14-Benzoyl­mesaconine hydro­chloride methanol monosolvate

Mu, Y.; Li, L.; Wei, H.-L.; Kuang, T.-C.; Hu, S.-Q.

doi:10.1107/S1600536811010300

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o974-o975

doi:10.1107/S1600536811010300

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14-Benzoylmesaconine hydrochloride methanol monosolvate

Yan Mu,^a Lin Li,^a Hai-Liu Wei,^a Tong-Chun Kuang ^b and Song-Qing Hu ^a ^*

^aCollege of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, People's Republic of China, and ^bAnalytical and Testing Center, South China University of Technology, Guangzhou 510640, People's Republic of China
^*Correspondence e-mail: fesqhu@scut.edu.cn

(Received 18 February 2011; accepted 18 March 2011; online 26 March 2011)

The title compound, C₃₁H₄₄N₃O₁₀⁺·Cl⁻·CH₄O, is the methanol solvate of 8-benzoyloxy-,9,11,11a-tetrahydroxy-6,10,13-trimethoxy-3-methoxymethyl-1-methyltetradecahydro-1H-3,6a,12-(epiethane-1,1,2-triyl)-7,9-methanonaphtho[2,3-b]azocin-1-ium chloride, the amine-protonated hydrochloride of 14-benzoylmesaconine hydrochloride. The cation has an aconitine carbon skeleton with four six-membered rings of which three display chair conformations and one a boat conformation, and two five-membered rings with envelope conformations. In the crystal, the components are connected into an infinite chain by inter- and intramolecular O—H⋯O, N—H⋯O and O—H⋯Cl hydrogen bonds.

Related literature

For general background to diterpenoid alkaloids, see: Ameri (1998 ); Desai et al. (1998 ); Suzuki et al. (1994 ). For the chemical structure of the title compound established from MS data, see: Zhang et al. (2005 ); Wang et al. (2009 ); Yue et al. (2009 ). For background to the strong toxicity of Aconitum alkaloids, see: Zhang et al. (2002 ). For ring numbering and ring conformations of the title compound, see: He et al. (2008 ).

Experimental

Crystal data

C₃₁H₄₄NO₁₀⁺·Cl⁻·CH₄O
M_r = 658.16
Orthorhombic, P 2₁ 2₁ 2₁
a = 12.919 (3) Å
b = 15.748 (3) Å
c = 16.045 (3) Å
V = 3264.2 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 123 K
0.30 × 0.20 × 0.20 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.969, T_max = 0.977
29100 measured reflections
6908 independent reflections
4585 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.151
S = 1.10
6908 reflections
422 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.50 e Å⁻³
Absolute structure: Flack (1983 ), 1726 Friedel pairs
Flack parameter: −0.01 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O5	0.82	2.11	2.612 (4)	119
O3—H3A⋯O11	0.82	2.22	2.923 (4)	144
O4—H4A⋯Cl1	0.82	2.30	3.083 (3)	161
O6—H6⋯Cl1	0.82	2.40	3.197 (3)	165
O9—H9⋯O11ⁱ	0.82	1.98	2.776 (4)	163
N1—H1⋯O8	0.90 (2)	2.11 (4)	2.808 (4)	134 (4)
N1—H1⋯O9	0.90 (2)	2.20 (4)	2.795 (5)	123 (4)
O11—H11⋯Cl1ⁱⁱ	0.82	2.30	3.084 (3)	158
Symmetry codes: (i) x+1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010300/zl2352sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010300/zl2352Isup2.hkl

checkCIF report

Comment top

Aconitum species such as e.g. Aconitum Caremichaeli Debx. have been widely used in Chinese Traditional Medicine, and its tubers and roots have found therapeutical use for the treatment of for example rheumatic pain, rheumatoid arthritis and some other inflammations. Aconitine-type alkaloid extracts from the roots of Aconitum Caremichaeli Debx. are reported to have, among others, analgetic, diuretics, anti-inflammatory and cardiotonic properties (Ameri, 1998; Desai et al., 1998; Suzuki et al., 1994). At the same time, owing to their strong toxicity, poisoning with these Aconitum alkaloids does frequently happen (Zhang et al., 2002). Therefore, in order to better understand the pharmacology of the Aconitum alkaloids it is desirable to establish their molecular structures. The diterpenoid alkaloid 14-benzoylmesaconine, the title compound, was previously isolated from Aconitum Caremichaeli Debx., and its structure was established from the MS data (Zhang et al., 2005; Wang et al., 2009; Yue et al., 2009). However, there are no reports on the crystal structure or the NMR data of 14-benzoylmesaconine. In this paper, we would like to present the crystal structure and NMR data of the title compound, the hydrochloride salt of 14-benzoylmesaconine as its mono methanol solvate.

