1-[4-(β-d-Allopyranos­yloxy)benzyl­idene]semicarbazide hemihydrate

Chen, H.-F.; Bai, X.; Zhang, K.; Li, Y.; Yin, S.-F.

doi:10.1107/S1600536809055664

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o321

https://doi.org/10.1107/S1600536809055664

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1-[4-(β-D-Allopyranosyloxy)benzylidene]semicarbazide hemihydrate

Hua-Feng Chen,^a Xue Bai,^a Kuan Zhang,^a Ying Li ^a ^* and Shu-Fan Yin ^a

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: chuandayouji217@163.com

(Received 29 November 2009; accepted 29 December 2009; online 9 January 2010)

The molecule of the title compound, C₁₄H₁₉N₃O₇·0.5H₂O, exhibits an E conformation about the C=N double bond. The water molecule possesses crystallographically imposed twofold symmetry. In the crystal structure, the molecules are connected by intermolecular O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the properties of helicid (systematic name: 4-formylphenl-β-D-allopyranoside), see: Chen et al. (1981 ); Sha & Mao (1987 ). For the synthesis of the title compound, see: Zhu et al. (2008 ). For related structures, see: Fan et al. (2007 ); Yang et al. (2008 )

Experimental

Crystal data

C₁₄H₁₉N₃O₇·0.5H₂O
M_r = 350.33
Trigonal, P 3₁ 21
a = 8.6373 (12) Å
c = 37.021 (7) Å
V = 2391.8 (7) Å³
Z = 6
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 113 K
0.28 × 0.25 × 0.21 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.967, T_max = 0.975
15783 measured reflections
2242 independent reflections
2161 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.09
2242 reflections
235 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O7ⁱ	0.84	1.85	2.6905 (19)	175
O3—H3⋯O8ⁱⁱ	0.84	1.94	2.7447 (16)	159
O4—H4⋯O5ⁱⁱⁱ	0.84	2.05	2.8277 (19)	154
O4—H4⋯O5	0.84	2.34	2.7725 (19)	113
O5—H5⋯O2^iv	0.84	1.85	2.693 (2)	178
N3—H3A⋯O4^v	0.88	2.24	3.096 (2)	165
N3—H3A⋯O3^v	0.88	2.46	2.896 (2)	111
O8—H8O⋯O7^vi	0.84 (3)	1.95 (3)	2.7163 (17)	151 (4)
N2—H2N⋯O3^vii	0.88 (3)	2.14 (3)	3.014 (2)	176 (2)
Symmetry codes: (i) $[-x+y, -x+2, z-{\script{1\over 3}}]$ ; (ii) $[-x+y, -x+1, z-{\script{1\over 3}}]$ ; (iii) $[-x+2, -x+y+1, -z+{\script{4\over 3}}]$ ; (iv) $[-x+1, -x+y, -z+{\script{4\over 3}}]$ ; (v) $[-y+2, x-y+1, z+{\script{1\over 3}}]$ ; (vi) x-1, y-1, z; (vii) $[-x+2, -x+y+2, -z+{\script{4\over 3}}]$ .

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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809055664/rz2403sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055664/rz2403Isup2.hkl

checkCIF report

Comment top

The natural product helicid, 4-formylphenl-β-D-allopyranoside, which is a major active ingredient of herbal medicine, is extracted from the fruit of Helicia nilagirica Beed growing at the Yunnan mountain of China (Chen et al., 1981). It has showed great biological effects on the central nervous system with low toxicity (Sha & Mao, 1987), and has been used to treating ache and insomnia for a long time. Some derivatives of this compound have been reported with good pharmacological activity (Fan et al., 2007; Yang et al., 2008). The title compound has been synthetized via condensation reaction of helicid and semicarbazide hydrochloride in ethanol (Zhu et al., 2008).

