8β-Acet-oxy-14α-benzo-yloxy-N-methyl-13β,15α-dihy-droxy-1α,6α,16β-trimeth-oxy-4β-(meth-oxy-meth-yl)aconitane: hypaconitine isolated from 'fuzi'.

The title compound, C(33)H(45)NO(10), has an aconitine carbon skeleton with four six-membered rings and two five-membered rings. The five-membered rings adopt envelope configurations and the six-membered N-containing heterocyclic ring displays a chair conformation. Two intra-molecular O-H⋯O hydrogen bonds occur.

Related literature

The title compound is an aconitine-type C19-diterpenoid alkaloid, which is isolated from the roots of Aconitum carmichaeli Debx., known as fuzi. For reviews of diterpenoid alkaloids, see Wang et al. (2009 ▶, 2010 ▶); Wang & Chen (2010 ▶). For the chemical structure of the title compound established from NMR and MS data, see: Pelletier et al. (1984 ▶). For the crystal structures of related C19-diterpenoid alkaloids, see: Gao et al. (2010 ▶); Tashkhodjaev & Sultankhodjaev (2009 ▶); He et al. (2008 ▶). For the absolute configuration of aconitine-type diterpenoid alkaloids, see: Pelletier & Djarmati (1976 ▶); Tsuda & Marion (1963 ▶); Zhapova et al. (1986 ▶).

Experimental

Crystal data

C33H45NO10

M = 615.70

Orthorhombic,

a = 12.457 (2) Å

b = 15.689 (3) Å

c = 15.771 (3) Å

V = 3082.3 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 113 K

0.32 × 0.29 × 0.21 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.969, T max = 0.980

28410 measured reflections

4094 independent reflections

3805 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.083

S = 1.02

4094 reflections

406 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP03 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810039887/ng5034sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039887/ng5034Isup2.hkl

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

C33H45NO10	F(000) = 1320
Mr = 615.70	Dx = 1.327 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11109 reflections
a = 12.457 (2) Å	θ = 1.3–27.9°
b = 15.689 (3) Å	µ = 0.10 mm−1
c = 15.771 (3) Å	T = 113 K
V = 3082.3 (10) Å3	Block, colourless
Z = 4	0.32 × 0.29 × 0.21 mm

Rigaku Saturn CCD area-detector diffractometer	4094 independent reflections
Radiation source: rotating anode	3805 reflections with I > 2σ(I)
multiplayer	Rint = 0.040
Detector resolution: 14.63 pixels mm-1	θmax = 27.9°, θmin = 1.8°
ω and φ scans	h = −16→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −20→20
Tmin = 0.969, Tmax = 0.980	l = −20→20
28410 measured reflections

