Tuberostemoamide hemihydrate

Zhang, R.-R.; Ma, Z.-G.; Li, G.-Q.; But, P.P.-H.; Jiang, R.-W.

doi:10.1107/S1600536811043340

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3056

doi:10.1107/S1600536811043340

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Tuberostemoamide hemihydrate

Rong-Rong Zhang,^a Zhi-Guo Ma,^a Guo-Qiang Li,^a Paul Pui-Hay But ^b and Ren-Wang Jiang ^a ^*

^aGuangdong Province Key Laboratory of Pharmacodynamic Constituents of, Traditional Chinese Medicine and New Drugs Research, Institute of Traditional Chinese Medicine and Natural Products, Jinan University, Guangzhou 510632, People's Republic of China, and ^bSchool of Biological Sciences, The Chinese University of Hong Kong, Hong Kong, People's Republic of China
^*Correspondence e-mail: trwjiang@jnu.edu.cn

(Received 2 October 2011; accepted 19 October 2011; online 29 October 2011)

In the crystal structure of the title compound {systematic name: (1′S,2R,2′R,3′S,6′R)-3′-ethyl-4-methyl-5H-5′-oxa-10′-azaspiro[furan-2,4′-tricyclo[8.3.0.0^2,6]tridecane]-5,11′-dione hemihydrate}, C₁₇H₂₃NO₄·0.5H₂O, the asymmetric unit contains two molecules of tuberostemoamide with similar conformations and one water molecule. The tuberostemoamide molecule is composed of one seven-membered ring (A) and three five-membered rings (B, C and D). Ring A exists in a chair conformation, both rings B and C exist in envelope conformations, and ring D is almost planar with a mean deviation of 0.0143 (4) Å in one molecule and 0.0095 (3) Å in the other.. The dihedral angles between the planes of rings C and D are 75.1 (3)° in one molecule and 74.5 (3)° for the other. The solvent water molecule links the tuberostemoamide molecules through O—H⋯O(ketone) hydrogen bonds. Weak C—H⋯O interactions are also present, involving both the water molecule and a heterocyclic ether O-atom acceptor.

Related literature

For general background, see: Pilli & Ferreira de Oliveira (2000 ); Jiang et al. (2006 ). For the biological activity of Stemona alkaloids, see: Xu et al. (2010 ); Lin et al. (2008 ); Hu et al. (2009 ).

Experimental

Crystal data

C₁₇H₂₃NO₄·0.5H₂O
M_r = 314.37
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.6412 (2) Å
b = 10.7998 (2) Å
c = 36.1685 (7) Å
V = 3375.36 (12) Å³
Z = 8
Cu Kα radiation
μ = 0.73 mm⁻¹
T = 298 K
0.42 × 0.30 × 0.27 mm

Data collection

Oxford Diffraction Gemini S Ultra CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.822, T_max = 1.000
8573 measured reflections
4837 independent reflections
4514 reflections with I > 2I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.142
S = 1.06
4837 reflections
412 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1743 Friedel pairs
Flack parameter: −0.1 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O1	0.81	1.98	2.796 (3)	175
O1W—H1WB⋯O1′	0.83	1.97	2.784 (3)	171
C5′—H5′A⋯O3ⁱ	0.97	2.58	3.545 (4)	178
C10—H10A⋯O1Wⁱⁱ	0.98	2.58	3.450 (4)	149
Symmetry codes: (i) $[x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811043340/zs2152sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043340/zs2152Isup2.hkl

checkCIF report

Comment top

The title compound 2(C₁₇H₂₃NO₄) . H₂O (Fig. 1) is a hydrate of tuberostemoamide which has been isolated from the roots of Stemona tuberosa. This plant is a rich source of Stemona alkaloids (Pilli & Ferreira de Oliveira, 2000; Jiang et al., 2006) with anti-tussive activity (Xu et al., 2010). Although the phytochemical properties of tuberostemoamide have been studied Hu et al., 2009); Lin et al., 2008) the crystal structure has not previously been reported. In this study, we report the structure of tuberostemoamide hemihydrate.

The asymmetric unit contains two molecules of tuberostemoamide [(1) and (2)] with similar conformations and one water molecule (Fig. 1). The tuberostemoamide molecule is composed of one seven-membered ring (A) and three five-membered rings (B, C and D). Ring A exists in a chair conformation. Ring B exists in an envelope conformation with C1 displaced by 0.4695 Å from the least-squares plane of the remaining four atoms (C2, C3, N4 and C9A), and the corresponding value for molecule (2) is 0.4868 Å. Ring C also exhibits an envelope conformation with C10 displaced by 0.5930 Å from the least-squares plane of the remaining four atoms (C8, C8, O2 and C11), and the corresponding value for molecule (2) is 0.5886 Å. Ring D is planar with a mean deviation 0.0142 Å for (1) and 0.0101 Å for (2). The dihedral angles between the planes of the rings C and D in molecule (1) is 75.1 (3)° and 74.5 (3)° for molecule (2). The absolute configuration for the compound was not determined with certainty in this analysis.

The water molecule links the tuberostemoamide molecules through O—H···O(ketone) hydrogen bonds (Table 1) with only weak intermolecular C—H···O interactions present, involving both the water molecule and a hetero-ring ether O-acceptor (Fig. 2).

