Mesaconitine

He, D.-H.; Zhu, Y.-C.; Hu, A.-X.

doi:10.1107/S1600536808013147

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1033-o1034

doi:10.1107/S1600536808013147

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Mesaconitine

Dao-Hang He,^a ^* Yong-Chuang Zhu ^a and Ai-Xi Hu ^b

^aSchool of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Hunan University of Technology, Changsha 410082, People's Republic of China
^*Correspondence e-mail: daohanghe@yahoo.com.cn

(Received 26 April 2008; accepted 4 May 2008; online 10 May 2008)

The title compound, (1α,3α,6α,14α,15α,16β)-3,8,13,14,15-pentahydroxy-1,6,16-trimethoxy-4-methoxymethyl-20-methylaconitan-8,14-diyl 8-acetate 14-benzoate, C₃₃H₄₅NO₁₁, a C₁₉ diterpenoid alkaloid, obtained from the roots of Aconitum kusnezoffii, has been crystallographically characterized in this study. Rings A, B and E have chair conformations, rings C and F display envelope conformations, and ring D adopts a boat conformation. There are inter- and intramolecular O—H⋯O hydrogen bonds, the latter resulting in the formation of a non-planar seven-membered ring. The intermolecular interactions link the molecules into a two-dimensional network.

Related literature

For general background, see: Hikino et al. (1980 ); Li et al. (1997 ); Mitamura et al. (2002 ); Saito et al. (1982 ); For ring conformation details, see: Codding (1982 ); De Camp & Pelletier (1977 ); Parvez et al. (1999 ); Pelletier et al. (1982 ). For related literature, see: Pelletier & Djarmati (1976 ); Tsuda & Marion (1963 ); Zhapova et al. (1986 ).

Experimental

Crystal data

C₃₃H₄₅NO₁₁
M_r = 631.70
Orthorhombic, P 2₁ 2₁ 2₁
a = 12.6820 (6) Å
b = 15.3848 (7) Å
c = 15.6110 (7) Å
V = 3045.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 (2) K
0.46 × 0.35 × 0.12 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.954, T_max = 0.988
18319 measured reflections
3713 independent reflections
3026 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.081
S = 1.07
3713 reflections
418 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10A⋯O2	0.84	2.11	2.788 (3)	138
O7—H7⋯O8	0.84	2.04	2.560 (3)	120
O4—H4⋯O11ⁱ	0.84	2.20	3.018 (3)	163
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013147/wn2256sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013147/wn2256Isup2.hkl

checkCIF report

Comment top

As an important Chinese herbal medicine belonging to the genus Aconitum, A. kusnzoffii has been therapeutically used to treat rheumatic pain, paralysis due to stroke, rheumatoid arthritis and some other inflammations. Mesaconitine, a C₁₉ diterpenoid alkaloid, is pharmacologically one of the most active components obtained from the roots of A. kusnezoffii (Li et al., 1997). Mesaconitine has been reported to have an anti-inflammatory activity (Hikino et al.,1980; Saito et al., 1982), and the vasorelaxant effect of mesaconitine may contribute to the therapeutical effectiveness on persons with a weak constitution and poor metabolism, by improving peripheral blood circulation (Mitamura et al., 2002). The three-dimensional structure of most biologically active molecules plays a role in governing their interactions and activities. It is important to obtain information on the mode of action and selectivity of mesaconitine so that it can be used safely and efficiently. Many X-ray crystal structure determinations of C₁₉ diterpenoid alkaloids have been reported, such as pseudaconitine, delphinine (Parvez et al., 1999; Pelletier et al., 1982.). However, the crystal structure of mesaconitine has not been reported. In view of this, the crystal structure determination of the title compound was carried out and the results are presented here.

The structure of mesaconitine is similar to that of aconitine (Codding, 1982). The only difference between aconitine and mesaconitine is a methylene group at the tertiary nitrogen atom. The bond lengths and angles in the title compound are in good agreement with expected values. In the molecule of the title compound, (Fig. 1), rings A, B and E have a chair conformation, rings C and F display an envelope conformation, ring D adopts a boat conformation. The packing of the title compound is shown in Fig. 2. In the crystal structure, there are inter- and intramolecular O—H···O hydrogen bonds. The former link the molecules into a two-dimensional network, while the latter results in the formation of a non-planar seven-membered ring. These intramolecular hydrogen bonds may be effective in the stabilization of the structure.

Related literature top

For general background, see: Hikino et al. (1980); Li et al. (1997); Mitamura et al. (2002); Saito et al. (1982); For ring conformation details, see: Codding (1982); De Camp & Pelletier (1977); Parvez et al. (1999); Pelletier et al. (1982). For related literature, see: Pelletier & Djarmati (1976); Tsuda & Marion (1963); Zhapova et al. (1986).