In this title compound (Fig. 1), the pyranoside ring adopts a stable chair conformation with the hydroxyl group at C3 in axial position and the other substituents at C1, C2 and C4 in equatorial position. The N1═C13 double bond in the molecule exhibits an E conformation, as indicated by the values of the C(13)–N(1)–N(2)–C(14) and C(11)–C(10)–C(13)–N(1) torsion angles of 176.28(0.19) and -160.45 (1/5)°, respectively. The average C–C bond lengths in the pyranoside ring is 1.52 (3) Å. The average C(sp³)–O and C(sp²)–O bond lengths are 1.426 (2) and 1.319 (2)Å, respectively. Intermolecular O—H···.O and N—H···.O hydrogen bonds (Table 1) are present in the crystal structure, generating a three-dimensional network.

Related literature top

For the properties of helicid (systematic name: 4-formylphenl-β-D-allopyranoside), see: Chen et al. (1981); Sha & Mao (1987). For the synthesis of the title compound, see: Zhu et al. (2008). For related structures, see: Fan et al. (2007); Yang et al. (2008)

Experimental top

Sodium acetate was added to a solution of semicarbazide hydrochloride (3.52 mmol) in water (5 ml) until pH 5–6. The solution was added to a solution of helicid (3.52 mmol) in ethanol (40 ml), then some drops of glacial acetic acid were added and the mixture was refluxed for 5 h. The reaction mixture was then cooled at room temperature. The colourless solid obtained was filtered, washed with water and recrystallized from ethanol/water (Zhu et al., 2008). Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol/water (5:1 v/v) solution at room temperature.

Structure description top

For the properties of helicid (systematic name: 4-formylphenl-β-D-allopyranoside), see: Chen et al. (1981); Sha & Mao (1987). For the synthesis of the title compound, see: Zhu et al. (2008). For related structures, see: Fan et al. (2007); Yang et al. (2008)

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. The water H atoms are related by the symmetry operation 1+x-y, 2-y, 5/3-z.

1-[4-(β-D-Allopyranosyloxy)benzylidene]semicarbazide hemihydrate top

Crystal data top

C₁₄H₁₉N₃O₇·0.5H₂O	D_x = 1.459 Mg m⁻³
M_r = 350.33	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 6972 reflections
Hall symbol: P 31 2"	θ = 2.7–27.9°
a = 8.6373 (12) Å	µ = 0.12 mm⁻¹
c = 37.021 (7) Å	T = 113 K
V = 2391.8 (7) Å³	Block, colourless
Z = 6	0.28 × 0.25 × 0.21 mm
F(000) = 1110

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2242 independent reflections
Radiation source: rotating anode	2161 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.038
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 2.7°
ω and φ scans	h = −8→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −11→8
T_min = 0.967, T_max = 0.975	l = −46→47
15783 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.034P)² + 1.0221P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2242 reflections	Δρ_max = 0.45 e Å⁻³
235 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0188 (16)

Crystal data top

C₁₄H₁₉N₃O₇·0.5H₂O	Z = 6
M_r = 350.33	Mo Kα radiation
Trigonal, P3₁21	µ = 0.12 mm⁻¹
a = 8.6373 (12) Å	T = 113 K
c = 37.021 (7) Å	0.28 × 0.25 × 0.21 mm
V = 2391.8 (7) Å³