Related literature top

For general background, see: Pilli & Ferreira de Oliveira (2000); Jiang et al. (2006). For the biological activity of Stemona alkaloids, see: Xu et al. (2010); Lin et al. (2008); Hu et al. (2009).

Experimental top

The dry ground herbal sample Radix stemonae (8.0 kg) was refluxed with 95% EtOH. After evaporation of the solvent, the crude extract was acidified with 4% HCl and filtered, and the filtrate was washed with diethyl ether (800 ml). The pH of the aqueous layer was raised to 9 with aqueous ammonia (35%) and then extracted with Et₂O (800 ml). The Et₂O layer was evaporated to afford the crude alkaloids (25 g), which was subjected to column chromatography over silica gel, and eluted with cyclohexane-ethyl acetate (10:1 to 0:1) to yield fourteen fractions. Fraction 8 (4 g) was subjected to reverse phase silica gel chromatography to yield seven subfractions, after which the second subfraction (60% CH₃CN, 8 mg) was purified by preparative HPLC eluted by 25% CH₃CN to yield tuberostemoamide (4 mg). The colorless crystals were obtained from a methanol solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme. Inter-species hydrogen bonds are shown as dashed lines.
	Fig. 2. Packing diagram viewed down the a axis showing O—H···O and C—H···O hydrogen bonds as dashed lines.

(1'S,2R,2'R,3'S,6'R)-3'-ethyl-4-methyl- 5H-5'-oxa-10'-azaspiro[furan-2,4'-tricyclo[8.3.0.0^2,6]tridecane]- 5,11'-dione hemihydrate top

Crystal data top

C₁₇H₂₃NO₄·0.5H₂O	F(000) = 1352
M_r = 314.37	D_x = 1.237 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4774 reflections
a = 8.6412 (2) Å	θ = 3.7–62.5°
b = 10.7998 (2) Å	µ = 0.73 mm⁻¹
c = 36.1685 (7) Å	T = 298 K
V = 3375.36 (12) Å³	Block, colorless
Z = 8	0.42 × 0.30 × 0.27 mm

Data collection top

Oxford Diffraction Gemini S Ultra CCD diffractometer	4837 independent reflections
Radiation source: fine-focus sealed tube	4514 reflections with I > 2˘I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 62.6°, θ_min = 4.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
T_min = 0.822, T_max = 1.000	k = −12→10
8573 measured reflections	l = −19→41

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0913P)² + 0.4948P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4837 reflections	Δρ_max = 0.51 e Å⁻³
412 parameters	Δρ_min = −0.24 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1743 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.1 (2)

Crystal data top

C₁₇H₂₃NO₄·0.5H₂O	V = 3375.36 (12) Å³
M_r = 314.37	Z = 8
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 8.6412 (2) Å	µ = 0.73 mm⁻¹
b = 10.7998 (2) Å	T = 298 K
c = 36.1685 (7) Å	0.42 × 0.30 × 0.27 mm

Data collection top

Oxford Diffraction Gemini S Ultra CCD diffractometer	4837 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	4514 reflections with I > 2˘I)
T_min = 0.822, T_max = 1.000	R_int = 0.021
8573 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.142	Δρ_max = 0.51 e Å⁻³
S = 1.06	Δρ_min = −0.24 e Å⁻³
4837 reflections	Absolute structure: Flack (1983), 1743 Friedel pairs
412 parameters	Absolute structure parameter: −0.1 (2)
2 restraints