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) = 0.083	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0542P)2] where P = (Fo2 + 2Fc2)/3
4094 reflections	(Δ/σ)max < 0.001
406 parameters	Δρmax = 0.25 e Å−3
3 restraints	Δρmin = −0.21 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.23858 (11)	0.89466 (8)	0.31289 (9)	0.0302 (3)
O2	1.07598 (11)	0.84457 (8)	0.13939 (9)	0.0302 (3)
O3	0.91073 (10)	0.62972 (8)	0.42341 (8)	0.0256 (3)
O4	0.79646 (10)	0.87205 (8)	0.12467 (8)	0.0224 (3)
O5	0.80028 (12)	0.78668 (9)	0.00869 (8)	0.0314 (3)
O6	0.66939 (11)	1.02025 (8)	0.23958 (11)	0.0381 (4)
O7	0.60560 (10)	0.88599 (8)	0.23532 (8)	0.0245 (3)
O8	0.74141 (11)	0.66278 (8)	0.12664 (9)	0.0278 (3)
H8	0.7649	0.6749	0.0782	0.042*
O9	0.52663 (10)	0.71641 (9)	0.22035 (8)	0.0286 (3)
O10	0.55459 (10)	0.76257 (9)	0.37461 (9)	0.0302 (3)
H10O	0.5011	0.7562	0.3428	0.045*
N1	1.03362 (12)	0.64061 (9)	0.23693 (10)	0.0228 (3)
C1	0.98310 (14)	0.69978 (11)	0.41053 (11)	0.0216 (4)
H1	0.9735	0.7401	0.4591	0.026*
C2	1.09733 (14)	0.66559 (12)	0.41484 (12)	0.0252 (4)
H2A	1.1154	0.6519	0.4744	0.030*
H2B	1.1023	0.6124	0.3814	0.030*
C3	1.17712 (15)	0.72968 (12)	0.38090 (12)	0.0254 (4)
H3A	1.2493	0.7033	0.3798	0.030*
H3B	1.1800	0.7792	0.4198	0.030*
C4	1.14877 (14)	0.76100 (12)	0.29144 (11)	0.0226 (4)
C5	1.04062 (14)	0.80980 (11)	0.29511 (11)	0.0213 (4)
H5	1.0466	0.8612	0.3323	0.026*
C6	0.99822 (14)	0.83478 (12)	0.20478 (11)	0.0222 (4)
H6	0.9574	0.8894	0.2099	0.027*
C7	0.91787 (14)	0.76308 (11)	0.18088 (11)	0.0208 (4)
H7	0.9326	0.7409	0.1226	0.025*
C8	0.80427 (15)	0.80051 (11)	0.18664 (11)	0.0206 (4)
C9	0.79423 (14)	0.84829 (11)	0.27182 (11)	0.0210 (4)
H9	0.8295	0.9054	0.2679	0.025*
C10	0.84333 (14)	0.79591 (11)	0.34650 (11)	0.0217 (4)
H10	0.8581	0.8372	0.3934	0.026*
C11	0.95087 (14)	0.74792 (11)	0.32833 (11)	0.0197 (4)
C12	0.74725 (14)	0.73924 (12)	0.37588 (12)	0.0258 (4)
H12A	0.7630	0.6783	0.3653	0.031*
H12B	0.7339	0.7471	0.4373	0.031*
C13	0.64957 (14)	0.76738 (12)	0.32456 (11)	0.0238 (4)
C14	0.67831 (14)	0.85795 (12)	0.30017 (11)	0.0231 (4)
H14	0.6738	0.8963	0.3507	0.028*
C15	0.70879 (14)	0.73879 (11)	0.16864 (11)	0.0224 (4)
H15	0.6605	0.7694	0.1282	0.027*