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2242 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2161 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.975	R_int = 0.038
15783 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.45 e Å⁻³
2242 reflections	Δρ_min = −0.18 e Å⁻³
235 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
O1	0.61554 (18)	0.67753 (19)	0.64253 (3)	0.0159 (3)
O2	0.35880 (19)	0.6142 (2)	0.59033 (4)	0.0214 (3)
H2	0.3061	0.5826	0.5703	0.032*
O3	0.6592 (2)	0.4735 (2)	0.55878 (3)	0.0198 (3)
H3	0.5811	0.4704	0.5448	0.030*
O4	0.90103 (18)	0.5337 (2)	0.61006 (3)	0.0172 (3)
H4	0.9643	0.5345	0.6274	0.026*
O5	0.79887 (18)	0.41000 (19)	0.68003 (3)	0.0174 (3)
H5	0.7474	0.3599	0.6994	0.026*
O6	0.67202 (18)	0.64621 (18)	0.70151 (3)	0.0168 (3)
O7	1.4664 (2)	1.6732 (2)	0.85781 (4)	0.0209 (3)
O8	0.5415 (3)	1.0000	0.8333	0.0238 (5)
N1	1.1795 (2)	1.3137 (2)	0.80203 (4)	0.0184 (4)
N2	1.2921 (3)	1.4869 (2)	0.81373 (5)	0.0223 (4)
C6	0.5446 (3)	0.7359 (3)	0.58453 (5)	0.0186 (4)
H6A	0.5749	0.8567	0.5929	0.022*
H6B	0.5716	0.7429	0.5584	0.022*
N3	1.3533 (2)	1.3743 (2)	0.86433 (5)	0.0221 (4)
H3A	1.4048	1.3879	0.8855	0.027*
H3B	1.2877	1.2666	0.8552	0.027*
C1	0.6556 (3)	0.6741 (3)	0.60486 (5)	0.0151 (4)
H1	0.7854	0.7592	0.6005	0.018*
C2	0.6120 (3)	0.4842 (3)	0.59529 (5)	0.0157 (4)
H2A	0.4811	0.4004	0.5987	0.019*
C3	0.7162 (3)	0.4258 (3)	0.61925 (5)	0.0154 (4)
H3C	0.6766	0.2975	0.6143	0.018*
C4	0.6833 (3)	0.4471 (3)	0.65893 (5)	0.0147 (4)
H4A	0.5561	0.3603	0.6652	0.018*
C5	0.7213 (3)	0.6362 (3)	0.66559 (5)	0.0148 (4)
H5A	0.8511	0.7235	0.6618	0.018*
C7	0.7687 (2)	0.8103 (3)	0.71830 (5)	0.0152 (4)
C8	0.7913 (3)	0.8084 (3)	0.75549 (5)	0.0192 (4)
H8	0.7354	0.6986	0.7684	0.023*
C9	0.8963 (3)	0.9682 (3)	0.77356 (5)	0.0194 (4)
H9	0.9122	0.9672	0.7989	0.023*
C10	0.9789 (3)	1.1305 (3)	0.75499 (5)	0.0173 (4)
C11	0.9447 (3)	1.1300 (3)	0.71811 (5)	0.0179 (4)
H11	0.9930	1.2403	0.7055	0.021*
C12	0.8411 (3)	0.9710 (3)	0.69954 (5)	0.0172 (4)
H12	0.8200	0.9721	0.6744	0.021*
C13	1.1015 (3)	1.3027 (3)	0.77191 (5)	0.0182 (4)
H13	1.1240	1.4097	0.7601	0.022*
C14	1.3745 (3)	1.5160 (3)	0.84621 (5)	0.0167 (4)
H8O	0.555 (5)	0.913 (5)	0.8381 (10)	0.070 (12)*
H2N	1.304 (4)	1.579 (4)	0.8014 (7)	0.031 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0173 (7)	0.0204 (7)	0.0126 (6)	0.0114 (6)	−0.0008 (5)	−0.0020 (5)
O2	0.0171 (7)	0.0322 (9)	0.0146 (6)	0.0122 (7)	−0.0017 (5)	−0.0015 (6)
O3	0.0229 (8)	0.0301 (8)	0.0120 (6)	0.0174 (7)	−0.0025 (6)	−0.0048 (6)
O4	0.0149 (7)	0.0242 (7)	0.0132 (6)	0.0103 (6)	0.0006 (5)	0.0007 (5)
O5	0.0170 (7)	0.0209 (7)	0.0148 (6)	0.0099 (6)	0.0021 (5)	0.0046 (5)
O6	0.0170 (7)	0.0178 (7)	0.0123 (6)	0.0063 (6)	0.0014 (5)	−0.0022 (5)
O7	0.0250 (8)	0.0192 (7)	0.0170 (6)	0.0100 (6)	−0.0016 (6)	−0.0026 (6)
O8	0.0316 (10)	0.0150 (10)	0.0194 (10)	0.0075 (5)	−0.0008 (4)	−0.0016 (8)
N1	0.0222 (9)	0.0152 (8)	0.0181 (8)	0.0095 (7)	−0.0023 (7)	−0.0023 (6)
N2	0.0326 (10)	0.0155 (9)	0.0187 (8)	0.0121 (8)	−0.0074 (8)	−0.0017 (7)
C6	0.0200 (9)	0.0194 (10)	0.0165 (9)	0.0099 (8)	0.0015 (8)	0.0010 (8)
N3	0.0242 (9)	0.0194 (9)	0.0207 (8)	0.0093 (7)	−0.0056 (7)	0.0018 (7)
C1	0.0155 (9)	0.0172 (9)	0.0120 (8)	0.0077 (8)	0.0014 (7)	−0.0001 (7)
C2	0.0152 (9)	0.0177 (9)	0.0129 (8)	0.0072 (7)	0.0010 (7)	−0.0016 (7)
C3	0.0154 (9)	0.0152 (9)	0.0152 (8)	0.0072 (7)	0.0009 (7)	0.0001 (7)
C4	0.0126 (9)	0.0153 (9)	0.0140 (8)	0.0054 (7)	−0.0001 (7)	0.0005 (7)
C5	0.0137 (8)	0.0181 (9)	0.0119 (8)	0.0074 (7)	0.0010 (7)	−0.0003 (7)
C7	0.0137 (8)	0.0167 (9)	0.0158 (8)	0.0081 (7)	−0.0009 (7)	−0.0025 (7)
C8	0.0234 (10)	0.0182 (9)	0.0162 (9)	0.0106 (8)	0.0002 (7)	0.0020 (7)
C9	0.0258 (10)	0.0218 (10)	0.0126 (8)	0.0133 (9)	−0.0012 (8)	0.0005 (7)
C10	0.0196 (10)	0.0179 (9)	0.0179 (9)	0.0121 (8)	−0.0016 (7)	−0.0020 (7)
C11	0.0204 (10)	0.0174 (9)	0.0175 (9)	0.0106 (8)	−0.0002 (8)	0.0007 (7)
C12	0.0194 (9)	0.0210 (10)	0.0127 (8)	0.0113 (8)	0.0001 (7)	0.0003 (7)
C13	0.0237 (10)	0.0178 (9)	0.0155 (9)	0.0123 (8)	−0.0008 (8)	−0.0001 (7)
C14	0.0183 (9)	0.0185 (10)	0.0148 (8)	0.0104 (8)	0.0006 (7)	−0.0001 (7)