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'	0.3987 (3)	0.6908 (2)	0.08626 (7)	0.0818 (7)
O2'	0.9749 (2)	0.7450 (2)	0.18688 (6)	0.0688 (6)
O3'	1.0512 (3)	0.9441 (2)	0.20168 (6)	0.0792 (7)
O4'	1.2437 (4)	1.0530 (3)	0.22680 (11)	0.1210 (12)
C1'	0.4852 (4)	0.7634 (3)	0.18058 (9)	0.0663 (8)
H1'A	0.4397	0.8047	0.2018	0.080*
H1'B	0.5442	0.6924	0.1890	0.080*
C2'	0.3601 (4)	0.7249 (4)	0.15240 (10)	0.0828 (10)
H2'A	0.3262	0.6405	0.1567	0.099*
H2'B	0.2713	0.7797	0.1537	0.099*
C3'	0.4403 (3)	0.7360 (3)	0.11593 (9)	0.0614 (7)
N4'	0.5691 (3)	0.8034 (2)	0.12056 (6)	0.0530 (5)
C5'	0.6762 (4)	0.8299 (3)	0.09050 (7)	0.0583 (7)
H5'A	0.7141	0.9140	0.0931	0.070*
H5'B	0.6214	0.8244	0.0672	0.070*
C6'	0.8127 (4)	0.7416 (3)	0.08984 (7)	0.0617 (7)
H6'A	0.7732	0.6575	0.0902	0.074*
H6'B	0.8673	0.7527	0.0666	0.074*
C7'	0.9266 (3)	0.7555 (3)	0.12079 (8)	0.0612 (7)
H7'A	0.9796	0.8341	0.1181	0.073*
H7'B	1.0035	0.6904	0.1188	0.073*
C8'	0.8538 (3)	0.7500 (3)	0.15902 (7)	0.0513 (6)
H8'A	0.7900	0.6752	0.1609	0.062*
C9'	0.7566 (3)	0.8615 (2)	0.16928 (7)	0.0477 (6)
H9'A	0.8006	0.9338	0.1567	0.057*
C9A'	0.5859 (3)	0.8521 (2)	0.15822 (7)	0.0514 (6)
H9AB	0.5397	0.9349	0.1592	0.062*
C10'	0.7858 (4)	0.8767 (3)	0.21083 (7)	0.0547 (6)
H10B	0.7249	0.8140	0.2239	0.066*
C11'	0.9562 (4)	0.8396 (3)	0.21282 (8)	0.0596 (7)
C12'	1.0220 (4)	0.8032 (3)	0.24871 (9)	0.0681 (8)
H12B	0.9854	0.7383	0.2632	0.082*
C13'	1.1403 (4)	0.8751 (4)	0.25765 (9)	0.0762 (9)
C14'	1.1569 (4)	0.9670 (4)	0.22847 (11)	0.0810 (10)
C15'	1.2413 (6)	0.8803 (6)	0.29114 (12)	0.1187 (17)
H15D	1.2159	0.8129	0.3073	0.178*
H15E	1.2251	0.9574	0.3038	0.178*
H15F	1.3478	0.8739	0.2838	0.178*
C16'	0.7445 (6)	1.0033 (4)	0.22668 (10)	0.0858 (11)
H16C	0.8230	1.0618	0.2188	0.103*
H16D	0.6473	1.0294	0.2158	0.103*
C17'	0.7300 (10)	1.0123 (6)	0.26649 (16)	0.157 (3)
H17D	0.7049	1.0960	0.2732	0.236*
H17E	0.8260	0.9891	0.2779	0.236*
H17F	0.6493	0.9579	0.2748	0.236*
O1	−0.0168 (3)	0.5873 (2)	0.01640 (7)	0.0779 (6)
O2	−0.5911 (2)	0.31108 (18)	−0.03973 (5)	0.0528 (4)
O3	−0.6774 (2)	0.36455 (16)	−0.09836 (5)	0.0564 (5)
O4	−0.8917 (3)	0.3499 (2)	−0.13237 (6)	0.0742 (6)
C1	−0.1041 (3)	0.3420 (3)	−0.04581 (9)	0.0591 (7)
H1A	−0.1618	0.2844	−0.0305	0.071*
H1B	−0.0599	0.2974	−0.0665	0.071*
C2	0.0210 (3)	0.4071 (3)	−0.02354 (9)	0.0595 (7)
H2A	0.0564	0.3556	−0.0033	0.071*
H2B	0.1087	0.4283	−0.0390	0.071*
C3	−0.0582 (3)	0.5213 (3)	−0.00945 (8)	0.0545 (6)
N4	−0.1863 (2)	0.5401 (2)	−0.02972 (6)	0.0515 (5)
C5	−0.2939 (3)	0.6411 (3)	−0.02211 (9)	0.0610 (7)
H5A	−0.3387	0.6697	−0.0452	0.073*
H5B	−0.2378	0.7097	−0.0111	0.073*
C6	−0.4218 (3)	0.6016 (3)	0.00366 (9)	0.0610 (7)
H6A	−0.4763	0.6751	0.0120	0.073*
H6B	−0.3755	0.5633	0.0252	0.073*
C7	−0.5400 (3)	0.5116 (3)	−0.01270 (8)	0.0544 (7)
H7A	−0.6114	0.4867	0.0066	0.065*
H7B	−0.5992	0.5543	−0.0316	0.065*
C8	−0.4694 (3)	0.3976 (2)	−0.02940 (7)	0.0437 (5)
H8A	−0.4020	0.3583	−0.0111	0.052*
C9	−0.3777 (3)	0.4177 (2)	−0.06508 (7)	0.0457 (6)
H9A	−0.4245	0.4879	−0.0781	0.055*
C9A	−0.2073 (3)	0.4480 (2)	−0.05906 (7)	0.0493 (6)
H9AA	−0.1645	0.4812	−0.0821	0.059*
C10	−0.4123 (3)	0.3013 (3)	−0.08746 (7)	0.0529 (6)
H10A	−0.3504	0.2334	−0.0772	0.063*
C11	−0.5799 (3)	0.2795 (2)	−0.07690 (7)	0.0500 (6)
C12	−0.6566 (3)	0.1570 (2)	−0.08304 (8)	0.0576 (7)
H12A	−0.6192	0.0819	−0.0742	0.069*
C13	−0.7846 (3)	0.1697 (2)	−0.10266 (7)	0.0536 (6)
C14	−0.7969 (3)	0.3011 (2)	−0.11322 (7)	0.0523 (6)
C15	−0.9043 (4)	0.0787 (3)	−0.11504 (10)	0.0691 (8)
H15A	−0.8783	−0.0022	−0.1059	0.104*
H15B	−0.9079	0.0770	−0.1416	0.104*
H15C	−1.0036	0.1028	−0.1056	0.104*
C16	−0.3768 (5)	0.3105 (4)	−0.12896 (9)	0.0858 (11)
H16A	−0.4557	0.3617	−0.1404	0.103*
H16B	−0.2787	0.3530	−0.1319	0.103*
C17	−0.3690 (9)	0.1966 (7)	−0.14874 (13)	0.158 (3)