The molecular structure of the title compound is shown in Fig. 1. There is one cation, protonated at the amine N atom, one chloride anion and one methanol solvate molecule in the asymmetric unit of the structure. The bond lengths and angles are in good agreement with expected values. For ring naming (Figure 2) and ring conformations please refer to He et al. (2008). The cation of the title compound has an aconitine carbon skeleton with four six-membered rings and two five-membered rings. Six-membered rings A (C16/C21/C23/C24/C25/C26) and B (C9/C10/C15/C16/C17/C18) adopt chair conformations, six-membered heterocyclic ring E (N1/C17/C21/C22/C23) adopts a chair conformation, and the six-membered ring D (C8/C9/C12/C13/C14/C15) adopts a boat conformation. The two five-membered rings C (C16/C17/C18/C19/C21) and F (C8/C9/C10/C11/C12) adopt envelope conformations (Fig. 2). Intermolecular O—H···O hydrogen bonds between the hydroxyls of the cations and the hydroxy O atoms of the methanol solvate molecules lead to infinite chains. The chains are further connected with each other via intermolecular O—H···Cl hydrogen bonding interactions involving the hydroxyls of methanol molecules and the cations as donors and the chloride anions as acceptors to form 1D double-chains along to the a axis (Table 1, Fig. 3). Within the hydrogen-bonded double-chain the chloride anions are bonded to three hydroxyl groups, two from one cation and another one from a methanol solvate molecule. Each cation donates four hydrogen bonds to two methanol solvate molecules and one chloride anion, whilst each methanol solvate molecule donates one hydrogen bond to chloride anion and acceptes two hydrogen bonds from two hydroxyl groups of two cations. In addition, intramolecular N—H···O and O—H···O hydrogen bonds are also observed within the double-chain. Finally, the chains are linked into a three-dimensional supramolecular network through intermolecular O—H···O and O—H···Cl hydrogen-bonding interactions.

Related literature top

For general background to diterpenoid alkaloids, see: Ameri (1998); Desai et al. (1998); Suzuki et al. (1994). For the chemical structure of the title compound established from MS data, see: Zhang et al. (2005); Wang et al. (2009); Yue et al. (2009). For background to the strong toxicity of Aconitum alkaloids, see: Zhang et al. (2002). For ring numbering and ring conformations of the title compound, see: He et al. (2008).

Experimental top

Air-dried and powdered roots of Aconitum Caremichaeli Debx. (20 kg) were extracted with 90% EtOH (40 L) under reflux with a Soxhlet extractor. After the removal of solvent, the extract residue (200 g) was successively eluted in a macroporous resin by elution with water (5 L), 30% EtOH (5 L), 60% EtOH (5 L) and 90% EtOH (5 L), and different extract fractions were obtained. From the 30% EtOH fraction, a black amorphous powder (50 g) was obtained after the removal of the solvent under reduced pressure, which then was chromatographed on a silica gel (200–300 mesh) column, eluted with a chloroform-MeOH (99:1 to 1:1) gradient system, to give 25 fractions (2 L per fraction). The title compound (2 g) can be isolated between the eighteenth and twentieth fractions (yield 0.01%). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in CHCl₃ at room temperature. [¹H NMR(CDCl₃, δ, p.p.m.) 8.08 (d, 2H), 7.58 (t, 1H), 7.45 (t, 2H), 5.01 (d, 1H), 4.58 (d, 1H), 4.17 (t, 2H), 3.70 (s, 3H), 3.57 (d, 2H), 3.39 (t, 2H), 3.30–3.34 (m, 15H), 3.21 (d, 1H), 2.94 (s, 3H), 2.56 (s, 2H), 2.40 (d, 2H), 2.23 (t, 2H), 1.81 (d, 1H), 1.56 (d, 1H); ¹³C NMR (CDCl₃, δ, p.p.m.) 167.88, 134.45, 131.68, 131.20, 129.66, 93.60, 83.20, 81.48, 83.20, 81.48, 80.90, 79.15, 78.38, 76.36, 70.79, 68.38, 62.44, 59.67, 58.76, 55.76, 53.13, 52.06, 50.07, 45.55, 44.86, 43.76, 42.20, 41.91, 37.41, 30.62].

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Thermal ellipsoid plot of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms were omitted for clarity.
	Fig. 2. View of the structure of the title compound with naming of the rings (He et al., 2008), showing 50% probability displacement ellipsoids.
	Fig. 3. View of a one-dimensional chain of the title compound that stretches along to the a axis of the cell. O—H···O, N—H···O and O—H···Cl hydrogen bonds interactions are shown as dashed pink lines.