Geometric parameters (Å, º) top

O1—C5	1.419 (2)	N3—H3B	0.8800
O1—C1	1.441 (2)	C1—C2	1.530 (3)
O2—C6	1.428 (2)	C1—H1	1.0000
O2—H2	0.8400	C2—C3	1.518 (3)
O3—C2	1.428 (2)	C2—H2A	1.0000
O3—H3	0.8400	C3—C4	1.524 (2)
O4—C3	1.430 (2)	C3—H3C	1.0000
O4—H4	0.8400	C4—C5	1.517 (3)
O5—C4	1.424 (2)	C4—H4A	1.0000
O5—H5	0.8400	C5—H5A	1.0000
O6—C7	1.381 (2)	C7—C12	1.390 (3)
O6—C5	1.412 (2)	C7—C8	1.392 (2)
O7—C14	1.257 (2)	C8—C9	1.387 (3)
O8—H8O	0.84 (3)	C8—H8	0.9500
N1—C13	1.281 (2)	C9—C10	1.395 (3)
N1—N2	1.385 (2)	C9—H9	0.9500
N2—C14	1.355 (2)	C10—C11	1.397 (3)
N2—H2N	0.88 (3)	C10—C13	1.466 (3)
C6—C1	1.511 (3)	C11—C12	1.390 (3)
C6—H6A	0.9900	C11—H11	0.9500
C6—H6B	0.9900	C12—H12	0.9500
N3—C14	1.326 (3)	C13—H13	0.9500
N3—H3A	0.8800