Experimental top

The title compound was isolated from the roots of A. kusnezoffii according to the literature procedure of Li et al. (1997) and crystals of X-ray quality were grown from methanol at room temperature by slow evaporation.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. The packing of molecules of the title compound, viewed down the c axis. Dashed lines indicate hydrogen bonds.

3,8,13,14,15-pentahydroxy-1α,3α,6α,14α,15α,16β-20-methyl-1,6,16- trimethoxy-4-methoxymethylaconitan-8,14-diyl 8-acetate 14-benzoate top

Crystal data top

C₃₃H₄₅NO₁₁	F(000) = 1352
M_r = 631.70	D_x = 1.378 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6314 reflections
a = 12.6820 (6) Å	θ = 2.5–26.8°
b = 15.3848 (7) Å	µ = 0.10 mm⁻¹
c = 15.6110 (7) Å	T = 173 K
V = 3045.9 (2) Å³	Block, colorless
Z = 4	0.46 × 0.35 × 0.12 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3713 independent reflections
Radiation source: fine-focus sealed tube	3026 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→15
T_min = 0.954, T_max = 0.988	k = −16→19
18319 measured reflections	l = −16→19

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0245P)² + 1.2755P] where P = (F_o² + 2F_c²)/3
3713 reflections	(Δ/σ)_max = 0.001
418 parameters	Δρ_max = 0.21 e Å⁻³
2 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₃₃H₄₅NO₁₁	V = 3045.9 (2) Å³
M_r = 631.70	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 12.6820 (6) Å	µ = 0.10 mm⁻¹
b = 15.3848 (7) Å	T = 173 K
c = 15.6110 (7) Å	0.46 × 0.35 × 0.12 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3713 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3026 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.988	R_int = 0.042
18319 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	2 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.21 e Å⁻³
3713 reflections	Δρ_min = −0.22 e Å⁻³
418 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.0391 (2)	0.81198 (18)	0.21029 (19)	0.0220 (6)
H1	−0.0477	0.8647	0.1734	0.026*
C2	0.0052 (2)	0.8377 (2)	0.3007 (2)	0.0246 (7)
C3	0.0859 (2)	0.76493 (18)	0.32284 (18)	0.0218 (6)
H3	0.0727	0.7412	0.3815	0.026*
C4	0.1968 (2)	0.80413 (18)	0.31663 (18)	0.0209 (6)
C5	0.2045 (2)	0.85444 (18)	0.23165 (18)	0.0219 (6)
H5	0.1701	0.9126	0.2373	0.026*
C6	0.1544 (2)	0.80248 (19)	0.15592 (18)	0.0220 (6)
H6	0.1380	0.8456	0.1099	0.026*
C7	0.0505 (2)	0.75172 (18)	0.17449 (18)	0.0207 (6)
C8	0.0175 (2)	0.70445 (19)	0.09137 (19)	0.0226 (6)
H8	0.0235	0.7470	0.0432	0.027*
C9	−0.0936 (2)	0.6672 (2)	0.0894 (2)	0.0256 (7)
H9A	−0.1126	0.6534	0.0294	0.031*
H9B	−0.0949	0.6123	0.1225	0.031*
C10	−0.1744 (2)	0.72861 (19)	0.12591 (19)	0.0241 (6)
H10	−0.1762	0.7807	0.0877	0.029*
C11	−0.1439 (2)	0.76086 (19)	0.21596 (19)	0.0236 (6)
C12	−0.1281 (2)	0.68527 (19)	0.2794 (2)	0.0254 (7)
H12A	−0.1312	0.7082	0.3386	0.030*
H12B	−0.1866	0.6432	0.2724	0.030*
C13	0.0663 (2)	0.69431 (18)	0.25371 (18)	0.0226 (6)
H13	0.1306	0.6574	0.2466	0.027*
C14	0.2486 (2)	0.7463 (2)	0.1230 (2)	0.0275 (7)
H14A	0.2335	0.6837	0.1313	0.033*
H14B	0.2606	0.7570	0.0612	0.033*