8-benzoyloxy-4,9,11,11a-tetrahydroxy-6,10,13-trimethoxy-3-methoxymethyl- 1-methyltetradecahydro-1H-3,6a,12-(epiethane-1,1,2-triyl)-7,9- methanonaphtho[2,3-b]azocin-1-ium chloride methanol monosolvate top

Crystal data top

C₃₁H₄₄NO₁₀⁺·Cl⁻·CH₄O	F(000) = 1408
M_r = 658.16	D_x = 1.339 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5837 reflections
a = 12.919 (3) Å	θ = 2.8–27.9°
b = 15.748 (3) Å	µ = 0.18 mm⁻¹
c = 16.045 (3) Å	T = 123 K
V = 3264.2 (11) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Rigaku/MSC Mercury CCD diffractometer	6908 independent reflections
Radiation source: fine-focus sealed tube	4585 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 26.8°, θ_min = 3.0°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	h = −16→16
T_min = 0.969, T_max = 0.977	k = −19→19
29100 measured reflections	l = −20→20

Refinement top

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)] = 0.047	w = 1/[σ²(F_o²) + (0.040P)² + 3.5P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.151	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 0.36 e Å⁻³
6908 reflections	Δρ_min = −0.50 e Å⁻³
422 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0187 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1726 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (11)

Crystal data top

C₃₁H₄₄NO₁₀⁺·Cl⁻·CH₄O	V = 3264.2 (11) Å³
M_r = 658.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 12.919 (3) Å	µ = 0.18 mm⁻¹
b = 15.748 (3) Å	T = 123 K
c = 16.045 (3) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Rigaku/MSC Mercury CCD diffractometer	6908 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	4585 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.977	R_int = 0.050
29100 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.151	Δρ_max = 0.36 e Å⁻³
S = 1.10	Δρ_min = −0.50 e Å⁻³
6908 reflections	Absolute structure: Flack (1983), 1726 Friedel pairs
422 parameters	Absolute structure parameter: −0.01 (11)
1 restraint

