C17	104.61 (12)	O3—C23—H23C	109.5
C8—C7—H7A	111.1	H23A—C23—H23C	109.5
C6—C7—H7A	111.1	H23B—C23—H23C	109.5
C17—C7—H7A	111.1	O4—C24—H24A	109.5
O6—C8—C7	107.49 (11)	O4—C24—H24B	109.5
O6—C8—C9	101.06 (11)	H24A—C24—H24B	109.5
C7—C8—C9	108.54 (12)	O4—C24—H24C	109.5
O6—C8—C15	108.32 (11)	H24A—C24—H24C	109.5
C7—C8—C15	116.32 (12)	H24B—C24—H24C	109.5
C9—C8—C15	113.84 (12)	O5—C25—O6	124.70 (15)
C14—C9—C8	111.83 (12)	O5—C25—C26	125.10 (15)
C14—C9—C10	102.08 (11)	O6—C25—C26	110.20 (14)
C8—C9—C10	112.24 (11)	C25—C26—H26A	109.5
C14—C9—H9A	110.1	C25—C26—H26B	109.5
C8—C9—H9A	110.1	H26A—C26—H26B	109.5
C10—C9—H9A	110.1	C25—C26—H26C	109.5
O7—C10—C12	105.10 (11)	H26A—C26—H26C	109.5
O7—C10—C9	107.18 (11)	H26B—C26—H26C	109.5
C12—C10—C9	102.33 (11)	O10—C27—O9	123.76 (14)
O7—C10—C11	110.21 (12)	O10—C27—C28	126.00 (14)
C12—C10—C11	114.45 (11)	O9—C27—C28	110.24 (13)
C9—C10—C11	116.62 (12)	C33—C28—C29	120.07 (14)
C17—C11—C1	116.46 (12)	C33—C28—C27	121.94 (14)
C17—C11—C10	107.55 (11)	C29—C28—C27	117.98 (14)
C1—C11—C10	107.94 (12)	C30—C29—C28	119.43 (15)
C17—C11—C5	98.50 (11)	C30—C29—H29	120.3
C1—C11—C5	112.60 (12)	C28—C29—H29	120.3
C10—C11—C5	113.66 (11)	C31—C30—C29	120.43 (15)
C13—C12—C10	107.57 (11)	C31—C30—H30	119.8
C13—C12—H12A	110.2	C29—C30—H30	119.8
C10—C12—H12A	110.2	C30—C31—C32	119.99 (15)
C13—C12—H12B	110.2	C30—C31—H31	120.0
C10—C12—H12B	110.2	C32—C31—H31	120.0
H12A—C12—H12B	108.5	C33—C32—C31	120.20 (15)
O8—C13—C14	113.43 (12)	C33—C32—H32	119.9
O8—C13—C12	109.50 (12)	C31—C32—H32	119.9
C14—C13—C12	102.26 (11)	C32—C33—C28	119.88 (14)
O8—C13—C16	111.35 (12)	C32—C33—H33	120.1
C14—C13—C16	110.12 (12)	C28—C33—H33	120.1
C12—C13—C16	109.79 (12)	O12—C34—H34A	109.5
O9—C14—C13	108.67 (11)	O12—C34—H34B	109.5
O9—C14—C9	113.52 (12)	H34A—C34—H34B	109.5
C13—C14—C9	101.84 (11)	O12—C34—H34C	109.5
O9—C14—H14A	110.8	H34A—C34—H34C	109.5
C13—C14—H14A	110.8	H34B—C34—H34C	109.5
C9—C14—H14A	110.8

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O5	0.83 (3)	2.07 (3)	2.791 (2)	146 (3)
O8—H8···O12	0.83 (3)	2.11 (3)	2.598 (2)	117 (3)
O2—H2···O7i	0.87 (3)	2.21 (3)	3.066 (2)	168 (3)
O8—H8···O2ii	0.83 (3)	2.39 (3)	2.928 (2)	123 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O5	0.83 (3)	2.07 (3)	2.791 (2)	146 (3)
O8—H8⋯O12	0.83 (3)	2.11 (3)	2.598 (2)	117 (3)
O2—H2⋯O7i	0.87 (3)	2.21 (3)	3.066 (2)	168 (3)
O8—H8⋯O2ii	0.83 (3)	2.39 (3)	2.928 (2)	123 (3)

Symmetry codes: (i) ; (ii) .