H17A	−0.3458	0.2129	−0.1742	0.238*
H17B	−0.4666	0.1546	−0.1470	0.238*
H17C	−0.2892	0.1455	−0.1383	0.238*
O1W	0.1914 (4)	0.5014 (3)	0.06972 (10)	0.1025 (9)
H1WA	0.128 (6)	0.529 (6)	0.0552 (14)	0.154*
H1WB	0.256 (6)	0.553 (5)	0.0765 (16)	0.154*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1'	0.0742 (14)	0.0875 (15)	0.0837 (14)	−0.0204 (13)	−0.0242 (12)	−0.0017 (13)
O2'	0.0611 (12)	0.0800 (13)	0.0653 (11)	0.0199 (11)	−0.0105 (10)	−0.0137 (10)
O3'	0.0698 (14)	0.0857 (15)	0.0821 (14)	−0.0206 (13)	−0.0149 (12)	0.0174 (13)
O4'	0.091 (2)	0.112 (2)	0.160 (3)	−0.042 (2)	−0.032 (2)	0.014 (2)
C1'	0.0494 (15)	0.082 (2)	0.0676 (16)	−0.0068 (16)	0.0064 (14)	0.0036 (15)
C2'	0.0488 (17)	0.102 (3)	0.098 (2)	−0.0145 (18)	0.0042 (17)	0.005 (2)
C3'	0.0522 (15)	0.0579 (16)	0.0743 (18)	−0.0020 (14)	−0.0125 (15)	0.0050 (14)
N4'	0.0514 (12)	0.0490 (11)	0.0584 (12)	−0.0085 (10)	−0.0059 (10)	0.0023 (10)
C5'	0.0723 (18)	0.0559 (15)	0.0468 (13)	−0.0160 (15)	−0.0060 (13)	0.0078 (11)
C6'	0.0733 (19)	0.0614 (16)	0.0504 (13)	−0.0130 (16)	0.0116 (14)	−0.0043 (12)
C7'	0.0525 (15)	0.0713 (17)	0.0600 (15)	−0.0030 (14)	0.0116 (14)	−0.0109 (14)
C8'	0.0498 (14)	0.0514 (13)	0.0527 (13)	0.0004 (12)	−0.0008 (12)	−0.0050 (11)
C9'	0.0488 (14)	0.0443 (13)	0.0499 (12)	−0.0011 (11)	0.0021 (11)	−0.0011 (10)
C9A'	0.0452 (14)	0.0500 (14)	0.0590 (13)	0.0032 (12)	−0.0023 (11)	−0.0015 (12)
C10'	0.0597 (16)	0.0550 (15)	0.0495 (13)	−0.0005 (14)	0.0021 (12)	−0.0034 (12)
C11'	0.0627 (17)	0.0599 (17)	0.0562 (14)	−0.0039 (15)	−0.0038 (13)	−0.0001 (13)
C12'	0.078 (2)	0.0655 (18)	0.0606 (15)	−0.0022 (17)	−0.0118 (15)	0.0012 (14)
C13'	0.077 (2)	0.081 (2)	0.0708 (18)	−0.0006 (19)	−0.0223 (17)	−0.0044 (17)
C14'	0.063 (2)	0.083 (2)	0.097 (3)	−0.0072 (19)	−0.0125 (18)	−0.006 (2)
C15'	0.115 (4)	0.149 (4)	0.092 (3)	−0.008 (3)	−0.049 (3)	−0.011 (3)
C16'	0.113 (3)	0.071 (2)	0.073 (2)	0.017 (2)	0.002 (2)	−0.0231 (16)
C17'	0.199 (7)	0.147 (5)	0.126 (4)	0.035 (5)	0.007 (5)	−0.050 (4)
O1	0.0652 (13)	0.0750 (14)	0.0937 (15)	−0.0013 (12)	−0.0213 (12)	−0.0129 (12)
O2	0.0478 (10)	0.0594 (10)	0.0513 (9)	−0.0123 (9)	0.0013 (8)	−0.0019 (8)
O3	0.0622 (11)	0.0405 (9)	0.0666 (10)	−0.0009 (9)	−0.0147 (9)	0.0045 (8)
O4	0.0718 (13)	0.0615 (12)	0.0894 (14)	−0.0005 (11)	−0.0272 (12)	0.0171 (11)
C1	0.0472 (14)	0.0535 (15)	0.0766 (17)	0.0057 (13)	0.0086 (14)	−0.0014 (13)
C2	0.0387 (13)	0.0603 (16)	0.0796 (17)	0.0042 (12)	0.0029 (13)	0.0114 (14)
C3	0.0432 (13)	0.0489 (14)	0.0715 (16)	−0.0047 (12)	−0.0008 (13)	0.0056 (13)
N4	0.0423 (11)	0.0430 (11)	0.0694 (13)	0.0004 (10)	−0.0003 (10)	0.0047 (10)
C5	0.0508 (14)	0.0412 (13)	0.0910 (19)	0.0048 (12)	−0.0096 (15)	−0.0014 (13)
C6	0.0551 (16)	0.0517 (15)	0.0762 (17)	0.0089 (13)	−0.0022 (14)	−0.0142 (14)
C7	0.0451 (14)	0.0561 (15)	0.0621 (15)	0.0054 (12)	0.0043 (12)	−0.0048 (12)
C8	0.0390 (12)	0.0449 (12)	0.0471 (12)	−0.0019 (11)	−0.0027 (10)	0.0023 (10)
C9	0.0458 (12)	0.0465 (13)	0.0449 (12)	0.0005 (11)	0.0003 (11)	0.0059 (10)
C9A	0.0465 (13)	0.0511 (14)	0.0504 (13)	−0.0016 (12)	0.0086 (11)	0.0050 (11)
C10	0.0575 (15)	0.0511 (13)	0.0501 (13)	0.0047 (13)	0.0009 (12)	−0.0020 (11)
C11	0.0543 (15)	0.0437 (13)	0.0520 (13)	0.0039 (12)	−0.0072 (12)	0.0008 (11)
C12	0.0657 (17)	0.0416 (13)	0.0656 (15)	0.0039 (13)	−0.0101 (14)	0.0035 (12)
C13	0.0589 (15)	0.0397 (13)	0.0621 (14)	0.0011 (12)	−0.0061 (13)	−0.0011 (11)
C14	0.0556 (15)	0.0461 (13)	0.0553 (13)	0.0025 (13)	−0.0057 (13)	0.0019 (11)
C15	0.0646 (18)	0.0528 (16)	0.090 (2)	−0.0069 (15)	−0.0156 (17)	−0.0028 (15)
C16	0.102 (3)	0.097 (3)	0.0583 (17)	0.010 (2)	0.0197 (19)	−0.0043 (17)
C17	0.192 (6)	0.202 (6)	0.081 (3)	0.027 (6)	0.009 (4)	−0.047 (4)
O1W	0.104 (2)	0.0833 (18)	0.120 (2)	−0.0337 (17)	−0.0342 (18)	0.0232 (15)