C15	0.3455 (2)	0.7728 (2)	0.17473 (18)	0.0247 (6)
C16	0.3180 (2)	0.86471 (19)	0.20170 (19)	0.0242 (6)
H16	0.3214	0.9048	0.1513	0.029*
C17	0.3584 (2)	0.71420 (19)	0.25396 (19)	0.0253 (7)
H17	0.3397	0.6533	0.2376	0.030*
C18	0.2910 (2)	0.74092 (19)	0.33247 (18)	0.0240 (6)
H18	0.3398	0.7717	0.3726	0.029*
C19	0.3869 (2)	0.97097 (19)	0.3007 (2)	0.0257 (7)
C20	0.4690 (2)	0.98015 (19)	0.3682 (2)	0.0250 (6)
C21	0.5301 (3)	0.9093 (2)	0.3930 (2)	0.0299 (7)
H21	0.5187	0.8540	0.3677	0.036*
C22	0.6072 (3)	0.9198 (2)	0.4544 (2)	0.0356 (8)
H22	0.6489	0.8715	0.4713	0.043*
C23	0.6240 (3)	0.9998 (2)	0.4915 (2)	0.0365 (8)
H23	0.6767	1.0065	0.5342	0.044*
C24	0.5643 (3)	1.0702 (2)	0.4664 (2)	0.0401 (9)
H24	0.5768	1.1255	0.4914	0.048*
C25	0.4865 (3)	1.0608 (2)	0.4053 (2)	0.0362 (8)
H25	0.4451	1.1094	0.3887	0.043*
C26	0.2065 (2)	0.8593 (2)	0.46489 (19)	0.0284 (7)
C27	0.2139 (3)	0.9414 (2)	0.5150 (2)	0.0452 (9)
H27A	0.1483	0.9745	0.5086	0.068*
H27B	0.2731	0.9762	0.4937	0.068*
H27C	0.2251	0.9277	0.5756	0.068*
C28	−0.0892 (3)	0.9341 (3)	0.3905 (3)	0.0584 (12)
H28A	−0.0235	0.9626	0.4079	0.088*
H28B	−0.1399	0.9362	0.4378	0.088*
H28C	−0.1187	0.9641	0.3406	0.088*
C29	0.1046 (3)	0.6183 (2)	−0.0140 (2)	0.0339 (8)
H29A	0.0383	0.5980	−0.0393	0.051*
H29B	0.1589	0.5735	−0.0212	0.051*
H29C	0.1272	0.6718	−0.0427	0.051*
C30	−0.0119 (3)	0.5751 (2)	0.3337 (2)	0.0311 (7)
H30A	0.0555	0.5451	0.3248	0.047*
H30B	−0.0696	0.5328	0.3315	0.047*
H30C	−0.0115	0.6038	0.3897	0.047*
C31	−0.2345 (2)	0.81935 (19)	0.2462 (2)	0.0284 (7)
H31A	−0.3027	0.7887	0.2400	0.034*
H31B	−0.2249	0.8348	0.3073	0.034*
C32	−0.3153 (3)	0.9539 (2)	0.2150 (2)	0.0399 (8)
H32A	−0.3834	0.9252	0.2058	0.060*
H32B	−0.3104	1.0054	0.1783	0.060*
H32C	−0.3092	0.9714	0.2751	0.060*
C33	0.5015 (3)	0.6510 (2)	0.3335 (2)	0.0445 (9)
H33A	0.4696	0.6603	0.3899	0.067*
H33B	0.5785	0.6529	0.3386	0.067*
H33C	0.4800	0.5941	0.3113	0.067*
N1	−0.02662 (19)	0.63950 (15)	0.26699 (16)	0.0239 (5)
O1	0.20493 (15)	0.87584 (12)	0.38022 (12)	0.0241 (4)
O2	0.2048 (2)	0.78785 (15)	0.49642 (14)	0.0402 (6)
O3	0.08940 (16)	0.63488 (13)	0.07442 (13)	0.0263 (5)
O4	−0.27732 (15)	0.68993 (14)	0.12299 (15)	0.0316 (5)
H4	−0.2766	0.6427	0.1499	0.047*
O5	−0.23341 (17)	0.89599 (14)	0.19455 (15)	0.0349 (6)
O6	−0.06838 (16)	0.84649 (14)	0.36913 (14)	0.0328 (5)
O7	0.43716 (15)	0.76827 (15)	0.12268 (13)	0.0309 (5)
H7	0.4897	0.7566	0.1534	0.046*
O8	0.46752 (16)	0.71676 (14)	0.27663 (14)	0.0305 (5)
O9	0.39220 (15)	0.89139 (13)	0.26615 (14)	0.0257 (5)
O10	0.25977 (17)	0.66318 (13)	0.37478 (14)	0.0290 (5)
H10A	0.2344	0.6755	0.4230	0.044*
O11	0.32507 (17)	1.02599 (13)	0.27820 (16)	0.0349 (5)
H2	0.037 (2)	0.8949 (9)	0.297 (2)	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0223 (14)	0.0175 (14)	0.0261 (15)	−0.0007 (12)	0.0000 (12)	0.0027 (12)
C2	0.0242 (15)	0.0225 (15)	0.0272 (16)	−0.0032 (12)	0.0023 (13)	−0.0019 (13)
C3	0.0241 (14)	0.0210 (14)	0.0204 (14)	−0.0024 (12)	0.0003 (12)	0.0007 (12)
C4	0.0231 (14)	0.0190 (14)	0.0207 (14)	−0.0019 (12)	−0.0004 (12)	−0.0012 (12)
C5	0.0216 (14)	0.0180 (14)	0.0261 (15)	−0.0037 (12)	−0.0013 (12)	0.0012 (12)