C5—O1—C1	112.67 (14)	O5—C4—C5	110.79 (15)
C6—O2—H2	109.5	O5—C4—C3	107.90 (15)
C2—O3—H3	109.5	C5—C4—C3	109.50 (15)
C3—O4—H4	109.5	O5—C4—H4A	109.5
C4—O5—H5	109.5	C5—C4—H4A	109.5
C7—O6—C5	116.12 (15)	C3—C4—H4A	109.5
C13—N1—N2	114.29 (17)	O6—C5—O1	107.44 (14)
C14—N2—N1	119.87 (16)	O6—C5—C4	108.02 (15)
C14—N2—H2N	118.8 (18)	O1—C5—C4	110.68 (15)
N1—N2—H2N	121.1 (18)	O6—C5—H5A	110.2
O2—C6—C1	110.08 (16)	O1—C5—H5A	110.2
O2—C6—H6A	109.6	C4—C5—H5A	110.2
C1—C6—H6A	109.6	O6—C7—C12	122.61 (16)
O2—C6—H6B	109.6	O6—C7—C8	116.71 (17)
C1—C6—H6B	109.6	C12—C7—C8	120.69 (18)
H6A—C6—H6B	108.2	C9—C8—C7	119.40 (19)
C14—N3—H3A	120.0	C9—C8—H8	120.3
C14—N3—H3B	120.0	C7—C8—H8	120.3
H3A—N3—H3B	120.0	C8—C9—C10	120.94 (17)
O1—C1—C6	105.85 (14)	C8—C9—H9	119.5
O1—C1—C2	108.28 (15)	C10—C9—H9	119.5
C6—C1—C2	113.83 (16)	C9—C10—C11	118.51 (18)
O1—C1—H1	109.6	C9—C10—C13	123.76 (17)
C6—C1—H1	109.6	C11—C10—C13	117.73 (18)
C2—C1—H1	109.6	C12—C11—C10	121.15 (18)
O3—C2—C3	107.20 (15)	C12—C11—H11	119.4
O3—C2—C1	111.32 (15)	C10—C11—H11	119.4
C3—C2—C1	110.59 (15)	C11—C12—C7	119.07 (17)
O3—C2—H2A	109.2	C11—C12—H12	120.5
C3—C2—H2A	109.2	C7—C12—H12	120.5
C1—C2—H2A	109.2	N1—C13—C10	122.22 (18)
O4—C3—C2	107.37 (15)	N1—C13—H13	118.9
O4—C3—C4	111.43 (15)	C10—C13—H13	118.9
C2—C3—C4	110.23 (15)	O7—C14—N3	123.06 (18)
O4—C3—H3C	109.3	O7—C14—N2	119.55 (17)
C2—C3—H3C	109.3	N3—C14—N2	117.39 (18)
C4—C3—H3C	109.3