Geometric parameters (Å, º) top

O1'—C3'	1.233 (4)	O2—C11	1.390 (3)
O2'—C11'	1.396 (4)	O2—C8	1.455 (3)
O2'—C8'	1.454 (3)	O3—C14	1.351 (3)
O3'—C14'	1.354 (4)	O3—C11	1.468 (3)
O3'—C11'	1.453 (4)	O4—C14	1.195 (3)
O4'—C14'	1.195 (5)	C1—C2	1.521 (4)
C1'—C9A'	1.525 (4)	C1—C9A	1.528 (4)
C1'—C2'	1.542 (5)	C1—H1A	0.9700
C1'—H1'A	0.9700	C1—H1B	0.9700
C1'—H1'B	0.9700	C2—C3	1.499 (4)
C2'—C3'	1.495 (5)	C2—H2A	0.9700
C2'—H2'A	0.9700	C2—H2B	0.9700
C2'—H2'B	0.9700	C3—N4	1.343 (4)
C3'—N4'	1.340 (4)	N4—C5	1.460 (3)
N4'—C5'	1.456 (4)	N4—C9A	1.466 (3)
N4'—C9A'	1.467 (3)	C5—C6	1.507 (4)
C5'—C6'	1.517 (4)	C5—H5A	0.9700
C5'—H5'A	0.9700	C5—H5B	0.9700
C5'—H5'B	0.9700	C6—C7	1.529 (4)
C6'—C7'	1.498 (4)	C6—H6A	0.9700
C6'—H6'A	0.9700	C6—H6B	0.9700
C6'—H6'B	0.9700	C7—C8	1.501 (4)
C7'—C8'	1.520 (4)	C7—H7A	0.9700
C7'—H7'A	0.9700	C7—H7B	0.9700
C7'—H7'B	0.9700	C8—C9	1.530 (3)
C8'—C9'	1.515 (4)	C8—H8A	0.9800
C8'—H8'A	0.9800	C9—C10	1.524 (4)
C9'—C9A'	1.532 (4)	C9—C9A	1.524 (4)
C9'—C10'	1.533 (3)	C9—H9A	0.9800
C9'—H9'A	0.9800	C9A—H9AA	0.9800
C9A'—H9AB	0.9800	C10—C11	1.517 (4)
C10'—C16'	1.525 (4)	C10—C16	1.535 (4)
C10'—C11'	1.528 (4)	C10—H10A	0.9800
C10'—H10B	0.9800	C11—C12	1.496 (4)
C11'—C12'	1.470 (4)	C12—C13	1.321 (4)
C12'—C13'	1.324 (5)	C12—H12A	0.9300
C12'—H12B	0.9300	C13—C14	1.473 (4)
C13'—C14'	1.456 (5)	C13—C15	1.496 (4)
C13'—C15'	1.494 (5)	C15—H15A	0.9600
C15'—H15D	0.9600	C15—H15B	0.9600
C15'—H15E	0.9600	C15—H15C	0.9600
C15'—H15F	0.9600	C16—C17	1.425 (7)
C16'—C17'	1.449 (6)	C16—H16A	0.9700
C16'—H16C	0.9700	C16—H16B	0.9700
C16'—H16D	0.9700	C17—H17A	0.9600
C17'—H17D	0.9600	C17—H17B	0.9600
C17'—H17E	0.9600	C17—H17C	0.9600
C17'—H17F	0.9600	O1W—H1WA	0.81 (2)
O1—C3	1.229 (4)	O1W—H1WB	0.82 (2)

