1-[4-(2,3,4,6-Tetra-O-acetyl-β-d-allo­pyranos­yloxy)benzyl­idene]thio­semi­carbazide

Fu, L.; Yin, X.; Zheng, L.; Li, Y.; Yin, S.

doi:10.1107/S1600536809007260

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o679

doi:10.1107/S1600536809007260

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1-[4-(2,3,4,6-Tetra-O-acetyl-β-D-allopyranosyloxy)benzylidene]thiosemicarbazide

Li Fu,^a Xiu-juan Yin,^a Lei Zheng,^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 15 February 2009; accepted 27 February 2009; online 6 March 2009)

The title compound, C₂₂H₂₇N₃O₁₀S, was synthesized by reaction of an ethanol solution of helicid (systematic name: 4-formylphenl-β-D-allopyranoside), thiosemicarbazide and 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.

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
M_r = 525.53
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.848 (3) Å
b = 11.515 (3) Å
c = 23.250 (4) Å
V = 2636.5 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 292 K
0.54 × 0.46 × 0.24 mm

Data collection

Enraf-Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.909, T_max = 0.958
5423 measured reflections
4940 independent reflections
2851 reflections with I > 2σ(I)
R_int = 0.008
3 standard reflections every 200 reflections intensity decay: 1.0%

Refinement

R[F² > 2σ(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
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack, (1983 ), 2108 Friedel pairs
Flack parameter: 0.35 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N1⋯O10ⁱ	0.75 (5)	2.33 (5)	3.076 (6)	172 (6)
N3—H3A⋯O8ⁱⁱ	0.86	2.60	3.229 (7)	131
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (ii) x, y+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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007260/rz2297sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007260/rz2297Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For the synthesis and biological activities of helicid, see: Chen et al. (1981); Sha & Mao (1987); Zhu et al. (2006); Yang et al. (2008); Wen et al. (2007).

Experimental top

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.

Computing details top

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

1-[4-(2,3,4,6-Tetra-O-acetyl-β-D- allopyranosyloxy)benzylidene]thiosemicarbazide top

Crystal data top

C₂₂H₂₇N₃O₁₀S	F(000) = 1104
M_r = 525.53	D_x = 1.324 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 19 reflections
a = 9.848 (3) Å	θ = 4.5–7.5°
b = 11.515 (3) Å	µ = 0.18 mm⁻¹
c = 23.250 (4) Å	T = 292 K
V = 2636.5 (12) Å³	Block, colourless
Z = 4	0.54 × 0.46 × 0.24 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	2851 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.008
Graphite monochromator	θ_max = 26.0°, θ_min = 1.8°
ω/2–θ scans	h = −10→12
Absorption correction: ψ scan (North et al., 1968)	k = −14→14
T_min = 0.909, T_max = 0.958	l = −28→28
5423 measured reflections	3 standard reflections every 200 reflections
4940 independent reflections	intensity decay: 1.0%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.195	w = 1/[σ²(F_o²) + (0.1108P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4940 reflections	Δρ_max = 0.30 e Å⁻³
329 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Absolute structure: Flack, (1983), 2108 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.35 (19)

