1-(2,3,4,6-Tetra-O-acetyl-β-d-gluco­pyranos­yl)-3-thio­ureidothio­urea monohydrate

Weidong Sun; Jin Yao; Lifei Bai; Xiaoming Wang

doi:10.1107/S1600536808043833

. 2009 Jan 8;65(Pt 2):o242. doi: 10.1107/S1600536808043833

1-(2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl)-3-thioureidothiourea monohydrate

Weidong Sun ^a, Jin Yao ^b, Lifei Bai ^c, Xiaoming Wang ^d,^*

PMCID: PMC2968307 PMID: 21581859

Abstract

In the title compound, C₁₆H₂₄N₄O₉S₂·H₂O, the hexopyranosyl ring adopts a chair conformation (⁴ C ₁), and the five substituents are in equatorial positions. In the crystal structure, extensive O—H⋯O, N—H⋯S and N—H⋯O hydrogen bonding leads to the formation of a three-dimensional network.

Related literature

For cycloaddition and nucleophilic addition, see: Pearson et al. (2003 ▶); Reitz et al. (1989 ▶). For the crystal structure of glycosyl isothiosyanate, see: Jiang et al. (2003 ▶). For the crystal structures of glycosyl isothiosyanate methanol and ethanol derivatives, see: Zhang et al. (2001 ▶).

Experimental

Crystal data

C₁₆H₂₄N₄O₉S₂·H₂O
M _r = 498.53
Monoclinic,
a = 22.286 (2) Å
b = 7.2005 (7) Å
c = 15.8772 (17) Å
β = 110.119 (2)°
V = 2392.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 (2) K
0.45 × 0.22 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
6322 measured reflections
3525 independent reflections
3021 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.141
S = 1.07
3525 reflections
289 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ▶), 1229 Friedel pairs
Flack parameter: −0.16 (12)

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043833/su2088sup1.cif

e-65-0o242-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043833/su2088Isup2.hkl

e-65-0o242-Isup2.hkl^{(172.9KB, 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
O1W—H10⋯O5ⁱ	0.87	2.64	3.382 (11)	146
O1W—H20⋯O9ⁱⁱ	0.87	2.56	3.181 (9)	129
N1—H1A⋯S2ⁱⁱⁱ	0.86	2.62	3.400 (4)	151
N2—H2A⋯O3^iv	0.86	2.09	2.856 (5)	147
N3—H3A⋯O1W^v	0.86	2.13	2.973 (9)	167
N4—H4B⋯O1W^vi	0.86	2.43	3.244 (9)	159
N4—H4C⋯O1ⁱⁱⁱ	0.86	2.49	3.323 (5)	164

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

Acknowledgments

The project was supported by the National Natural Science Foundation of China (No. 30701041) and the Scientific Research Project of Inner Mongolia Autonomous Region Colleges and Universities (No. NJZY08149).

supplementary crystallographic information

Comment

Over the past decade, many organic chemists have been engaged in the synthesis of glycosyl isothiosyanates and its derivatives. These compound are versatile reagents in organic synthesis and easily undergo many important reactions, such as cycloaddition (Pearson et al., 2003) and nucleophilic addition (Reitz et al., 1989). Recently, the crystal structures of glycosyl isothiosyanate (Jiang et al., 2003) and the methanol and ethanol derivatives (Zhang et al., 2001) have been reported. However, other derivatives of glycosyl isothiosyanate are still rare. Here we report on the synthesis of a new thiosemicarbazide derivative of glycosyl isothiosyanate, 2,3,4,6-tetra-O-acetyl- β-D-glucopyranosyl dithiourea, (I).

The molecular structure of compound (I) is illustrated in Fig. 1. The hexopyranosyl ring adopts a chair conformation (⁴C₁), and the four substituents are in equatorial positions.

In the crystal extensive O—H···O, N—H···S and N—H···O hydrogen bonding (Table 1) leads to the formation of a three-dimensional network.

Experimental

Compound (I) was prepared by refluxing together equimolar amounts of β-D-2,3,4,6-tetra-O- acetyl-glucopyranosyl isothiocyanate and thiosemicarbazide. After cooling to room temperature, water was added to the mixture and compound (I) was isolated as a white solid. Crystals, suitable for X-ray analysis, were grown from an ethyl acetate and acetonitrile (1:1 / v:v) solution by slow evaporation at room temperature.