C11'—O2'—C8'	110.8 (2)	C14—O3—C11	109.35 (19)
C14'—O3'—C11'	108.9 (3)	C2—C1—C9A	103.5 (2)
C9A'—C1'—C2'	102.6 (3)	C2—C1—H1A	111.1
C9A'—C1'—H1'A	111.2	C9A—C1—H1A	111.1
C2'—C1'—H1'A	111.2	C2—C1—H1B	111.1
C9A'—C1'—H1'B	111.2	C9A—C1—H1B	111.1
C2'—C1'—H1'B	111.2	H1A—C1—H1B	109.0
H1'A—C1'—H1'B	109.2	C3—C2—C1	103.6 (2)
C3'—C2'—C1'	103.7 (2)	C3—C2—H2A	111.0
C3'—C2'—H2'A	111.0	C1—C2—H2A	111.0
C1'—C2'—H2'A	111.0	C3—C2—H2B	111.0
C3'—C2'—H2'B	111.0	C1—C2—H2B	111.0
C1'—C2'—H2'B	111.0	H2A—C2—H2B	109.0
H2'A—C2'—H2'B	109.0	O1—C3—N4	124.6 (3)
O1'—C3'—N4'	124.5 (3)	O1—C3—C2	127.0 (3)
O1'—C3'—C2'	126.9 (3)	N4—C3—C2	108.4 (2)
N4'—C3'—C2'	108.6 (3)	C3—N4—C5	122.3 (2)
C3'—N4'—C5'	122.8 (2)	C3—N4—C9A	113.2 (2)
C3'—N4'—C9A'	113.1 (2)	C5—N4—C9A	124.4 (2)
C5'—N4'—C9A'	124.0 (2)	N4—C5—C6	111.9 (2)
N4'—C5'—C6'	112.5 (2)	N4—C5—H5A	109.2
N4'—C5'—H5'A	109.1	C6—C5—H5A	109.2
C6'—C5'—H5'A	109.1	N4—C5—H5B	109.2
N4'—C5'—H5'B	109.1	C6—C5—H5B	109.2
C6'—C5'—H5'B	109.1	H5A—C5—H5B	107.9
H5'A—C5'—H5'B	107.8	C5—C6—C7	115.5 (2)
C7'—C6'—C5'	115.9 (2)	C5—C6—H6A	108.4
C7'—C6'—H6'A	108.3	C7—C6—H6A	108.4
C5'—C6'—H6'A	108.3	C5—C6—H6B	108.4
C7'—C6'—H6'B	108.3	C7—C6—H6B	108.4
C5'—C6'—H6'B	108.3	H6A—C6—H6B	107.5
H6'A—C6'—H6'B	107.4	C8—C7—C6	113.9 (2)
C6'—C7'—C8'	113.8 (2)	C8—C7—H7A	108.8
C6'—C7'—H7'A	108.8	C6—C7—H7A	108.8
C8'—C7'—H7'A	108.8	C8—C7—H7B	108.8
C6'—C7'—H7'B	108.8	C6—C7—H7B	108.8
C8'—C7'—H7'B	108.8	H7A—C7—H7B	107.7
H7'A—C7'—H7'B	107.7	O2—C8—C7	109.7 (2)
O2'—C8'—C9'	105.0 (2)	O2—C8—C9	104.40 (18)
O2'—C8'—C7'	109.5 (2)	C7—C8—C9	115.7 (2)
C9'—C8'—C7'	114.9 (2)	O2—C8—H8A	108.9
O2'—C8'—H8'A	109.1	C7—C8—H8A	108.9
C9'—C8'—H8'A	109.1	C9—C8—H8A	108.9
C7'—C8'—H8'A	109.1	C10—C9—C9A	116.2 (2)
C8'—C9'—C9A'	114.6 (2)	C10—C9—C8	103.3 (2)
C8'—C9'—C10'	103.5 (2)	C9A—C9—C8	114.2 (2)
C9A'—C9'—C10'	114.9 (2)	C10—C9—H9A	107.5
C8'—C9'—H9'A	107.8	C9A—C9—H9A	107.5
C9A'—C9'—H9'A	107.8	C8—C9—H9A	107.5
C10'—C9'—H9'A	107.8	N4—C9A—C9	111.6 (2)
N4'—C9A'—C1'	102.2 (2)	N4—C9A—C1	102.1 (2)
N4'—C9A'—C9'	111.2 (2)	C9—C9A—C1	116.6 (2)
C1'—C9A'—C9'	116.9 (2)	N4—C9A—H9AA	108.7
N4'—C9A'—H9AB	108.7	C9—C9A—H9AA	108.7
C1'—C9A'—H9AB	108.7	C1—C9A—H9AA	108.7
C9'—C9A'—H9AB	108.7	C11—C10—C9	100.5 (2)
C16'—C10'—C11'	116.3 (3)	C11—C10—C16	116.5 (3)
C16'—C10'—C9'	115.2 (3)	C9—C10—C16	115.3 (3)
C11'—C10'—C9'	100.2 (2)	C11—C10—H10A	108.0
C16'—C10'—H10B	108.2	C9—C10—H10A	108.0
C11'—C10'—H10B	108.2	C16—C10—H10A	108.0
C9'—C10'—H10B	108.2	O2—C11—O3	108.5 (2)
O2'—C11'—O3'	108.5 (2)	O2—C11—C12	109.3 (2)
O2'—C11'—C12'	110.7 (3)	O3—C11—C12	102.7 (2)
O3'—C11'—C12'	103.6 (2)	O2—C11—C10	105.8 (2)
O2'—C11'—C10'	105.7 (2)	O3—C11—C10	108.5 (2)
O3'—C11'—C10'	109.1 (2)	C12—C11—C10	121.6 (2)
C12'—C11'—C10'	119.0 (3)	C13—C12—C11	111.0 (2)
C13'—C12'—C11'	110.9 (3)	C13—C12—H12A	124.5
C13'—C12'—H12B	124.5	C11—C12—H12A	124.5
C11'—C12'—H12B	124.5	C12—C13—C14	107.5 (2)
C12'—C13'—C14'	107.4 (3)	C12—C13—C15	132.2 (3)
C12'—C13'—C15'	132.1 (4)	C14—C13—C15	120.4 (2)
C14'—C13'—C15'	120.3 (4)	O4—C14—O3	122.0 (2)
O4'—C14'—O3'	121.9 (4)	O4—C14—C13	128.7 (3)
O4'—C14'—C13'	128.9 (4)	O3—C14—C13	109.3 (2)
O3'—C14'—C13'	109.1 (3)	C13—C15—H15A	109.5
C13'—C15'—H15D	109.5	C13—C15—H15B	109.5
C13'—C15'—H15E	109.5	H15A—C15—H15B	109.5
H15D—C15'—H15E	109.5	C13—C15—H15C	109.5
C13'—C15'—H15F	109.5	H15A—C15—H15C	109.5
H15D—C15'—H15F	109.5	H15B—C15—H15C	109.5
H15E—C15'—H15F	109.5	C17—C16—C10	116.4 (4)
C17'—C16'—C10'	117.0 (4)	C17—C16—H16A	108.2
C17'—C16'—H16C	108.0	C10—C16—H16A	108.2
C10'—C16'—H16C	108.0	C17—C16—H16B	108.2
C17'—C16'—H16D	108.0	C10—C16—H16B	108.2
C10'—C16'—H16D	108.0	H16A—C16—H16B	107.3
H16C—C16'—H16D	107.3	C16—C17—H17A	109.5
C16'—C17'—H17D	109.5	C16—C17—H17B	109.5
C16'—C17'—H17E	109.5	H17A—C17—H17B	109.5
H17D—C17'—H17E	109.5	C16—C17—H17C	109.5
C16'—C17'—H17F	109.5	H17A—C17—H17C	109.5
H17D—C17'—H17F	109.5	H17B—C17—H17C	109.5
H17E—C17'—H17F	109.5	H1WA—O1W—H1WB	113 (6)
C11—O2—C8	110.84 (19)