C6	0.0224 (14)	0.0220 (15)	0.0215 (15)	−0.0024 (12)	−0.0015 (12)	0.0018 (12)
C7	0.0203 (14)	0.0180 (14)	0.0239 (15)	−0.0014 (11)	−0.0029 (12)	−0.0007 (12)
C8	0.0251 (15)	0.0201 (15)	0.0227 (14)	0.0031 (12)	−0.0018 (12)	0.0023 (12)
C9	0.0263 (15)	0.0254 (16)	0.0251 (16)	−0.0045 (13)	−0.0068 (13)	−0.0003 (13)
C10	0.0192 (14)	0.0249 (15)	0.0283 (15)	−0.0032 (12)	−0.0032 (12)	0.0052 (13)
C11	0.0217 (14)	0.0211 (15)	0.0281 (15)	−0.0004 (12)	−0.0001 (12)	0.0029 (13)
C12	0.0231 (14)	0.0248 (15)	0.0282 (16)	−0.0053 (12)	−0.0001 (13)	0.0023 (13)
C13	0.0218 (14)	0.0198 (14)	0.0263 (16)	−0.0016 (12)	−0.0013 (12)	0.0010 (13)
C14	0.0273 (15)	0.0290 (16)	0.0263 (15)	−0.0029 (14)	0.0031 (13)	−0.0012 (13)
C15	0.0242 (14)	0.0255 (15)	0.0243 (15)	−0.0033 (13)	0.0022 (12)	0.0001 (13)
C16	0.0244 (15)	0.0248 (15)	0.0235 (15)	−0.0030 (13)	−0.0028 (12)	0.0058 (12)
C17	0.0230 (15)	0.0217 (15)	0.0311 (16)	−0.0013 (12)	0.0002 (13)	−0.0003 (13)
C18	0.0259 (15)	0.0225 (15)	0.0237 (15)	−0.0018 (13)	0.0000 (13)	0.0021 (12)
C19	0.0233 (15)	0.0203 (15)	0.0337 (18)	−0.0055 (13)	0.0016 (13)	0.0034 (13)
C20	0.0217 (14)	0.0266 (15)	0.0267 (16)	−0.0045 (13)	0.0035 (13)	0.0004 (13)
C21	0.0336 (17)	0.0256 (16)	0.0307 (18)	−0.0019 (14)	−0.0003 (14)	0.0026 (14)
C22	0.0373 (18)	0.0350 (19)	0.0343 (19)	0.0011 (16)	−0.0072 (15)	0.0090 (16)
C23	0.0339 (18)	0.047 (2)	0.0284 (18)	−0.0087 (16)	−0.0056 (15)	0.0040 (16)
C24	0.0358 (19)	0.036 (2)	0.049 (2)	−0.0075 (16)	−0.0028 (17)	−0.0144 (17)
C25	0.0302 (17)	0.0269 (17)	0.051 (2)	0.0008 (14)	−0.0034 (16)	−0.0027 (16)
C26	0.0288 (16)	0.0304 (18)	0.0260 (16)	−0.0039 (14)	0.0002 (14)	−0.0031 (14)
C27	0.064 (3)	0.035 (2)	0.036 (2)	−0.0062 (19)	−0.0018 (19)	−0.0077 (16)
C28	0.043 (2)	0.050 (2)	0.082 (3)	−0.0042 (19)	0.019 (2)	−0.034 (2)
C29	0.0347 (17)	0.0335 (18)	0.0335 (18)	0.0068 (15)	0.0028 (15)	−0.0042 (15)
C30	0.0338 (17)	0.0234 (16)	0.0362 (18)	−0.0041 (14)	−0.0038 (15)	0.0080 (14)
C31	0.0241 (15)	0.0279 (16)	0.0332 (17)	−0.0026 (13)	0.0009 (13)	0.0014 (14)
C32	0.041 (2)	0.0364 (19)	0.043 (2)	0.0109 (16)	0.0066 (17)	0.0022 (17)
C33	0.0345 (19)	0.045 (2)	0.054 (2)	0.0089 (17)	−0.0026 (17)	0.0134 (19)
N1	0.0250 (13)	0.0197 (12)	0.0269 (13)	−0.0043 (11)	−0.0018 (11)	0.0047 (11)
O1	0.0270 (10)	0.0215 (10)	0.0238 (11)	−0.0029 (9)	−0.0012 (9)	−0.0031 (9)
O2	0.0527 (15)	0.0367 (14)	0.0313 (12)	−0.0038 (12)	0.0017 (11)	0.0005 (11)
O3	0.0290 (11)	0.0230 (11)	0.0270 (11)	0.0031 (9)	−0.0036 (9)	−0.0029 (9)
O4	0.0239 (11)	0.0305 (12)	0.0405 (13)	−0.0063 (9)	−0.0056 (10)	0.0057 (11)
O5	0.0348 (12)	0.0273 (12)	0.0424 (14)	0.0098 (10)	0.0107 (11)	0.0074 (10)
O6	0.0293 (11)	0.0338 (12)	0.0354 (12)	−0.0005 (10)	0.0084 (10)	−0.0081 (11)
O7	0.0232 (10)	0.0401 (13)	0.0293 (11)	−0.0012 (10)	0.0048 (9)	0.0014 (11)
O8	0.0248 (11)	0.0300 (12)	0.0367 (12)	0.0019 (9)	0.0003 (10)	0.0067 (10)
O9	0.0231 (10)	0.0224 (10)	0.0318 (12)	−0.0035 (9)	−0.0030 (9)	0.0003 (9)
O10	0.0326 (11)	0.0249 (11)	0.0297 (12)	−0.0004 (9)	0.0023 (10)	0.0080 (10)
O11	0.0287 (12)	0.0229 (11)	0.0532 (15)	0.0023 (10)	−0.0106 (11)	0.0011 (11)