C16	0.63726 (15)	0.71180 (12)	0.24422 (12)	0.0240 (4)
H16	0.6546	0.6514	0.2593	0.029*
C17	0.93745 (14)	0.69281 (11)	0.24888 (11)	0.0209 (4)
H17	0.8726	0.6556	0.2544	0.025*
C18	1.24163 (15)	0.81852 (12)	0.26341 (13)	0.0267 (4)
H18A	1.3109	0.7889	0.2719	0.032*
H18B	1.2344	0.8325	0.2025	0.032*
C19	1.13661 (15)	0.68636 (12)	0.22852 (12)	0.0254 (4)
H19A	1.1429	0.7087	0.1700	0.031*
H19B	1.1961	0.6456	0.2376	0.031*
C20	1.02178 (17)	0.57792 (12)	0.16930 (13)	0.0306 (4)
H20A	0.9539	0.5472	0.1765	0.046*
H20B	1.0816	0.5374	0.1716	0.046*
H20C	1.0219	0.6070	0.1143	0.046*
C21	0.89680 (16)	0.60786 (13)	0.50979 (12)	0.0308 (4)
H21A	0.9656	0.5893	0.5336	0.046*
H21B	0.8444	0.5615	0.5144	0.046*
H21C	0.8707	0.6576	0.5412	0.046*
C22	1.32008 (17)	0.95307 (13)	0.29058 (14)	0.0355 (5)
H22A	1.3905	0.9271	0.3007	0.053*
H22B	1.3130	1.0047	0.3251	0.053*
H22C	1.3133	0.9679	0.2305	0.053*
C23	1.0854 (9)	0.9162 (7)	0.0954 (9)	0.058 (3)*	0.333 (16)
H23A	1.0189	0.9267	0.0639	0.087*	0.333 (16)
H23B	1.1454	0.9109	0.0555	0.087*	0.333 (16)
H23C	1.0990	0.9637	0.1342	0.087*	0.333 (16)
C23'	1.0983 (3)	0.9342 (2)	0.1242 (3)	0.0289 (12)*	0.667 (16)
H23D	1.1498	0.9396	0.0775	0.043*	0.667 (16)
H23E	1.1286	0.9598	0.1756	0.043*	0.667 (16)
H23F	1.0315	0.9636	0.1092	0.043*	0.667 (16)
C24	0.79618 (15)	0.85677 (13)	0.04047 (12)	0.0267 (4)
C25	0.78886 (19)	0.93861 (14)	−0.00785 (14)	0.0385 (5)
H25A	0.7831	0.9263	−0.0686	0.058*
H25B	0.8534	0.9728	0.0026	0.058*
H25C	0.7254	0.9704	0.0107	0.058*
C26	0.49317 (17)	0.65471 (14)	0.15989 (14)	0.0386 (5)
H26A	0.5280	0.6662	0.1054	0.058*
H26B	0.4151	0.6577	0.1530	0.058*
H26C	0.5134	0.5977	0.1796	0.058*
C27	0.61137 (15)	0.96722 (11)	0.20869 (13)	0.0255 (4)
C28	0.53567 (14)	0.98128 (12)	0.13698 (12)	0.0254 (4)
C29	0.47300 (16)	0.91484 (13)	0.10516 (12)	0.0292 (4)
H29	0.4788	0.8593	0.1287	0.035*
C30	0.40216 (18)	0.93033 (14)	0.03905 (14)	0.0370 (5)
H30	0.3594	0.8853	0.0173	0.044*
C31	0.39364 (18)	1.01139 (15)	0.00471 (13)	0.0383 (5)
H31	0.3456	1.0216	−0.0409	0.046*
C32	0.45470 (18)	1.07705 (15)	0.03665 (15)	0.0415 (5)
H32	0.4483	1.1327	0.0134	0.050*
C33	0.52578 (16)	1.06205 (13)	0.10295 (15)	0.0353 (5)
H33	0.5677	1.1075	0.1249	0.042*

