1-[4-(2,3,4,6-Tetra-O-acetyl-β-d-allo-pyranos-yloxy)benzyl-idene]thio-semi-carbazide.

Abstract

The title compound, C(22)H(27)N(3)O(10)S, was synthesized by reaction of an ethanol solution of helicid (systematic name: 4-formylphenl-β-d-allopyranoside), thio-semicarbazide and acetic acid. The mol-ecule exhibits a trans conformation with respect to the C=N double bond. The pyran ring adopts a chair conformation. In the crystal structure, the mol-ecules are linked into chains parallel to the b axis by inter-molecular N-H⋯O hydrogen bonds.

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1-[4-(2,3,4,6-Tetra-O-acetyl-b-D-allo-
pyranosyloxy)benzylidene]thiosemi-
carbazide
Li Fu, Xiu-juan Yin, Lei Zheng, Ying Li and Shu-fan Yin*
College of Chemistry, Sichuan University, Chengdu 610064, People’s Republic of
China
Correspondence e-mail: chuandayouji217@163.com
Received 15 February 2009; accepted 27 February 2009
Key indicators: single-crystal X-ray study; T = 292 K; mean ?(C–C) = 0.007 A ˚;
R factor = 0.062; wR factor = 0.195; data-to-parameter ratio = 15.0.
The title compound, C22H27N3O10S, was synthesized by
reaction of an ethanol solution of helicid (systematic name:
4-formylphenl-?-d-allopyranoside),
acetic acid. The molecule exhibits a trans conformation with
respect to the C
N double bond. The pyran ring adopts a
chair conformation. In the crystal structure, the molecules are
linked into chains parallel to the b axis by intermolecular N—
H???O hydrogen bonds.
thiosemicarbazideand
Related literature
For the synthesis and biological activity of helicid, see: Chen et
al. (1981); Sha & Mao (1987); Zhu et al. (2006); Yang et al.
(2008); Wen et al. (2007).
Experimental
Crystal data
C22H27N3O10S
Mr= 525.53
Orthorhombic, P212121
a = 9.848 (3) A˚
b = 11.515 (3) A˚
c = 23.250 (4) A˚
V = 2636.5 (12) A˚3
Z = 4
Mo K? radiation
? = 0.18 mm?1
T = 292 K
0.54 ? 0.46 ? 0.24 mm
Data collection
Enraf-Nonius CAD-4
diffractometer
Absorption correction: scan
(North et al., 1968)
Tmin= 0.909, Tmax= 0.958
5423 measured reflections
4940 independent reflections
2851 reflections with I > 2?(I)
Rint= 0.008
3 standard reflections
every 200 reflections
intensity decay: 1.0%
Refinement
R[F2> 2?(F2)] = 0.062
wR(F2) = 0.195
S = 1.07
4940 reflections
329 parameters
H atoms treated by a mixture of
independent and constrained
refinement
??max= 0.30 e A˚?3
??min= ?0.27 e A˚?3
Absolute structure: Flack, (1983),
2108 Friedel pairs
Flack parameter: 0.35 (19)
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
N2—H2N1???O10i
N3—H3A???O8ii
Symmetry codes: (i) x þ1
D—HH???AD???AD—H???A
0.75 (5)
0.86
2.33 (5)
2.60
3.076 (6)
3.229 (7)
172 (6)
131
2;?y þ1
2;?z þ 2; (ii) x;y þ 1;z.
Data collection: DIFRAC (Gabe et al., 1993); cell refinement:
DIFRAC; data reduction: NRCVAX (Gabe et al., 1989); 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.
The authors thank Mr Zhi-Hua Mao of Sichuan University
for the X-ray data collection.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: RZ2297).
References
Chen, W. S., Lu, S. D. & Eberhard, B. (1981). Liebigs Ann. Chem. 10, 1893–
1897.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Gabe,E. J., Le Page, Y., Charland, J.-P., Lee, F. L. &White, P. S. (1989). J. Appl.
Cryst. 22, 384–387.
Gabe, E. J., White, P. S. & Enright, G. D. (1993). DIFRAC. American
Crystallographic Association, Pittsburgh Meeting Abstract, PA 104.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–
359.
Sha, J. Z. & Mao, H. K. (1987). Chin. Pharm. Bull. 22, 21–27.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wen, H., Wang, Z. T., Zhou, Y. Y., Lin, C. L., Gou, H., Peng, W. L., Song, H. C.,
Cao, R. H., Dai, X. C., Hu, L. N., Zhang, L. S. & Wang, Y. H. (2007). Faming
Zhuanli Shengqing Gongkai Shuomingshu. Chinese Patent CN 101 029 064.
Yang, H. J., Hu, C., LI, Y. & Yin, S. F. (2008). Chin. J. Org. Chem. 28, 899–902.
Zhu, Q. L., Tang, Q., Li, Y. & Yin, S. F. (2006). Chin. J. Org. Chem. 26, 1264–
1267.
organic compounds
Acta Cryst. (2009). E65, o679doi:10.1107/S1600536809007260 Fu et al.
o679
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
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Acta Cryst. (2009). E65, o679 [ doi:10.1107/S1600536809007260 ]
1-[4-(2,3,4,6-Tetra-O-acetyl- -D-allopyranosyloxy)benzylidene]thiosemicarbazide
L. Fu, X. Yin, L. Zheng, Y. Li and S. Yin
Comment
The natural compound helicid (systematic name: 4-formylphenl-β-D-allopyranoside), which is extracted from the fruit of
Helicia nilagirica Beed. (Chen et al., 1981), has been one major active ingredient of herb medicine used in China for a
long time. It has manifested good biological effects on the central nervous system and low toxicity (Sha & Mao, 1987).
Some derivatives of this compound have been reported to possess good pharmacological activity (Zhu et al., 2006; Yang et
al., 2008). We report here the crystal structure of the title compound, whose synthesis has been already reported elsewhere
(Wen et al., 2007).
In the molecule of the title compound (Fig. 1), the pyran ring adopts a chair conformation, with the hydroxy group at C3
in axial position and the other substituents at C1, C2 and C4 in equatorial positions. The average C–C bond length within
the pyran ring is 1.524 (3) Å. The molecule exhibits a trans conformation with respect to the N1═C21 double bond, as
indicated by the value of the C21–N1–N2–C22 torsion angle of -171.8 (6)°. In the crystal packing, intermolecular N—H···O
hydrogen bonds (Table 1) link the molecules into chains running parallel to the b axis.
Experimental
A mixture of helicid (0.45 g, 1 mmol), acetic acid (0.5 ml) and thiosemicarbazide (0.09 g, 1 mmol) in ethanol (15 ml) was
refluxed for 3 h. After cooling to room temperature, the precipitate was filtered, washed with ether and recrystallized from
95% alcohol to give a white powder. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of
an ethanol/dichloromethane (4:1 v/v) solution at room temperature.
Refinement
The H atom bound to N2 was located in a difference Fourier map and refined freely. All other H atoms were positioned
geometrically and refined using a riding model, with C—H = 0.93–0.97 Å, N—H = 0.86 Å, and Uiso(H) = 1.2Ueq (C, N)
or 1.5Ueq (C) for methyl H atoms.
Figures
Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at
the 30% probability level.