Geometric parameters (Å, º) top

C1—C11	1.547 (4)	C18—O10	1.422 (3)
C1—C7	1.570 (4)	C18—H18	1.0000
C1—C2	1.570 (4)	C19—O11	1.206 (3)
C1—H1	1.0000	C19—O9	1.339 (3)
C2—O6	1.424 (4)	C19—C20	1.489 (4)
C2—C3	1.556 (4)	C20—C25	1.387 (4)
C2—H2	0.970 (16)	C20—C21	1.391 (4)
C3—C4	1.533 (4)	C21—C22	1.379 (4)
C3—C13	1.551 (4)	C21—H21	0.9500
C3—H3	1.0000	C22—C23	1.376 (5)
C4—O1	1.488 (3)	C22—H22	0.9500
C4—C5	1.539 (4)	C23—C24	1.377 (5)
C4—C18	1.560 (4)	C23—H23	0.9500
C5—C16	1.522 (4)	C24—C25	1.380 (5)
C5—C6	1.562 (4)	C24—H24	0.9500
C5—H5	1.0000	C25—H25	0.9500
C6—C7	1.559 (4)	C26—O2	1.204 (4)
C6—C14	1.561 (4)	C26—O1	1.346 (4)
C6—H6	1.0000	C26—C27	1.490 (4)
C7—C13	1.533 (4)	C27—H27A	0.9800
C7—C8	1.545 (4)	C27—H27B	0.9800
C8—O3	1.431 (3)	C27—H27C	0.9800
C8—C9	1.521 (4)	C28—O6	1.413 (4)
C8—H8	1.0000	C28—H28A	0.9800
C9—C10	1.506 (4)	C28—H28B	0.9800
C9—H9A	0.9900	C28—H28C	0.9800
C9—H9B	0.9900	C29—O3	1.417 (4)
C10—O4	1.435 (3)	C29—H29A	0.9800
C10—C11	1.540 (4)	C29—H29B	0.9800
C10—H10	1.0000	C29—H29C	0.9800
C11—C31	1.534 (4)	C30—N1	1.449 (4)
C11—C12	1.540 (4)	C30—H30A	0.9800
C12—N1	1.480 (4)	C30—H30B	0.9800
C12—H12A	0.9900	C30—H30C	0.9800
C12—H12B	0.9900	C31—O5	1.429 (4)
C13—N1	1.464 (4)	C31—H31A	0.9900
C13—H13	1.0000	C31—H31B	0.9900
C14—C15	1.526 (4)	C32—O5	1.405 (4)
C14—H14A	0.9900	C32—H32A	0.9800
C14—H14B	0.9900	C32—H32B	0.9800
C15—O7	1.420 (3)	C32—H32C	0.9800
C15—C16	1.516 (4)	C33—O8	1.413 (4)
C15—C17	1.539 (4)	C33—H33A	0.9800
C16—O9	1.437 (3)	C33—H33B	0.9800
C16—H16	1.0000	C33—H33C	0.9800
C17—O8	1.429 (3)	O4—H4	0.8400
C17—C18	1.550 (4)	O7—H7	0.8400
C17—H17	1.0000	O10—H10A	0.8400