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
O1	0.2155 (3)	0.3580 (2)	0.1441 (2)	0.0676 (9)
O2	0.2226 (2)	0.37571 (18)	0.28249 (16)	0.0457 (7)
O3	0.2193 (2)	0.53973 (19)	0.3747 (2)	0.0562 (8)
H3A	0.1791	0.5138	0.4050	0.084*
O4	0.4338 (2)	0.30793 (17)	0.47185 (17)	0.0462 (7)
H4A	0.4359	0.2560	0.4693	0.069*
O5	0.2329 (2)	0.40600 (19)	0.47032 (18)	0.0525 (7)
O6	0.4216 (2)	0.26331 (16)	0.27517 (17)	0.0448 (7)
H6	0.4352	0.2220	0.3044	0.067*
O7	0.6872 (2)	0.28611 (17)	0.23706 (19)	0.0500 (7)
O8	0.6159 (2)	0.59029 (17)	0.42349 (19)	0.0523 (7)
O9	0.8284 (2)	0.5542 (2)	0.4047 (2)	0.0591 (8)
H9	0.8901	0.5451	0.4126	0.089*
O10	0.8654 (2)	0.4637 (2)	0.1640 (2)	0.0633 (9)
N1	0.6874 (2)	0.4220 (2)	0.4292 (2)	0.0434 (8)
H1	0.696 (4)	0.4762 (16)	0.446 (3)	0.076 (17)*
C1	0.0994 (3)	0.2805 (2)	0.2312 (2)	0.0414 (9)
C2	0.0520 (3)	0.2385 (3)	0.1659 (3)	0.0452 (9)
H2	0.0758	0.2469	0.1118	0.054*
C3	−0.0302 (3)	0.1842 (3)	0.1797 (3)	0.0560 (11)
H3	−0.0619	0.1566	0.1353	0.067*
C4	−0.0649 (4)	0.1712 (3)	0.2602 (3)	0.0586 (11)
H4	−0.1205	0.1349	0.2699	0.070*
C5	−0.0174 (4)	0.2119 (3)	0.3265 (3)	0.0595 (12)
H5	−0.0404	0.2027	0.3807	0.071*
C6	0.0649 (3)	0.2668 (3)	0.3116 (3)	0.0517 (10)
H6A	0.0968	0.2943	0.3559	0.062*
C7	0.1852 (3)	0.3401 (3)	0.2127 (3)	0.0450 (9)
C8	0.2993 (3)	0.4412 (3)	0.2759 (2)	0.0410 (9)
H8	0.2795	0.4810	0.2317	0.049*
C9	0.4112 (3)	0.4122 (2)	0.2622 (2)	0.0394 (8)
H9A	0.4209	0.3946	0.2042	0.047*
C10	0.4718 (3)	0.4964 (2)	0.2794 (3)	0.0410 (9)
H10	0.4736	0.5284	0.2270	0.049*
C11	0.3996 (3)	0.5450 (2)	0.3401 (3)	0.0468 (10)
H11A	0.4360	0.5578	0.3915	0.056*
H11B	0.3771	0.5980	0.3152	0.056*
C12	0.3068 (3)	0.4881 (2)	0.3577 (3)	0.0423 (9)
C13	0.3285 (3)	0.4250 (2)	0.4295 (3)	0.0424 (9)
H13	0.3749	0.4523	0.4697	0.051*
C14	0.3773 (3)	0.3403 (2)	0.4020 (2)	0.0380 (8)
H14	0.3197	0.3009	0.3927	0.046*
C15	0.4424 (3)	0.3400 (2)	0.3210 (2)	0.0380 (8)
C16	0.5854 (3)	0.4909 (2)	0.3125 (2)	0.0403 (9)
C17	0.5845 (3)	0.4256 (2)	0.3837 (2)	0.0388 (9)
H17	0.5283	0.4382	0.4229	0.047*
C18	0.5609 (3)	0.3453 (2)	0.3357 (2)	0.0379 (8)
H18A	0.5859	0.2952	0.3658	0.045*
C19	0.6176 (3)	0.3550 (2)	0.2510 (3)	0.0411 (9)
H19	0.5653	0.3538	0.2067	0.049*
C20	0.7003 (4)	0.2693 (3)	0.1503 (3)	0.0655 (13)
H20A	0.6348	0.2541	0.1263	0.098*
H20B	0.7483	0.2234	0.1431	0.098*
H20C	0.7265	0.3192	0.1231	0.098*
C21	0.6640 (3)	0.4455 (2)	0.2540 (3)	0.0413 (9)
H21	0.6640	0.4715	0.1985	0.050*
C22	0.7736 (3)	0.3949 (3)	0.3727 (3)	0.0470 (10)
H22A	0.7645	0.3358	0.3574	0.056*
H22B	0.8393	0.4004	0.4015	0.056*
C23	0.7741 (3)	0.4501 (3)	0.2944 (3)	0.0449 (9)
C24	0.8054 (3)	0.5448 (3)	0.3170 (3)	0.0510 (10)
H24	0.8672	0.5601	0.2850	0.061*
C25	0.7206 (3)	0.6064 (3)	0.2961 (3)	0.0488 (10)
H25A	0.7130	0.6090	0.2360	0.059*
H25B	0.7405	0.6625	0.3153	0.059*
C26	0.6178 (3)	0.5833 (2)	0.3343 (3)	0.0450 (9)
H26	0.5653	0.6218	0.3117	0.054*
C27	0.6260 (5)	0.6758 (3)	0.4529 (4)	0.0805 (17)
H27A	0.6957	0.6950	0.4442	0.121*
H27B	0.6101	0.6778	0.5113	0.121*
H27C	0.5791	0.7118	0.4230	0.121*
C28	0.8615 (3)	0.4165 (3)	0.2395 (3)	0.0529 (11)
H28A	0.9270	0.4215	0.2688	0.064*
H28B	0.8499	0.3569	0.2272	0.064*
C29	0.9648 (4)	0.4617 (4)	0.1275 (3)	0.0717 (15)
H29A	1.0140	0.4871	0.1648	0.108*
H29B	0.9638	0.4927	0.0760	0.108*
H29C	0.9842	0.4038	0.1168	0.108*
C30	0.6832 (4)	0.3678 (3)	0.5058 (3)	0.0565 (11)
H30A	0.6665	0.3105	0.4904	0.085*
H30B	0.6311	0.3893	0.5429	0.085*
H30C	0.7492	0.3688	0.5332	0.085*
C31	0.2372 (4)	0.4038 (5)	0.5574 (3)	0.093 (2)
H31A	0.2842	0.3600	0.5748	0.140*
H31B	0.1695	0.3922	0.5793	0.140*
H31C	0.2609	0.4576	0.5780	0.140*
