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

Hua-Feng Chen; Xue Bai; Kuan Zhang; Ying Li; Shu-Fan Yin

doi:10.1107/S1600536809055664

. 2010 Jan 9;66(Pt 2):o321. doi: 10.1107/S1600536809055664

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

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

PMCID: PMC2979748 PMID: 21579751

Abstract

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,
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[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 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

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.

Supplementary Material

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

e-66-0o321-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055664/rz2403Isup2.hkl

e-66-0o321-Isup2.hkl^{(110.3KB, hkl)}

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

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)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.