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1-[4-(2,3,4,6-Tetra-O-acetyl-β-D- allopyranosyloxy)benzylidene]thiosemicarbazide
Crystal data
C22H27N3O10S
F000 = 1104
Dx = 1.324 Mg m−3
Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 19 reflections
θ = 4.5–7.5º
µ = 0.18 mm−1
T = 292 K
Mr = 525.53
Orthorhombic, P212121
Hall symbol: P 2ac 2ab
a = 9.848 (3) Å
b = 11.515 (3) Å
c = 23.250 (4) Å
V = 2636.5 (12) Å3
Z = 4
Block, colourless
0.54 × 0.46 × 0.24 mm
Data collection
Enraf-Nonius CAD-4
diffractometer
Radiation source: fine-focus sealed tube
Monochromator: graphite
T = 292 K
ω/2–θ scans
Absorption correction: ψ scan
(North et al., 1968)
Tmin = 0.909, Tmax = 0.958
5423 measured reflections
4940 independent reflections
2851 reflections with I > 2σ(I)
Rint = 0.008
θmax = 26.0º
θmin = 1.8º
h = −10→12
k = −14→14
l = −28→28
3 standard reflections
every 200 reflections
intensity decay: 1.0%
Refinement
Refinement on F2
Hydrogen site location: mixed
Least-squares matrix: full
H atoms treated by a mixture of
independent and constrained refinement
w = 1/[σ2(Fo2) + (0.1108P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.30 e Å−3
Δρmin = −0.27 e Å−3
Extinction correction: none
R[F2 > 2σ(F2)] = 0.062
wR(F2) = 0.195
S = 1.07
4940 reflections
329 parameters
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map Flack parameter: 0.35 (19)
Absolute structure: Flack, (1983), 2108 Friedel pairs