Cl1	0.44750 (9)	0.12099 (7)	0.41575 (8)	0.0623 (3)
O11	0.0250 (2)	0.51954 (19)	0.46583 (18)	0.0553 (8)
H11	0.0125	0.4738	0.4882	0.083*
C32	0.0388 (5)	0.5825 (4)	0.5277 (3)	0.0859 (18)
H32A	0.1112	0.5888	0.5394	0.129*
H32B	0.0030	0.5659	0.5776	0.129*
H32C	0.0115	0.6355	0.5081	0.129*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.065 (2)	0.091 (3)	0.0468 (18)	−0.0232 (19)	0.0066 (16)	0.0031 (17)
O2	0.0363 (14)	0.0545 (16)	0.0463 (16)	−0.0098 (13)	−0.0066 (12)	0.0044 (13)
O3	0.0364 (15)	0.0546 (18)	0.078 (2)	0.0108 (14)	0.0071 (15)	0.0074 (15)
O4	0.0481 (16)	0.0467 (15)	0.0437 (16)	0.0047 (13)	−0.0087 (13)	0.0078 (12)
O5	0.0400 (15)	0.0694 (19)	0.0480 (17)	−0.0030 (14)	0.0094 (13)	0.0029 (14)
O6	0.0535 (16)	0.0353 (13)	0.0455 (16)	−0.0068 (13)	−0.0035 (13)	−0.0059 (12)
O7	0.0474 (15)	0.0444 (16)	0.0583 (19)	0.0102 (13)	0.0082 (14)	0.0005 (13)
O8	0.0550 (17)	0.0406 (14)	0.0613 (19)	−0.0047 (13)	−0.0044 (15)	−0.0061 (13)
O9	0.0442 (16)	0.0607 (19)	0.073 (2)	−0.0027 (15)	−0.0088 (15)	−0.0015 (16)
O10	0.0484 (17)	0.078 (2)	0.064 (2)	0.0129 (16)	0.0109 (15)	0.0216 (17)
N1	0.0363 (17)	0.047 (2)	0.047 (2)	0.0004 (15)	−0.0043 (14)	0.0067 (16)
C1	0.0357 (19)	0.044 (2)	0.044 (2)	−0.0035 (17)	−0.0020 (17)	−0.0013 (17)
C2	0.038 (2)	0.049 (2)	0.049 (2)	0.0003 (18)	−0.0015 (18)	−0.0070 (18)
C3	0.049 (2)	0.056 (3)	0.063 (3)	−0.003 (2)	−0.002 (2)	−0.010 (2)
C4	0.051 (3)	0.055 (3)	0.069 (3)	−0.008 (2)	−0.009 (2)	0.000 (2)
C5	0.051 (2)	0.070 (3)	0.058 (3)	−0.015 (2)	0.005 (2)	0.008 (2)
C6	0.049 (2)	0.063 (3)	0.042 (2)	−0.009 (2)	−0.001 (2)	0.001 (2)
C7	0.0338 (19)	0.052 (2)	0.049 (2)	−0.0007 (18)	−0.0068 (18)	−0.0001 (19)
C8	0.0301 (18)	0.044 (2)	0.049 (2)	−0.0122 (16)	−0.0049 (16)	0.0044 (18)
C9	0.0366 (19)	0.040 (2)	0.042 (2)	−0.0006 (16)	−0.0022 (16)	0.0031 (16)
C10	0.0326 (19)	0.0377 (19)	0.053 (2)	−0.0016 (16)	−0.0046 (17)	0.0052 (17)
C11	0.034 (2)	0.039 (2)	0.067 (3)	−0.0009 (17)	−0.0008 (18)	−0.0007 (19)
C12	0.0273 (17)	0.043 (2)	0.056 (2)	0.0056 (16)	0.0023 (17)	0.0014 (18)
C13	0.0355 (19)	0.045 (2)	0.046 (2)	−0.0002 (17)	0.0008 (17)	0.0011 (17)
C14	0.0357 (18)	0.044 (2)	0.0344 (19)	−0.0005 (17)	−0.0001 (16)	0.0054 (16)
C15	0.0406 (19)	0.0355 (18)	0.038 (2)	−0.0005 (17)	−0.0038 (16)	−0.0002 (15)
C16	0.040 (2)	0.0340 (19)	0.047 (2)	0.0036 (16)	−0.0041 (17)	0.0042 (16)
C17	0.0305 (18)	0.040 (2)	0.046 (2)	0.0014 (16)	−0.0049 (16)	0.0057 (16)
C18	0.0368 (19)	0.0338 (17)	0.043 (2)	0.0000 (16)	−0.0075 (17)	0.0036 (15)
C19	0.039 (2)	0.038 (2)	0.046 (2)	0.0066 (16)	0.0077 (17)	0.0015 (16)
C20	0.069 (3)	0.065 (3)	0.063 (3)	0.004 (3)	0.011 (3)	−0.010 (2)
C21	0.036 (2)	0.039 (2)	0.049 (2)	−0.0008 (16)	−0.0003 (17)	0.0087 (17)
C22	0.0331 (19)	0.052 (2)	0.056 (3)	0.0042 (18)	−0.0018 (18)	0.0094 (19)
C23	0.038 (2)	0.043 (2)	0.054 (2)	−0.0018 (17)	−0.0015 (18)	0.0083 (18)
C24	0.037 (2)	0.052 (2)	0.064 (3)	0.0022 (19)	−0.002 (2)	0.008 (2)
C25	0.038 (2)	0.042 (2)	0.066 (3)	−0.0072 (18)	−0.0068 (19)	0.0109 (19)
C26	0.039 (2)	0.041 (2)	0.055 (3)	−0.0004 (17)	−0.0077 (18)	0.0049 (18)
C27	0.102 (4)	0.052 (3)	0.087 (4)	−0.016 (3)	0.001 (3)	−0.017 (3)
C28	0.040 (2)	0.055 (3)	0.063 (3)	0.006 (2)	0.008 (2)	0.009 (2)
C29	0.060 (3)	0.080 (3)	0.075 (3)	0.007 (3)	0.028 (3)	0.020 (3)
C30	0.057 (3)	0.066 (3)	0.047 (2)	0.003 (2)	−0.005 (2)	0.014 (2)
C31	0.062 (3)	0.171 (7)	0.047 (3)	0.008 (4)	0.011 (2)	0.017 (4)
Cl1	0.0678 (7)	0.0509 (6)	0.0683 (8)	0.0090 (6)	0.0048 (6)	0.0101 (5)
O11	0.0571 (18)	0.0564 (18)	0.0523 (18)	−0.0034 (16)	−0.0013 (15)	0.0072 (14)
C32	0.128 (5)	0.073 (3)	0.057 (3)	−0.012 (4)	−0.008 (3)	−0.008 (3)