	U11	U22	U33	U12	U13	U23
O1	0.0263 (7)	0.0297 (7)	0.0346 (8)	−0.0064 (6)	0.0061 (6)	−0.0036 (6)
O2	0.0296 (7)	0.0332 (7)	0.0277 (7)	−0.0010 (6)	0.0076 (6)	0.0077 (6)
O3	0.0288 (7)	0.0261 (6)	0.0218 (6)	−0.0049 (5)	−0.0031 (5)	0.0017 (5)
O4	0.0232 (6)	0.0241 (6)	0.0198 (6)	0.0034 (5)	−0.0013 (5)	0.0009 (5)
O5	0.0372 (8)	0.0343 (8)	0.0226 (7)	0.0021 (6)	0.0010 (6)	−0.0028 (6)
O6	0.0319 (8)	0.0268 (7)	0.0556 (10)	−0.0007 (6)	−0.0138 (7)	−0.0073 (7)
O7	0.0217 (6)	0.0249 (6)	0.0269 (7)	0.0033 (5)	−0.0036 (5)	−0.0022 (5)
O8	0.0304 (7)	0.0277 (6)	0.0254 (7)	0.0018 (6)	0.0020 (6)	−0.0085 (6)
O9	0.0212 (6)	0.0337 (7)	0.0311 (7)	−0.0025 (6)	−0.0012 (5)	−0.0059 (6)
O10	0.0196 (6)	0.0444 (8)	0.0267 (7)	0.0003 (6)	0.0049 (5)	−0.0018 (6)
N1	0.0244 (8)	0.0211 (7)	0.0228 (7)	0.0049 (6)	−0.0007 (6)	−0.0037 (6)
C1	0.0235 (9)	0.0219 (9)	0.0192 (8)	−0.0019 (7)	−0.0013 (7)	−0.0019 (7)
C2	0.0254 (9)	0.0281 (9)	0.0221 (9)	0.0027 (8)	−0.0041 (7)	0.0021 (8)
C3	0.0208 (9)	0.0307 (10)	0.0248 (9)	0.0026 (8)	−0.0024 (7)	−0.0013 (8)
C4	0.0200 (8)	0.0257 (9)	0.0222 (9)	0.0028 (7)	−0.0009 (7)	−0.0005 (8)
C5	0.0194 (8)	0.0232 (9)	0.0213 (8)	0.0017 (7)	−0.0001 (7)	−0.0026 (7)
C6	0.0200 (8)	0.0254 (9)	0.0212 (8)	0.0023 (7)	0.0014 (7)	0.0015 (7)
C7	0.0229 (9)	0.0215 (8)	0.0181 (8)	0.0025 (7)	0.0005 (7)	−0.0007 (7)
C8	0.0229 (9)	0.0224 (9)	0.0165 (8)	0.0018 (7)	−0.0002 (7)	0.0013 (7)
C9	0.0183 (8)	0.0231 (9)	0.0216 (8)	0.0018 (7)	−0.0012 (7)	−0.0037 (7)
C10	0.0217 (9)	0.0257 (9)	0.0176 (8)	0.0014 (7)	−0.0006 (7)	−0.0024 (7)
C11	0.0191 (8)	0.0218 (9)	0.0183 (8)	0.0015 (7)	0.0008 (6)	−0.0014 (7)
C12	0.0236 (9)	0.0337 (10)	0.0200 (9)	0.0020 (8)	0.0027 (7)	0.0001 (8)
C13	0.0201 (9)	0.0297 (9)	0.0217 (8)	0.0019 (8)	0.0042 (7)	−0.0035 (8)
C14	0.0200 (8)	0.0291 (9)	0.0201 (8)	0.0033 (7)	−0.0013 (7)	−0.0048 (8)
C15	0.0229 (9)	0.0231 (9)	0.0213 (8)	0.0026 (7)	0.0001 (7)	−0.0035 (7)
C16	0.0222 (9)	0.0261 (9)	0.0238 (9)	0.0014 (7)	0.0000 (7)	0.0000 (8)
C17	0.0207 (9)	0.0224 (9)	0.0195 (8)	0.0014 (7)	−0.0003 (7)	−0.0008 (7)
C18	0.0196 (9)	0.0321 (10)	0.0286 (10)	0.0033 (8)	0.0010 (7)	0.0005 (8)
C19	0.0225 (9)	0.0285 (10)	0.0254 (9)	0.0068 (7)	0.0019 (7)	−0.0025 (8)
C20	0.0350 (11)	0.0281 (10)	0.0288 (10)	0.0074 (9)	−0.0028 (8)	−0.0078 (8)
C21	0.0326 (10)	0.0352 (11)	0.0248 (10)	−0.0043 (9)	0.0039 (8)	0.0032 (8)
C22	0.0319 (11)	0.0380 (11)	0.0365 (11)	−0.0081 (9)	0.0043 (9)	0.0028 (9)
C24	0.0231 (9)	0.0355 (11)	0.0214 (9)	0.0013 (8)	−0.0002 (7)	0.0009 (8)
C25	0.0496 (13)	0.0383 (12)	0.0275 (11)	0.0059 (10)	0.0004 (10)	0.0052 (9)
C26	0.0293 (11)	0.0447 (13)	0.0417 (12)	−0.0089 (10)	−0.0035 (9)	−0.0124 (10)
C27	0.0208 (9)	0.0228 (9)	0.0330 (10)	0.0038 (8)	0.0018 (8)	−0.0047 (8)
C28	0.0206 (9)	0.0280 (10)	0.0275 (9)	0.0045 (7)	0.0021 (7)	−0.0023 (8)
C29	0.0308 (10)	0.0298 (10)	0.0269 (10)	0.0006 (9)	0.0001 (8)	−0.0024 (8)
C30	0.0366 (12)	0.0436 (12)	0.0307 (11)	0.0028 (10)	−0.0063 (9)	−0.0100 (10)
C31	0.0372 (12)	0.0546 (14)	0.0232 (10)	0.0161 (11)	−0.0019 (9)	−0.0016 (10)
C32	0.0402 (13)	0.0408 (13)	0.0436 (13)	0.0111 (11)	0.0004 (10)	0.0114 (11)
C33	0.0302 (11)	0.0290 (10)	0.0467 (13)	0.0015 (9)	−0.0034 (9)	0.0036 (9)