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Special details
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 mat-
rix. 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, convention-
al 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)
x
0.67386 (19)
0.0580 (3)
−0.0599 (4)
0.2305 (3)
0.1797 (6)
0.5080 (3)
0.6199 (5)
0.6077 (3)
0.5379 (4)
0.4971 (3)
0.3267 (3)
0.6208 (4)
0.6680 (5)
0.708 (5)
0.5385 (6)
0.5134
0.5078
0.2764 (4)
0.3406
0.2779 (4)
0.2159
0.4199 (5)
0.4230
0.4693 (4)
0.4119
0.4627 (4)
0.5245
0.1424 (4)
0.1602
0.0943
−0.0460 (5)
−0.1389 (6)
−0.1704
y
0.79792 (13)
0.0411 (3)
−0.0865 (4)
−0.1128 (3)
−0.3014 (4)
−0.0914 (3)
−0.2413 (4)
−0.1962 (3)
−0.3793 (3)
−0.0280 (3)
0.0069 (3)
0.4935 (4)
0.5844 (4)
0.569 (5)
0.7104 (5)
0.6535
0.7791
0.0066 (4)
0.0512
−0.1174 (4)
−0.1649
−0.1666 (4)
−0.2467
−0.1589 (4)
−0.2072
−0.0333 (4)
0.0149
0.0717 (5)
0.1546
0.0548
−0.0308 (5)
−0.0288 (6)
−0.1061
z
1.07682 (8)
0.84568 (15)
0.7938 (2)
0.71708 (14)
0.7185 (2)
0.74617 (14)
0.70896 (19)
0.84617 (15)
0.8569 (2)
0.92000 (13)
0.85614 (12)
1.00575 (18)
1.0393 (2)
1.066 (2)
0.9885 (2)
0.9670
0.9820
0.7979 (2)
0.7745
0.7760 (2)
0.7990
0.7796 (2)
0.7654
0.8422 (2)
0.8669
0.86160 (19)
0.8387
0.7977 (2)
0.7987
0.7623
0.8376 (3)
0.8892 (3)
0.8971
Uiso*/Ueq
0.0785 (5)
0.0535 (9)
0.0862 (14)
0.0522 (9)
0.1061 (18)
0.0482 (8)
0.0865 (14)
0.0501 (8)
0.0781 (13)
0.0443 (7)
0.0407 (7)
0.0548 (11)
0.0565 (12)
0.049 (17)*
0.0832 (17)
0.100*
0.100*
0.0402 (10)
0.048*
0.0433 (11)
0.052*
0.0459 (12)
0.055*
0.0396 (10)
0.048*
0.0367 (10)
0.044*
0.0496 (13)
0.060*
0.060*
0.0597 (14)
0.0787 (19)
0.118*
S1
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
N1
N2
H2N1
N3
H3A
H3B
C1
H1
C2
H2
C3
H3
C4
H4
C5
H5
C6
H6A
H6B
C7
C8
H8A