C9A'—C1'—C2'—C3'	28.3 (4)	C9A—C1—C2—C3	28.4 (3)
C1'—C2'—C3'—O1'	163.4 (3)	C1—C2—C3—O1	161.7 (3)
C1'—C2'—C3'—N4'	−15.8 (4)	C1—C2—C3—N4	−17.6 (3)
O1'—C3'—N4'—C5'	−0.5 (5)	O1—C3—N4—C5	−2.0 (4)
C2'—C3'—N4'—C5'	178.8 (3)	C2—C3—N4—C5	177.3 (2)
O1'—C3'—N4'—C9A'	176.5 (3)	O1—C3—N4—C9A	179.5 (3)
C2'—C3'—N4'—C9A'	−4.2 (3)	C2—C3—N4—C9A	−1.3 (3)
C3'—N4'—C5'—C6'	−97.1 (3)	C3—N4—C5—C6	−91.8 (3)
C9A'—N4'—C5'—C6'	86.2 (3)	C9A—N4—C5—C6	86.6 (3)
N4'—C5'—C6'—C7'	−69.8 (3)	N4—C5—C6—C7	−70.3 (3)
C5'—C6'—C7'—C8'	53.7 (4)	C5—C6—C7—C8	53.6 (3)
C11'—O2'—C8'—C9'	1.6 (3)	C11—O2—C8—C7	124.5 (2)
C11'—O2'—C8'—C7'	125.5 (3)	C11—O2—C8—C9	0.0 (3)
C6'—C7'—C8'—O2'	171.3 (3)	C6—C7—C8—O2	172.6 (2)
C6'—C7'—C8'—C9'	−70.9 (3)	C6—C7—C8—C9	−69.7 (3)
O2'—C8'—C9'—C9A'	−150.5 (2)	O2—C8—C9—C10	−23.5 (2)
C7'—C8'—C9'—C9A'	89.2 (3)	C7—C8—C9—C10	−144.1 (2)
O2'—C8'—C9'—C10'	−24.5 (3)	O2—C8—C9—C9A	−150.7 (2)
C7'—C8'—C9'—C10'	−144.9 (2)	C7—C8—C9—C9A	88.7 (3)
C3'—N4'—C9A'—C1'	22.5 (3)	C3—N4—C9A—C9	144.6 (2)
C5'—N4'—C9A'—C1'	−160.5 (2)	C5—N4—C9A—C9	−33.9 (3)
C3'—N4'—C9A'—C9'	147.9 (2)	C3—N4—C9A—C1	19.3 (3)
C5'—N4'—C9A'—C9'	−35.1 (3)	C5—N4—C9A—C1	−159.2 (2)
C2'—C1'—C9A'—N4'	−30.1 (3)	C10—C9—C9A—N4	−164.9 (2)
C2'—C1'—C9A'—C9'	−151.7 (3)	C8—C9—C9A—N4	−44.8 (3)
C8'—C9'—C9A'—N4'	−44.1 (3)	C10—C9—C9A—C1	−48.2 (3)
C10'—C9'—C9A'—N4'	−163.9 (2)	C8—C9—C9A—C1	72.0 (3)
C8'—C9'—C9A'—C1'	72.6 (3)	C2—C1—C9A—N4	−28.6 (3)
C10'—C9'—C9A'—C1'	−47.2 (3)	C2—C1—C9A—C9	−150.5 (2)
C8'—C9'—C10'—C16'	161.7 (3)	C9A—C9—C10—C11	162.2 (2)
C9A'—C9'—C10'—C16'	−72.5 (4)	C8—C9—C10—C11	36.3 (2)
C8'—C9'—C10'—C11'	36.2 (3)	C9A—C9—C10—C16	−71.6 (3)
C9A'—C9'—C10'—C11'	161.9 (2)	C8—C9—C10—C16	162.5 (3)
C8'—O2'—C11'—O3'	−94.7 (3)	C8—O2—C11—O3	−92.3 (2)
C8'—O2'—C11'—C12'	152.3 (3)	C8—O2—C11—C12	156.4 (2)
C8'—O2'—C11'—C10'	22.2 (3)	C8—O2—C11—C10	24.0 (3)
C14'—O3'—C11'—O2'	−118.9 (3)	C14—O3—C11—O2	−113.1 (2)
C14'—O3'—C11'—C12'	−1.3 (4)	C14—O3—C11—C12	2.5 (3)
C14'—O3'—C11'—C10'	126.3 (3)	C14—O3—C11—C10	132.4 (2)
C16'—C10'—C11'—O2'	−160.9 (3)	C9—C10—C11—O2	−37.4 (2)
C9'—C10'—C11'—O2'	−36.0 (3)	C16—C10—C11—O2	−162.7 (3)
C16'—C10'—C11'—O3'	−44.4 (3)	C9—C10—C11—O3	78.8 (2)
C9'—C10'—C11'—O3'	80.5 (3)	C16—C10—C11—O3	−46.4 (3)
C16'—C10'—C11'—C12'	74.0 (4)	C9—C10—C11—C12	−162.6 (2)
C9'—C10'—C11'—C12'	−161.1 (3)	C16—C10—C11—C12	72.2 (4)
O2'—C11'—C12'—C13'	115.6 (3)	O2—C11—C12—C13	111.1 (3)
O3'—C11'—C12'—C13'	−0.4 (4)	O3—C11—C12—C13	−4.0 (3)
C10'—C11'—C12'—C13'	−121.7 (3)	C10—C11—C12—C13	−125.3 (3)
C11'—C12'—C13'—C14'	1.9 (4)	C11—C12—C13—C14	3.8 (3)
C11'—C12'—C13'—C15'	177.3 (4)	C11—C12—C13—C15	−177.6 (3)
C11'—O3'—C14'—O4'	−175.9 (4)	C11—O3—C14—O4	−179.0 (3)
C11'—O3'—C14'—C13'	2.5 (4)	C11—O3—C14—C13	−0.5 (3)
C12'—C13'—C14'—O4'	175.5 (5)	C12—C13—C14—O4	176.3 (3)
C15'—C13'—C14'—O4'	−0.6 (7)	C15—C13—C14—O4	−2.5 (5)
C12'—C13'—C14'—O3'	−2.7 (4)	C12—C13—C14—O3	−2.1 (3)
C15'—C13'—C14'—O3'	−178.8 (4)	C15—C13—C14—O3	179.1 (2)
C11'—C10'—C16'—C17'	−79.4 (6)	C11—C10—C16—C17	−78.4 (5)
C9'—C10'—C16'—C17'	163.8 (5)	C9—C10—C16—C17	164.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.81	1.98	2.796 (3)	175
O1W—H1WB···O1′	0.83	1.97	2.784 (3)	171
C5′—H5′A···O3ⁱ	0.97	2.58	3.545 (4)	178
C10—H10A···O1Wⁱⁱ	0.98	2.58	3.450 (4)	149