C11—C1—C7	110.0 (2)	O9—C16—H16	110.3
C11—C1—C2	112.6 (2)	C15—C16—H16	110.3
C7—C1—C2	102.1 (2)	C5—C16—H16	110.3
C11—C1—H1	110.6	O8—C17—C15	106.6 (2)
C7—C1—H1	110.6	O8—C17—C18	109.3 (2)
C2—C1—H1	110.6	C15—C17—C18	114.9 (2)
O6—C2—C3	109.5 (2)	O8—C17—H17	108.6
O6—C2—C1	117.6 (2)	C15—C17—H17	108.6
C3—C2—C1	104.7 (2)	C18—C17—H17	108.6
O6—C2—H2	104 (2)	O10—C18—C17	107.3 (2)
C3—C2—H2	113 (2)	O10—C18—C4	112.6 (2)
C1—C2—H2	109 (2)	C17—C18—C4	117.6 (2)
C4—C3—C13	112.2 (2)	O10—C18—H18	106.2
C4—C3—C2	107.8 (2)	C17—C18—H18	106.2
C13—C3—C2	104.1 (2)	C4—C18—H18	106.2
C4—C3—H3	110.8	O11—C19—O9	123.9 (3)
C13—C3—H3	110.8	O11—C19—C20	126.5 (3)
C2—C3—H3	110.8	O9—C19—C20	109.7 (2)
O1—C4—C3	108.3 (2)	C25—C20—C21	119.7 (3)
O1—C4—C5	101.4 (2)	C25—C20—C19	119.5 (3)
C3—C4—C5	108.1 (2)	C21—C20—C19	120.8 (3)
O1—C4—C18	107.7 (2)	C22—C21—C20	119.7 (3)
C3—C4—C18	116.6 (2)	C22—C21—H21	120.1
C5—C4—C18	113.7 (2)	C20—C21—H21	120.1
C16—C5—C4	112.2 (2)	C23—C22—C21	120.5 (3)
C16—C5—C6	101.9 (2)	C23—C22—H22	119.8
C4—C5—C6	111.7 (2)	C21—C22—H22	119.8
C16—C5—H5	110.3	C22—C23—C24	119.9 (3)
C4—C5—H5	110.3	C22—C23—H23	120.1
C6—C5—H5	110.3	C24—C23—H23	120.1
C7—C6—C14	115.5 (2)	C23—C24—C25	120.4 (3)
C7—C6—C5	117.3 (2)	C23—C24—H24	119.8
C14—C6—C5	102.8 (2)	C25—C24—H24	119.8
C7—C6—H6	106.8	C24—C25—C20	119.8 (3)
C14—C6—H6	106.8	C24—C25—H25	120.1
C5—C6—H6	106.8	C20—C25—H25	120.1
C13—C7—C8	116.2 (2)	O2—C26—O1	125.0 (3)
C13—C7—C6	109.1 (2)	O2—C26—C27	124.1 (3)
C8—C7—C6	108.0 (2)	O1—C26—C27	110.8 (3)
C13—C7—C1	98.5 (2)	C26—C27—H27A	109.5
C8—C7—C1	112.4 (2)	C26—C27—H27B	109.5
C6—C7—C1	112.5 (2)	H27A—C27—H27B	109.5
O3—C8—C9	107.7 (2)	C26—C27—H27C	109.5
O3—C8—C7	109.5 (2)	H27A—C27—H27C	109.5
C9—C8—C7	116.4 (2)	H27B—C27—H27C	109.5
O3—C8—H8	107.6	O6—C28—H28A	109.5
C9—C8—H8	107.6	O6—C28—H28B	109.5
C7—C8—H8	107.6	H28A—C28—H28B	109.5
C10—C9—C8	112.7 (2)	O6—C28—H28C	109.5
C10—C9—H9A	109.0	H28A—C28—H28C	109.5
C8—C9—H9A	109.0	H28B—C28—H28C	109.5
C10—C9—H9B	109.0	O3—C29—H29A	109.5
C8—C9—H9B	109.0	O3—C29—H29B	109.5
H9A—C9—H9B	107.8	H29A—C29—H29B	109.5
O4—C10—C9	110.3 (2)	O3—C29—H29C	109.5
O4—C10—C11	113.0 (2)	H29A—C29—H29C	109.5
C9—C10—C11	112.1 (2)	H29B—C29—H29C	109.5
O4—C10—H10	107.0	N1—C30—H30A	109.5
C9—C10—H10	107.0	N1—C30—H30B	109.5
C11—C10—H10	107.0	H30A—C30—H30B	109.5
C31—C11—C10	106.4 (2)	N1—C30—H30C	109.5
C31—C11—C12	110.0 (2)	H30A—C30—H30C	109.5
C10—C11—C12	112.1 (2)	H30B—C30—H30C	109.5
C31—C11—C1	111.3 (2)	O5—C31—C11	107.6 (2)
C10—C11—C1	109.1 (2)	O5—C31—H31A	110.2
C12—C11—C1	108.0 (2)	C11—C31—H31A	110.2
N1—C12—C11	112.9 (2)	O5—C31—H31B	110.2
N1—C12—H12A	109.0	C11—C31—H31B	110.2
C11—C12—H12A	109.0	H31A—C31—H31B	108.5
N1—C12—H12B	109.0	O5—C32—H32A	109.5
C11—C12—H12B	109.0	O5—C32—H32B	109.5
H12A—C12—H12B	107.8	H32A—C32—H32B	109.5
N1—C13—C7	109.9 (2)	O5—C32—H32C	109.5
N1—C13—C3	115.7 (2)	H32A—C32—H32C	109.5
C7—C13—C3	100.3 (2)	H32B—C32—H32C	109.5
N1—C13—H13	110.2	O8—C33—H33A	109.5
C7—C13—H13	110.2	O8—C33—H33B	109.5
C3—C13—H13	110.2	H33A—C33—H33B	109.5
C15—C14—C6	107.1 (2)	O8—C33—H33C	109.5
C15—C14—H14A	110.3	H33A—C33—H33C	109.5
C6—C14—H14A	110.3	H33B—C33—H33C	109.5
C15—C14—H14B	110.3	C30—N1—C13	113.1 (2)
C6—C14—H14B	110.3	C30—N1—C12	110.1 (2)
H14A—C14—H14B	108.5	C13—N1—C12	116.4 (2)
O7—C15—C16	113.1 (2)	C26—O1—C4	121.0 (2)
O7—C15—C14	110.1 (2)	C29—O3—C8	113.7 (2)
C16—C15—C14	102.2 (2)	C10—O4—H4	109.5
O7—C15—C17	110.1 (2)	C32—O5—C31	112.8 (2)
C16—C15—C17	110.4 (2)	C28—O6—C2	112.9 (3)
C14—C15—C17	110.8 (2)	C15—O7—H7	109.5
O9—C16—C15	108.1 (2)	C33—O8—C17	115.5 (2)
O9—C16—C5	115.7 (2)	C19—O9—C16	120.7 (2)
C15—C16—C5	101.9 (2)	C18—O10—H10A	109.5