O1—C22	1.412 (2)	C11—C17	1.531 (2)
O1—C18	1.427 (2)	C12—C13	1.527 (3)
O2—C23	1.326 (9)	C12—H12A	0.9900
O2—C6	1.423 (2)	C12—H12B	0.9900
O2—C23'	1.453 (4)	C13—C14	1.515 (3)
O3—C21	1.416 (2)	C13—C16	1.546 (3)
O3—C1	1.436 (2)	C14—H14	1.0000
O4—C24	1.349 (2)	C15—C16	1.547 (2)
O4—C8	1.491 (2)	C15—H15	1.0000
O5—C24	1.210 (2)	C16—H16	1.0000
O6—C27	1.205 (2)	C17—H17	1.0000
O7—C27	1.344 (2)	C18—H18A	0.9900
O7—C14	1.435 (2)	C18—H18B	0.9900
O8—C15	1.423 (2)	C19—H19A	0.9900
O8—H8	0.8400	C19—H19B	0.9900
O9—C26	1.421 (2)	C20—H20A	0.9800
O9—C16	1.430 (2)	C20—H20B	0.9800
O10—C13	1.424 (2)	C20—H20C	0.9800
O10—H10O	0.8400	C21—H21A	0.9800
N1—C20	1.458 (2)	C21—H21B	0.9800
N1—C17	1.463 (2)	C21—H21C	0.9800
N1—C19	1.476 (2)	C22—H22A	0.9800
C1—C2	1.522 (2)	C22—H22B	0.9800
C1—C11	1.553 (2)	C22—H22C	0.9800
C1—H1	1.0000	C23—H23A	0.9800
C2—C3	1.512 (3)	C23—H23B	0.9800
C2—H2A	0.9900	C23—H23C	0.9800
C2—H2B	0.9900	C23'—H23D	0.9800
C3—C4	1.535 (2)	C23'—H23E	0.9800
C3—H3A	0.9900	C23'—H23F	0.9800
C3—H3B	0.9900	C24—C25	1.496 (3)
C4—C18	1.532 (3)	C25—H25A	0.9800
C4—C19	1.542 (2)	C25—H25B	0.9800
C4—C5	1.551 (2)	C25—H25C	0.9800
C5—C6	1.569 (2)	C26—H26A	0.9800
C5—C11	1.571 (2)	C26—H26B	0.9800
C5—H5	1.0000	C26—H26C	0.9800
C6—C7	1.552 (2)	C27—C28	1.489 (3)
C6—H6	1.0000	C28—C33	1.382 (3)
C7—C8	1.535 (2)	C28—C29	1.396 (3)
C7—C17	1.557 (2)	C29—C30	1.387 (3)
C7—H7	1.0000	C29—H29	0.9500
C8—C9	1.543 (2)	C30—C31	1.386 (3)
C8—C15	1.560 (2)	C30—H30	0.9500
C9—C14	1.519 (2)	C31—C32	1.376 (3)
C9—C10	1.561 (2)	C31—H31	0.9500
C9—H9	1.0000	C32—C33	1.390 (3)
C10—C12	1.561 (3)	C32—H32	0.9500
C10—C11	1.563 (2)	C33—H33	0.9500
C10—H10	1.0000
C22—O1—C18	112.81 (15)	C13—C14—H14	110.4
C23—O2—C6	122.1 (5)	C9—C14—H14	110.4
C23—O2—C23'	22.6 (6)	O8—C15—C16	107.08 (14)
C6—O2—C23'	110.7 (2)	O8—C15—C8	112.77 (14)
C21—O3—C1	113.49 (14)	C16—C15—C8	117.95 (14)
C24—O4—C8	120.76 (14)	O8—C15—H15	106.1
C27—O7—C14	118.66 (15)	C16—C15—H15	106.1
C15—O8—H8	109.5	C8—C15—H15	106.1
C26—O9—C16	115.13 (15)	O9—C16—C13	106.42 (14)
C13—O10—H10O	109.5	O9—C16—C15	109.77 (15)
C20—N1—C17	112.88 (14)	C13—C16—C15	114.84 (14)
C20—N1—C19	110.50 (15)	O9—C16—H16	108.5
C17—N1—C19	116.81 (13)	C13—C16—H16	108.5
O3—C1—C2	108.10 (14)	C15—C16—H16	108.5
O3—C1—C11	109.14 (13)	N1—C17—C11	109.39 (14)
C2—C1—C11	116.76 (15)	N1—C17—C7	115.83 (14)