Symmetry codes: (i) x+3/2, −y+3/2, −z; (ii) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₃NO₄·0.5H₂O
M_r	314.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	8.6412 (2), 10.7998 (2), 36.1685 (7)
V (Å³)	3375.36 (12)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.42 × 0.30 × 0.27

Data collection
Diffractometer	Oxford Diffraction Gemini S Ultra CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.822, 1.000
No. of measured, independent and observed [I > 2˘I)] reflections	8573, 4837, 4514
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.576

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.142, 1.06
No. of reflections	4837
No. of parameters	412
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)	0.51, −0.24
Absolute structure	Flack (1983), 1743 Friedel pairs
Absolute structure parameter	−0.1 (2)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.814	1.984	2.796 (3)	174.8
O1W—H1WB···O1'	0.825	1.966	2.784 (3)	171.4
C5'—H5'A···O3ⁱ	0.970	2.575	3.545 (4)	178.0
C10—H10A···O1Wⁱⁱ	0.980	2.576	3.450 (4)	148.5

Symmetry codes: (i) x+3/2, −y+3/2, −z; (ii) x−1/2, −y+1/2, −z.

Acknowledgements

This work was supported by a grant from the New Century Excellent Talents Scheme of the Ministry of Education (grant No. NCET-08–0612), the Guangdong High Level Talent Scheme (to RWJ) and the Fundamental Research Funds for the Central Universities (grant No. 21609202)

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