C11—C1—C2—O6	−26.0 (4)	C2—C3—C13—C7	40.7 (3)
C7—C1—C2—O6	−143.9 (2)	C7—C6—C14—C15	−133.1 (2)
C11—C1—C2—C3	95.8 (3)	C5—C6—C14—C15	−4.0 (3)
C7—C1—C2—C3	−22.2 (3)	C6—C14—C15—O7	−145.6 (2)
O6—C2—C3—C4	−124.5 (2)	C6—C14—C15—C16	−25.2 (3)
C1—C2—C3—C4	108.5 (2)	C6—C14—C15—C17	92.4 (3)
O6—C2—C3—C13	116.1 (2)	O7—C15—C16—O9	−73.8 (3)
C1—C2—C3—C13	−10.9 (3)	C14—C15—C16—O9	167.8 (2)
C13—C3—C4—O1	175.3 (2)	C17—C15—C16—O9	50.0 (3)
C2—C3—C4—O1	61.2 (3)	O7—C15—C16—C5	163.8 (2)
C13—C3—C4—C5	66.2 (3)	C14—C15—C16—C5	45.5 (3)
C2—C3—C4—C5	−47.9 (3)	C17—C15—C16—C5	−72.4 (3)
C13—C3—C4—C18	−63.2 (3)	C4—C5—C16—O9	−45.8 (3)
C2—C3—C4—C18	−177.4 (2)	C6—C5—C16—O9	−165.3 (2)
O1—C4—C5—C16	89.2 (3)	C4—C5—C16—C15	71.2 (3)
C3—C4—C5—C16	−157.1 (2)	C6—C5—C16—C15	−48.4 (3)
C18—C4—C5—C16	−26.0 (3)	O7—C15—C17—O8	33.8 (3)
O1—C4—C5—C6	−157.2 (2)	C16—C15—C17—O8	−91.8 (3)
C3—C4—C5—C6	−43.5 (3)	C14—C15—C17—O8	155.8 (2)
C18—C4—C5—C6	87.6 (3)	O7—C15—C17—C18	155.1 (2)
C16—C5—C6—C7	159.5 (2)	C16—C15—C17—C18	29.5 (3)
C4—C5—C6—C7	39.7 (3)	C14—C15—C17—C18	−82.9 (3)
C16—C5—C6—C14	31.6 (3)	O8—C17—C18—O10	−95.0 (3)
C4—C5—C6—C14	−88.3 (3)	C15—C17—C18—O10	145.2 (2)
C14—C6—C7—C13	69.8 (3)	O8—C17—C18—C4	136.9 (3)
C5—C6—C7—C13	−51.7 (3)	C15—C17—C18—C4	17.0 (4)
C14—C6—C7—C8	−57.4 (3)	O1—C4—C18—O10	104.2 (3)
C5—C6—C7—C8	−178.9 (2)	C3—C4—C18—O10	−17.5 (3)
C14—C6—C7—C1	178.0 (2)	C5—C4—C18—O10	−144.3 (2)
C5—C6—C7—C1	56.5 (3)	O1—C4—C18—C17	−130.2 (2)
C11—C1—C7—C13	−72.6 (3)	C3—C4—C18—C17	108.0 (3)
C2—C1—C7—C13	47.1 (2)	C5—C4—C18—C17	−18.7 (3)
C11—C1—C7—C8	50.4 (3)	O11—C19—C20—C25	−6.9 (5)
C2—C1—C7—C8	170.1 (2)	O9—C19—C20—C25	172.2 (3)
C11—C1—C7—C6	172.5 (2)	O11—C19—C20—C21	174.7 (3)
C2—C1—C7—C6	−67.8 (3)	O9—C19—C20—C21	−6.2 (4)
C13—C7—C8—O3	−52.6 (3)	C25—C20—C21—C22	0.2 (5)
C6—C7—C8—O3	70.3 (3)	C19—C20—C21—C22	178.6 (3)
C1—C7—C8—O3	−165.0 (2)	C20—C21—C22—C23	0.1 (5)
C13—C7—C8—C9	69.9 (3)	C21—C22—C23—C24	−0.7 (5)
C6—C7—C8—C9	−167.2 (2)	C22—C23—C24—C25	0.9 (5)
C1—C7—C8—C9	−42.5 (3)	C23—C24—C25—C20	−0.6 (5)
O3—C8—C9—C10	166.8 (2)	C21—C20—C25—C24	0.0 (5)
C7—C8—C9—C10	43.4 (3)	C19—C20—C25—C24	−178.4 (3)
C8—C9—C10—O4	−179.6 (2)	C10—C11—C31—O5	−68.7 (3)
C8—C9—C10—C11	−52.7 (3)	C12—C11—C31—O5	169.7 (2)