O3—C1—H1	107.5	C11—C17—C7	100.41 (13)
C2—C1—H1	107.5	N1—C17—H17	110.3
C11—C1—H1	107.5	C11—C17—H17	110.3
C3—C2—C1	111.37 (15)	C7—C17—H17	110.3
C3—C2—H2A	109.4	O1—C18—C4	108.36 (15)
C1—C2—H2A	109.4	O1—C18—H18A	110.0
C3—C2—H2B	109.4	C4—C18—H18A	110.0
C1—C2—H2B	109.4	O1—C18—H18B	110.0
H2A—C2—H2B	108.0	C4—C18—H18B	110.0
C2—C3—C4	112.77 (15)	H18A—C18—H18B	108.4
C2—C3—H3A	109.0	N1—C19—C4	113.38 (14)
C4—C3—H3A	109.0	N1—C19—H19A	108.9
C2—C3—H3B	109.0	C4—C19—H19A	108.9
C4—C3—H3B	109.0	N1—C19—H19B	108.9
H3A—C3—H3B	107.8	C4—C19—H19B	108.9
C18—C4—C3	106.26 (14)	H19A—C19—H19B	107.7
C18—C4—C19	109.61 (15)	N1—C20—H20A	109.5
C3—C4—C19	111.77 (15)	N1—C20—H20B	109.5
C18—C4—C5	112.08 (14)	H20A—C20—H20B	109.5
C3—C4—C5	108.89 (14)	N1—C20—H20C	109.5
C19—C4—C5	108.27 (14)	H20A—C20—H20C	109.5
C4—C5—C6	112.45 (14)	H20B—C20—H20C	109.5
C4—C5—C11	109.01 (14)	O3—C21—H21A	109.5
C6—C5—C11	102.57 (13)	O3—C21—H21B	109.5
C4—C5—H5	110.8	H21A—C21—H21B	109.5
C6—C5—H5	110.8	O3—C21—H21C	109.5
C11—C5—H5	110.8	H21A—C21—H21C	109.5
O2—C6—C7	109.96 (14)	H21B—C21—H21C	109.5
O2—C6—C5	117.11 (14)	O1—C22—H22A	109.5
C7—C6—C5	104.86 (14)	O1—C22—H22B	109.5
O2—C6—H6	108.2	H22A—C22—H22B	109.5
C7—C6—H6	108.2	O1—C22—H22C	109.5
C5—C6—H6	108.2	H22A—C22—H22C	109.5
C8—C7—C6	107.64 (14)	H22B—C22—H22C	109.5
C8—C7—C17	112.00 (14)	O2—C23—H23A	109.5
C6—C7—C17	104.17 (14)	O2—C23—H23B	109.5
C8—C7—H7	110.9	O2—C23—H23C	109.5
C6—C7—H7	110.9	O2—C23'—H23D	109.5
C17—C7—H7	110.9	O2—C23'—H23E	109.5
O4—C8—C7	108.02 (13)	H23D—C23'—H23E	109.5
O4—C8—C9	101.52 (13)	O2—C23'—H23F	109.5
C7—C8—C9	108.18 (14)	H23D—C23'—H23F	109.5
O4—C8—C15	107.34 (13)	H23E—C23'—H23F	109.5
C7—C8—C15	117.05 (14)	O5—C24—O4	124.69 (18)
C9—C8—C15	113.46 (14)	O5—C24—C25	124.88 (18)
C14—C9—C8	112.43 (14)	O4—C24—C25	110.43 (17)
C14—C9—C10	101.71 (14)	C24—C25—H25A	109.5
C8—C9—C10	111.67 (14)	C24—C25—H25B	109.5
C14—C9—H9	110.3	H25A—C25—H25B	109.5
C8—C9—H9	110.3	C24—C25—H25C	109.5
C10—C9—H9	110.3	H25A—C25—H25C	109.5
C9—C10—C12	102.90 (14)	H25B—C25—H25C	109.5
C9—C10—C11	116.81 (14)	O9—C26—H26A	109.5
C12—C10—C11	115.92 (14)	O9—C26—H26B	109.5
C9—C10—H10	106.8	H26A—C26—H26B	109.5
C12—C10—H10	106.8	O9—C26—H26C	109.5
C11—C10—H10	106.8	H26A—C26—H26C	109.5
C17—C11—C1	115.88 (14)	H26B—C26—H26C	109.5
C17—C11—C10	109.17 (14)	O6—C27—O7	124.10 (18)