Geometric parameters (Å, º) top

O1—C7	1.202 (5)	C13—H13	0.9800
O2—C7	1.342 (5)	C14—C15	1.548 (5)
O2—C8	1.434 (4)	C14—H14	0.9800
O3—C12	1.420 (4)	C15—C18	1.552 (5)
O3—H3A	0.8200	C16—C17	1.537 (5)
O4—C14	1.431 (4)	C16—C26	1.553 (5)
O4—H4A	0.8200	C16—C21	1.557 (6)
O5—C31	1.399 (5)	C17—C18	1.512 (5)
O5—C13	1.430 (4)	C17—H17	0.9800
O6—C15	1.439 (4)	C18—C19	1.551 (5)
O6—H6	0.8200	C18—H18A	0.9800
O7—C19	1.426 (4)	C19—C21	1.548 (5)
O7—C20	1.427 (5)	C19—H19	0.9800
O8—C27	1.433 (5)	C20—H20A	0.9600
O8—C26	1.436 (5)	C20—H20B	0.9600
O9—C24	1.445 (5)	C20—H20C	0.9600
O9—H9	0.8200	C21—C23	1.565 (5)
O10—C29	1.412 (5)	C21—H21	0.9800
O10—C28	1.423 (5)	C22—C23	1.528 (5)
N1—C22	1.498 (5)	C22—H22A	0.9700
N1—C30	1.497 (5)	C22—H22B	0.9700
N1—C17	1.518 (5)	C23—C28	1.526 (6)
N1—H1	0.901 (19)	C23—C24	1.587 (6)
C1—C2	1.382 (5)	C24—C25	1.501 (5)
C1—C6	1.383 (6)	C24—H24	0.9800
C1—C7	1.482 (5)	C25—C26	1.507 (5)
C2—C3	1.381 (6)	C25—H25A	0.9700
C2—H2	0.9300	C25—H25B	0.9700
C3—C4	1.383 (7)	C26—H26	0.9800
C3—H3	0.9300	C27—H27A	0.9600
C4—C5	1.386 (6)	C27—H27B	0.9600
C4—H4	0.9300	C27—H27C	0.9600
C5—C6	1.390 (6)	C28—H28A	0.9700
C5—H5	0.9300	C28—H28B	0.9700
C6—H6A	0.9300	C29—H29A	0.9600
C8—C12	1.509 (6)	C29—H29B	0.9600
C8—C9	1.532 (5)	C29—H29C	0.9600
C8—H8	0.9800	C30—H30A	0.9600
C9—C15	1.531 (5)	C30—H30B	0.9600
C9—C10	1.564 (5)	C30—H30C	0.9600
C9—H9A	0.9800	C31—H31A	0.9600
C10—C11	1.552 (6)	C31—H31B	0.9600
C10—C16	1.563 (5)	C31—H31C	0.9600
C10—H10	0.9800	O11—C32	1.414 (6)
C11—C12	1.523 (5)	O11—H11	0.8200
C11—H11A	0.9700	C32—H32A	0.9600
C11—H11B	0.9700	C32—H32B	0.9600
C12—C13	1.547 (5)	C32—H32C	0.9600
C13—C14	1.540 (5)