O4—C10—C11—C31	−52.4 (3)	C1—C11—C31—O5	50.1 (3)
C9—C10—C11—C31	−177.8 (2)	C7—C13—N1—C30	172.1 (2)
O4—C10—C11—C12	67.9 (3)	C3—C13—N1—C30	−75.2 (3)
C9—C10—C11—C12	−57.5 (3)	C7—C13—N1—C12	−59.0 (3)
O4—C10—C11—C1	−172.6 (2)	C3—C13—N1—C12	53.7 (3)
C9—C10—C11—C1	62.0 (3)	C11—C12—N1—C30	174.3 (2)
C7—C1—C11—C31	−177.0 (2)	C11—C12—N1—C13	44.0 (3)
C2—C1—C11—C31	69.9 (3)	O2—C26—O1—C4	2.3 (5)
C7—C1—C11—C10	−59.9 (3)	C27—C26—O1—C4	−179.4 (3)
C2—C1—C11—C10	−173.0 (2)	C3—C4—O1—C26	69.5 (3)
C7—C1—C11—C12	62.2 (3)	C5—C4—O1—C26	−176.9 (2)
C2—C1—C11—C12	−51.0 (3)	C18—C4—O1—C26	−57.3 (3)
C31—C11—C12—N1	−165.4 (2)	C9—C8—O3—C29	84.5 (3)
C10—C11—C12—N1	76.4 (3)	C7—C8—O3—C29	−148.0 (2)
C1—C11—C12—N1	−43.8 (3)	C11—C31—O5—C32	178.3 (3)
C8—C7—C13—N1	−51.9 (3)	C3—C2—O6—C28	136.2 (3)
C6—C7—C13—N1	−174.2 (2)	C1—C2—O6—C28	−104.5 (3)
C1—C7—C13—N1	68.3 (3)	C15—C17—O8—C33	−164.5 (3)
C8—C7—C13—C3	−174.2 (2)	C18—C17—O8—C33	70.7 (3)
C6—C7—C13—C3	63.4 (3)	O11—C19—O9—C16	−3.7 (4)
C1—C7—C13—C3	−54.0 (2)	C20—C19—O9—C16	177.3 (2)
C4—C3—C13—N1	166.2 (2)	C15—C16—O9—C19	179.1 (2)
C2—C3—C13—N1	−77.4 (3)	C5—C16—O9—C19	−67.5 (3)
C4—C3—C13—C7	−75.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O2	0.84	2.11	2.788 (3)	138
O7—H7···O8	0.84	2.04	2.560 (3)	120
O4—H4···O11ⁱ	0.84	2.20	3.018 (3)	163

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₃H₄₅NO₁₁
M_r	631.70
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	12.6820 (6), 15.3848 (7), 15.6110 (7)
V (Å³)	3045.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.46 × 0.35 × 0.12

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.954, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	18319, 3713, 3026
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.081, 1.07
No. of reflections	3713
No. of parameters	418
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O2	0.84	2.11	2.788 (3)	138
O7—H7···O8	0.84	2.04	2.560 (3)	120
O4—H4···O11ⁱ	0.84	2.20	3.018 (3)	163

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

The authors thank Guangdong Provincial Natural Science Foundation of China (No. 04300531) for financial assistance.

References

Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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