C1—C11—C10	107.62 (14)	O6—C27—C28	125.78 (18)
C17—C11—C5	98.85 (13)	O7—C27—C28	110.12 (15)
C1—C11—C5	113.26 (14)	C33—C28—C29	119.70 (18)
C10—C11—C5	111.93 (14)	C33—C28—C27	119.17 (18)
C13—C12—C10	106.80 (15)	C29—C28—C27	121.11 (17)
C13—C12—H12A	110.4	C30—C29—C28	119.68 (19)
C10—C12—H12A	110.4	C30—C29—H29	120.2
C13—C12—H12B	110.4	C28—C29—H29	120.2
C10—C12—H12B	110.4	C31—C30—C29	120.2 (2)
H12A—C12—H12B	108.6	C31—C30—H30	119.9
O10—C13—C14	112.75 (15)	C29—C30—H30	119.9
O10—C13—C12	110.67 (15)	C32—C31—C30	120.1 (2)
C14—C13—C12	102.56 (15)	C32—C31—H31	120.0
O10—C13—C16	110.00 (15)	C30—C31—H31	120.0
C14—C13—C16	110.15 (15)	C31—C32—C33	120.0 (2)
C12—C13—C16	110.52 (15)	C31—C32—H32	120.0
O7—C14—C13	108.62 (15)	C33—C32—H32	120.0
O7—C14—C9	114.88 (15)	C28—C33—C32	120.3 (2)
C13—C14—C9	101.87 (14)	C28—C33—H33	119.9
O7—C14—H14	110.4	C32—C33—H33	119.9
C21—O3—C1—C2	80.91 (18)	C27—O7—C14—C9	−71.7 (2)
C21—O3—C1—C11	−151.14 (15)	O10—C13—C14—O7	−74.30 (18)
O3—C1—C2—C3	165.95 (14)	C12—C13—C14—O7	166.65 (14)
C11—C1—C2—C3	42.5 (2)	C16—C13—C14—O7	48.99 (18)
C1—C2—C3—C4	−53.6 (2)	O10—C13—C14—C9	164.07 (14)
C2—C3—C4—C18	−175.02 (15)	C12—C13—C14—C9	45.02 (16)
C2—C3—C4—C19	−55.48 (19)	C16—C13—C14—C9	−72.64 (17)
C2—C3—C4—C5	64.08 (19)	C8—C9—C14—O7	−46.2 (2)
C18—C4—C5—C6	69.60 (19)	C10—C9—C14—O7	−165.74 (14)
C3—C4—C5—C6	−173.13 (15)	C8—C9—C14—C13	71.04 (17)
C19—C4—C5—C6	−51.42 (18)	C10—C9—C14—C13	−48.54 (16)
C18—C4—C5—C11	−177.36 (14)	O4—C8—C15—O8	105.06 (16)
C3—C4—C5—C11	−60.09 (18)	C7—C8—C15—O8	−16.5 (2)
C19—C4—C5—C11	61.63 (18)	C9—C8—C15—O8	−143.62 (15)
C23—O2—C6—C7	117.1 (8)	O4—C8—C15—C16	−129.25 (15)
C23'—O2—C6—C7	139.0 (2)	C7—C8—C15—C16	109.20 (17)
C23—O2—C6—C5	−123.4 (8)	C9—C8—C15—C16	−17.9 (2)
C23'—O2—C6—C5	−101.5 (3)	C26—O9—C16—C13	−166.15 (16)
C4—C5—C6—O2	−26.0 (2)	C26—O9—C16—C15	69.0 (2)
C11—C5—C6—O2	−142.99 (15)	O10—C13—C16—O9	33.85 (19)
C4—C5—C6—C7	96.14 (16)	C14—C13—C16—O9	−91.03 (17)
C11—C5—C6—C7	−20.81 (16)	C12—C13—C16—O9	156.36 (15)
O2—C6—C7—C8	−125.94 (15)	O10—C13—C16—C15	155.52 (15)
C5—C6—C7—C8	107.33 (15)	C14—C13—C16—C15	30.6 (2)
O2—C6—C7—C17	115.01 (15)	C12—C13—C16—C15	−81.97 (19)
C5—C6—C7—C17	−11.72 (17)	O8—C15—C16—O9	−96.10 (17)
C24—O4—C8—C7	69.82 (19)	C8—C15—C16—O9	135.47 (16)
C24—O4—C8—C9	−176.53 (15)	O8—C15—C16—C13	144.07 (15)
C24—O4—C8—C15	−57.24 (19)	C8—C15—C16—C13	15.6 (2)