C7—O2—C8	119.2 (3)	N1—C17—H17	110.3
C12—O3—H3A	109.5	C16—C17—H17	110.3
C14—O4—H4A	109.5	C17—C18—C19	105.6 (3)
C31—O5—C13	115.3 (4)	C17—C18—C15	108.7 (3)
C15—O6—H6	109.5	C19—C18—C15	109.8 (3)
C19—O7—C20	111.6 (3)	C17—C18—H18A	110.9
C27—O8—C26	113.5 (3)	C19—C18—H18A	110.9
C24—O9—H9	109.5	C15—C18—H18A	110.9
C29—O10—C28	111.9 (3)	O7—C19—C21	117.5 (3)
C22—N1—C30	111.2 (3)	O7—C19—C18	111.1 (3)
C22—N1—C17	111.8 (3)	C21—C19—C18	104.2 (3)
C30—N1—C17	112.6 (3)	O7—C19—H19	107.9
C22—N1—H1	111 (3)	C21—C19—H19	107.9
C30—N1—H1	108 (3)	C18—C19—H19	107.9
C17—N1—H1	103 (3)	O7—C20—H20A	109.5
C2—C1—C6	119.3 (4)	O7—C20—H20B	109.5
C2—C1—C7	118.9 (4)	H20A—C20—H20B	109.5
C6—C1—C7	121.8 (4)	O7—C20—H20C	109.5
C1—C2—C3	121.0 (4)	H20A—C20—H20C	109.5
C1—C2—H2	119.5	H20B—C20—H20C	109.5
C3—C2—H2	119.5	C19—C21—C16	100.9 (3)
C2—C3—C4	119.4 (4)	C19—C21—C23	114.0 (3)
C2—C3—H3	120.3	C16—C21—C23	108.8 (3)
C4—C3—H3	120.3	C19—C21—H21	110.9
C3—C4—C5	120.3 (4)	C16—C21—H21	110.9
C3—C4—H4	119.9	C23—C21—H21	110.9
C5—C4—H4	119.9	N1—C22—C23	109.8 (3)
C4—C5—C6	119.6 (4)	N1—C22—H22A	109.7
C4—C5—H5	120.2	C23—C22—H22A	109.7
C6—C5—H5	120.2	N1—C22—H22B	109.7
C1—C6—C5	120.3 (4)	C23—C22—H22B	109.7
C1—C6—H6A	119.8	H22A—C22—H22B	108.2
C5—C6—H6A	119.8	C28—C23—C22	106.3 (3)
O1—C7—O2	123.3 (4)	C28—C23—C21	114.7 (3)
O1—C7—C1	125.1 (4)	C22—C23—C21	108.1 (3)
O2—C7—C1	111.5 (3)	C28—C23—C24	105.6 (3)
O2—C8—C12	109.4 (3)	C22—C23—C24	110.3 (3)
O2—C8—C9	116.6 (3)	C21—C23—C24	111.7 (3)
C12—C8—C9	102.1 (3)	O9—C24—C25	107.5 (4)
O2—C8—H8	109.5	O9—C24—C23	111.8 (3)
C12—C8—H8	109.5	C25—C24—C23	111.7 (3)
C9—C8—H8	109.5	O9—C24—H24	108.6
C8—C9—C15	112.4 (3)	C25—C24—H24	108.6
C8—C9—C10	101.2 (3)	C23—C24—H24	108.6
C15—C9—C10	112.9 (3)	C24—C25—C26	113.3 (3)
C8—C9—H9A	110.0	C24—C25—H25A	108.9
C15—C9—H9A	110.0	C26—C25—H25A	108.9
C10—C9—H9A	110.0	C24—C25—H25B	108.9
C11—C10—C16	112.2 (3)	C26—C25—H25B	108.9
C11—C10—C9	103.2 (3)	H25A—C25—H25B	107.7
C16—C10—C9	118.9 (3)	O8—C26—C25	113.7 (3)
C11—C10—H10	107.3	O8—C26—C16	107.0 (3)
C16—C10—H10	107.3	C25—C26—C16	111.9 (3)
C9—C10—H10	107.3	O8—C26—H26	108.0
C12—C11—C10	107.3 (3)	C25—C26—H26	108.0
C12—C11—H11A	110.2	C16—C26—H26	108.0
C10—C11—H11A	110.2	O8—C27—H27A	109.5
C12—C11—H11B	110.2	O8—C27—H27B	109.5
C10—C11—H11B	110.2	H27A—C27—H27B	109.5
H11A—C11—H11B	108.5	O8—C27—H27C	109.5
O3—C12—C8	113.3 (3)	H27A—C27—H27C	109.5
O3—C12—C11	109.0 (3)	H27B—C27—H27C	109.5
C8—C12—C11	100.3 (3)	O10—C28—C23	109.6 (3)
O3—C12—C13	111.6 (3)	O10—C28—H28A	109.7
C8—C12—C13	110.2 (3)	C23—C28—H28A	109.7
C11—C12—C13	111.9 (3)	O10—C28—H28B	109.7
O5—C13—C14	107.7 (3)	C23—C28—H28B	109.7
O5—C13—C12	108.6 (3)	H28A—C28—H28B	108.2
C14—C13—C12	114.6 (3)	O10—C29—H29A	109.5
O5—C13—H13	108.6	O10—C29—H29B	109.5
C14—C13—H13	108.6	H29A—C29—H29B	109.5
C12—C13—H13	108.6	O10—C29—H29C	109.5
O4—C14—C13	107.0 (3)	H29A—C29—H29C	109.5
O4—C14—C15	112.3 (3)	H29B—C29—H29C	109.5
C13—C14—C15	117.7 (3)	N1—C30—H30A	109.5
O4—C14—H14	106.4	N1—C30—H30B	109.5
C13—C14—H14	106.4	H30A—C30—H30B	109.5
C15—C14—H14	106.4	N1—C30—H30C	109.5
O6—C15—C9	105.0 (3)	H30A—C30—H30C	109.5
O6—C15—C14	109.3 (3)	H30B—C30—H30C	109.5
C9—C15—C14	111.8 (3)	O5—C31—H31A	109.5
O6—C15—C18	107.8 (3)	O5—C31—H31B	109.5
C9—C15—C18	108.3 (3)	H31A—C31—H31B	109.5
C14—C15—C18	114.1 (3)	O5—C31—H31C	109.5
C17—C16—C26	117.4 (3)	H31A—C31—H31C	109.5
C17—C16—C21	98.4 (3)	H31B—C31—H31C	109.5
C26—C16—C21	112.9 (3)	C32—O11—H11	109.5
C17—C16—C10	106.4 (3)	O11—C32—H32A	109.5
C26—C16—C10	106.2 (3)	O11—C32—H32B	109.5
C21—C16—C10	115.6 (3)	H32A—C32—H32B	109.5
C18—C17—N1	112.9 (3)	O11—C32—H32C	109.5
C18—C17—C16	100.5 (3)	H32A—C32—H32C	109.5
N1—C17—C16	112.1 (3)	H32B—C32—H32C	109.5
C18—C17—H17	110.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5	0.82	2.11	2.612 (4)	119
O3—H3A···O11	0.82	2.22	2.923 (4)	144
O4—H4A···Cl1	0.82	2.30	3.083 (3)	161
O6—H6···Cl1	0.82	2.40	3.197 (3)	165
O9—H9···O11ⁱ	0.82	1.98	2.776 (4)	163
N1—H1···O8	0.90 (2)	2.11 (4)	2.808 (4)	134 (4)
N1—H1···O9	0.90 (2)	2.20 (4)	2.795 (5)	123 (4)
O11—H11···Cl1ⁱⁱ	0.82	2.30	3.084 (3)	158

Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₃₁H₄₄NO₁₀⁺·Cl⁻·CH₄O
M_r	658.16
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	123
a, b, c (Å)	12.919 (3), 15.748 (3), 16.045 (3)
V (Å³)	3264.2 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.969, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	29100, 6908, 4585
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.151, 1.10
No. of reflections	6908
No. of parameters	422
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.50
Absolute structure	Flack (1983), 1726 Friedel pairs
Absolute structure parameter	−0.01 (11)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O5	0.82	2.11	2.612 (4)	119
O3—H3A···O11	0.82	2.22	2.923 (4)	144
O4—H4A···Cl1	0.82	2.30	3.083 (3)	161
O6—H6···Cl1	0.82	2.40	3.197 (3)	165
O9—H9···O11ⁱ	0.82	1.98	2.776 (4)	163
N1—H1···O8	0.901 (19)	2.11 (4)	2.808 (4)	134 (4)
N1—H1···O9	0.901 (19)	2.20 (4)	2.795 (5)	123 (4)
O11—H11···Cl1ⁱⁱ	0.82	2.30	3.084 (3)	158

Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+1/2, −z+1.

Acknowledgements

This project was supported by the Fundamental Research Funds for the Central Universities, SCUT (grant No. 20092Z0011). We thank Dr Yan-Wei Ren and Professor Lei Zhang for technical support.

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