C13—N1—N2—C14	176.28 (19)	O5—C4—C5—O6	−67.07 (19)
C5—O1—C1—C6	−175.23 (15)	C3—C4—C5—O6	174.03 (15)
C5—O1—C1—C2	62.35 (19)	O5—C4—C5—O1	175.56 (14)
O2—C6—C1—O1	−62.49 (19)	C3—C4—C5—O1	56.7 (2)
O2—C6—C1—C2	56.3 (2)	C5—O6—C7—C12	31.4 (3)
O1—C1—C2—O3	−176.33 (15)	C5—O6—C7—C8	−148.63 (17)
C6—C1—C2—O3	66.3 (2)	O6—C7—C8—C9	176.08 (18)
O1—C1—C2—C3	−57.27 (19)	C12—C7—C8—C9	−3.9 (3)
C6—C1—C2—C3	−174.68 (15)	C7—C8—C9—C10	0.2 (3)
O3—C2—C3—O4	54.20 (19)	C8—C9—C10—C11	4.0 (3)
C1—C2—C3—O4	−67.32 (18)	C8—C9—C10—C13	−175.52 (19)
O3—C2—C3—C4	175.75 (15)	C9—C10—C11—C12	−4.5 (3)
C1—C2—C3—C4	54.2 (2)	C13—C10—C11—C12	174.99 (19)
O4—C3—C4—O5	−54.48 (19)	C10—C11—C12—C7	0.9 (3)
C2—C3—C4—O5	−173.59 (15)	O6—C7—C12—C11	−176.63 (17)
O4—C3—C4—C5	66.18 (19)	C8—C7—C12—C11	3.4 (3)
C2—C3—C4—C5	−52.9 (2)	N2—N1—C13—C10	179.26 (18)
C7—O6—C5—O1	−91.06 (18)	C9—C10—C13—N1	19.1 (3)
C7—O6—C5—C4	149.50 (15)	C11—C10—C13—N1	−160.4 (2)
C1—O1—C5—O6	179.21 (14)	N1—N2—C14—O7	−174.97 (17)
C1—O1—C5—C4	−63.07 (19)	N1—N2—C14—N3	5.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O7ⁱ	0.84	1.85	2.6905 (19)	175
O3—H3···O8ⁱⁱ	0.84	1.94	2.7447 (16)	159
O4—H4···O5ⁱⁱⁱ	0.84	2.05	2.8277 (19)	154
O4—H4···O5	0.84	2.34	2.7725 (19)	113
O5—H5···O2^iv	0.84	1.85	2.693 (2)	178
N3—H3A···O4^v	0.88	2.24	3.096 (2)	165
N3—H3A···O3^v	0.88	2.46	2.896 (2)	111
O8—H8O···O7^vi	0.84 (3)	1.95 (3)	2.7163 (17)	151 (4)
N2—H2N···O3^vii	0.88 (3)	2.14 (3)	3.014 (2)	176 (2)

Symmetry codes: (i) −x+y, −x+2, z−1/3; (ii) −x+y, −x+1, z−1/3; (iii) −x+2, −x+y+1, −z+4/3; (iv) −x+1, −x+y, −z+4/3; (v) −y+2, x−y+1, z+1/3; (vi) x−1, y−1, z; (vii) −x+2, −x+y+2, −z+4/3.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₉N₃O₇·0.5H₂O
M_r	350.33
Crystal system, space group	Trigonal, P3₁21
Temperature (K)	113
a, c (Å)	8.6373 (12), 37.021 (7)
V (Å³)	2391.8 (7)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.28 × 0.25 × 0.21

Data collection
Diffractometer	Rigaku Saturn CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.967, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	15783, 2242, 2161
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.09
No. of reflections	2242
No. of parameters	235
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.18

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O7ⁱ	0.84	1.85	2.6905 (19)	174.5
O3—H3···O8ⁱⁱ	0.84	1.94	2.7447 (16)	159.2
O4—H4···O5ⁱⁱⁱ	0.84	2.05	2.8277 (19)	154.3
O4—H4···O5	0.84	2.34	2.7725 (19)	112.8
O5—H5···O2^iv	0.84	1.85	2.693 (2)	177.9
N3—H3A···O4^v	0.88	2.24	3.096 (2)	165.4
N3—H3A···O3^v	0.88	2.46	2.896 (2)	111.1
O8—H8O···O7^vi	0.84 (3)	1.95 (3)	2.7163 (17)	151 (4)
N2—H2N···O3^vii	0.88 (3)	2.14 (3)	3.014 (2)	176 (2)

Acknowledgements

The authors thank Mr Zhi-Hua Mao of the Analytical & Testing Center of Sichuan University for the X-ray data collection.

References

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