C6—C7—C8—O4	61.11 (17)	C20—N1—C17—C11	172.24 (15)
C17—C7—C8—O4	175.03 (13)	C19—N1—C17—C11	−58.04 (19)
C6—C7—C8—C9	−48.02 (17)	C20—N1—C17—C7	−75.23 (19)
C17—C7—C8—C9	65.90 (18)	C19—N1—C17—C7	54.5 (2)
C6—C7—C8—C15	−177.69 (14)	C1—C11—C17—N1	−52.12 (19)
C17—C7—C8—C15	−63.77 (19)	C10—C11—C17—N1	−173.77 (14)
O4—C8—C9—C14	88.71 (16)	C5—C11—C17—N1	69.21 (15)
C7—C8—C9—C14	−157.77 (15)	C1—C11—C17—C7	−174.41 (14)
C15—C8—C9—C14	−26.1 (2)	C10—C11—C17—C7	63.93 (16)
O4—C8—C9—C10	−157.70 (14)	C5—C11—C17—C7	−53.09 (15)
C7—C8—C9—C10	−44.17 (18)	C8—C7—C17—N1	167.06 (14)
C15—C8—C9—C10	87.46 (18)	C6—C7—C17—N1	−76.90 (17)
C14—C9—C10—C12	32.56 (16)	C8—C7—C17—C11	−75.30 (16)
C8—C9—C10—C12	−87.55 (16)	C6—C7—C17—C11	40.75 (16)
C14—C9—C10—C11	160.74 (15)	C22—O1—C18—C4	−178.75 (16)
C8—C9—C10—C11	40.6 (2)	C3—C4—C18—O1	−69.66 (18)
O3—C1—C11—C17	−51.58 (19)	C19—C4—C18—O1	169.40 (14)
C2—C1—C11—C17	71.3 (2)	C5—C4—C18—O1	49.16 (19)
O3—C1—C11—C10	70.91 (17)	C20—N1—C19—C4	173.11 (15)
C2—C1—C11—C10	−166.17 (15)	C17—N1—C19—C4	42.3 (2)
O3—C1—C11—C5	−164.83 (14)	C18—C4—C19—N1	−165.02 (15)
C2—C1—C11—C5	−41.9 (2)	C3—C4—C19—N1	77.44 (18)
C9—C10—C11—C17	−52.69 (19)	C5—C4—C19—N1	−42.49 (19)
C12—C10—C11—C17	68.88 (19)	C8—O4—C24—O5	1.2 (3)
C9—C10—C11—C1	−179.23 (14)	C8—O4—C24—C25	−179.41 (16)
C12—C10—C11—C1	−57.65 (19)	C14—O7—C27—O6	−5.0 (3)
C9—C10—C11—C5	55.70 (19)	C14—O7—C27—C28	175.49 (14)
C12—C10—C11—C5	177.28 (14)	O6—C27—C28—C33	−2.5 (3)
C4—C5—C11—C17	−73.55 (16)	O7—C27—C28—C33	177.03 (18)
C6—C5—C11—C17	45.83 (15)	O6—C27—C28—C29	179.06 (19)
C4—C5—C11—C1	49.66 (18)	O7—C27—C28—C29	−1.4 (2)
C6—C5—C11—C1	169.05 (14)	C33—C28—C29—C30	0.7 (3)
C4—C5—C11—C10	171.55 (13)	C27—C28—C29—C30	179.11 (18)
C6—C5—C11—C10	−69.06 (16)	C28—C29—C30—C31	0.0 (3)
C9—C10—C12—C13	−5.33 (18)	C29—C30—C31—C32	−0.6 (3)
C11—C10—C12—C13	−134.06 (15)	C30—C31—C32—C33	0.6 (3)
C10—C12—C13—O10	−144.52 (15)	C29—C28—C33—C32	−0.7 (3)
C10—C12—C13—C14	−24.02 (18)	C27—C28—C33—C32	−179.21 (19)
C10—C12—C13—C16	93.37 (17)	C31—C32—C33—C28	0.1 (3)
C27—O7—C14—C13	175.00 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O5	0.84	2.11	2.7887 (19)	137
O10—H10O···O9	0.84	2.05	2.5620 (19)	118

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O5	0.84	2.11	2.7887 (19)	137
O10—H10O⋯O9	0.84	2.05	2.5620 (19)	118