Crystal data top

C₂₂H₂₇N₃O₁₀S	V = 2636.5 (12) Å³
M_r = 525.53	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.848 (3) Å	µ = 0.18 mm⁻¹
b = 11.515 (3) Å	T = 292 K
c = 23.250 (4) Å	0.54 × 0.46 × 0.24 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	2851 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.008
T_min = 0.909, T_max = 0.958	3 standard reflections every 200 reflections
5423 measured reflections	intensity decay: 1.0%
4940 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.195	Δρ_max = 0.30 e Å⁻³
S = 1.07	Δρ_min = −0.27 e Å⁻³
4940 reflections	Absolute structure: Flack, (1983), 2108 Friedel pairs
329 parameters	Absolute structure parameter: 0.35 (19)
0 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
S1	0.67386 (19)	0.79792 (13)	1.07682 (8)	0.0785 (5)
O1	0.0580 (3)	0.0411 (3)	0.84568 (15)	0.0535 (9)
O2	−0.0599 (4)	−0.0865 (4)	0.7938 (2)	0.0862 (14)
O3	0.2305 (3)	−0.1128 (3)	0.71708 (14)	0.0522 (9)
O4	0.1797 (6)	−0.3014 (4)	0.7185 (2)	0.1061 (18)
O5	0.5080 (3)	−0.0914 (3)	0.74617 (14)	0.0482 (8)
O6	0.6199 (5)	−0.2413 (4)	0.70896 (19)	0.0865 (14)
O7	0.6077 (3)	−0.1962 (3)	0.84617 (15)	0.0501 (8)
O8	0.5379 (4)	−0.3793 (3)	0.8569 (2)	0.0781 (13)
O9	0.4971 (3)	−0.0280 (3)	0.92000 (13)	0.0443 (7)
O10	0.3267 (3)	0.0069 (3)	0.85614 (12)	0.0407 (7)
N1	0.6208 (4)	0.4935 (4)	1.00575 (18)	0.0548 (11)
N2	0.6680 (5)	0.5844 (4)	1.0393 (2)	0.0565 (12)
H2N1	0.708 (5)	0.569 (5)	1.066 (2)	0.049 (17)*
N3	0.5385 (6)	0.7104 (5)	0.9885 (2)	0.0832 (17)
H3A	0.5134	0.6535	0.9670	0.100*
H3B	0.5078	0.7791	0.9820	0.100*
C1	0.2764 (4)	0.0066 (4)	0.7979 (2)	0.0402 (10)
H1	0.3406	0.0512	0.7745	0.048*
C2	0.2779 (4)	−0.1174 (4)	0.7760 (2)	0.0433 (11)
H2	0.2159	−0.1649	0.7990	0.052*
C3	0.4199 (5)	−0.1666 (4)	0.7796 (2)	0.0459 (12)
H3	0.4230	−0.2467	0.7654	0.055*
C4	0.4693 (4)	−0.1589 (4)	0.8422 (2)	0.0396 (10)
H4	0.4119	−0.2072	0.8669	0.048*
C5	0.4627 (4)	−0.0333 (4)	0.86160 (19)	0.0367 (10)
H5	0.5245	0.0149	0.8387	0.044*
C6	0.1424 (4)	0.0717 (5)	0.7977 (2)	0.0496 (13)
H6A	0.1602	0.1546	0.7987	0.060*
H6B	0.0943	0.0548	0.7623	0.060*
C7	−0.0460 (5)	−0.0308 (5)	0.8376 (3)	0.0597 (14)
C8	−0.1389 (6)	−0.0288 (6)	0.8892 (3)	0.0787 (19)
H8A	−0.1704	−0.1061	0.8971	0.118*
H8B	−0.2152	0.0206	0.8814	0.118*
H8C	−0.0903	0.0003	0.9220	0.118*
C9	0.1755 (6)	−0.2085 (6)	0.6944 (3)	0.0694 (16)
C10	0.1184 (7)	−0.1847 (6)	0.6369 (3)	0.083 (2)
H10A	0.0842	−0.2555	0.6206	0.125*
H10B	0.1880	−0.1535	0.6125	0.125*
H10C	0.0457	−0.1295	0.6403	0.125*
C11	0.6074 (5)	−0.1380 (5)	0.7148 (2)	0.0541 (14)
C12	0.6992 (6)	−0.0490 (6)	0.6898 (3)	0.0775 (19)
H12A	0.7702	−0.0867	0.6686	0.116*
H12B	0.7382	−0.0034	0.7202	0.116*
H12C	0.6484	0.0006	0.6645	0.116*
C13	0.6297 (6)	−0.3110 (5)	0.8532 (2)	0.0576 (14)
C14	0.7786 (6)	−0.3377 (6)	0.8568 (3)	0.084 (2)
H14A	0.8104	−0.3227	0.8951	0.126*
H14B	0.8272	−0.2896	0.8301	0.126*
H14C	0.7934	−0.4179	0.8475	0.126*
C15	0.5342 (4)	0.0805 (4)	0.9425 (2)	0.0401 (10)
C16	0.6049 (5)	0.0769 (4)	0.9935 (2)	0.0512 (12)
H16	0.6249	0.0062	1.0109	0.061*
C17	0.6458 (5)	0.1805 (5)	1.0185 (2)	0.0565 (14)
H17	0.6946	0.1788	1.0527	0.068*
C18	0.6155 (5)	0.2860 (4)	0.9935 (2)	0.0439 (11)
C19	0.5441 (5)	0.2877 (4)	0.9419 (2)	0.0516 (13)
H19	0.5235	0.3583	0.9245	0.062*
C20	0.5032 (5)	0.1840 (4)	0.9160 (2)	0.0483 (12)
H20	0.4558	0.1848	0.8814	0.058*
C21	0.6587 (5)	0.3937 (4)	1.0228 (2)	0.0500 (12)
H21	0.7155	0.3884	1.0546	0.060*
C22	0.6230 (6)	0.6925 (5)	1.0308 (2)	0.0585 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.1123 (13)	0.0390 (8)	0.0844 (11)	0.0062 (8)	−0.0385 (10)	−0.0059 (8)
O1	0.0362 (16)	0.058 (2)	0.067 (2)	−0.0041 (15)	0.0009 (15)	−0.0004 (19)
O2	0.077 (3)	0.083 (3)	0.098 (4)	−0.023 (2)	−0.002 (2)	−0.018 (3)
O3	0.062 (2)	0.044 (2)	0.050 (2)	−0.0105 (17)	−0.0127 (16)	−0.0017 (16)
O4	0.170 (5)	0.046 (3)	0.103 (4)	−0.036 (3)	−0.061 (3)	0.005 (3)
O5	0.0532 (18)	0.0387 (18)	0.0527 (19)	0.0070 (16)	0.0063 (15)	−0.0047 (15)
O6	0.096 (3)	0.075 (3)	0.088 (3)	0.035 (3)	0.004 (3)	−0.031 (3)
O7	0.0487 (17)	0.0349 (18)	0.067 (2)	0.0089 (15)	−0.0076 (17)	−0.0047 (16)
O8	0.082 (3)	0.031 (2)	0.122 (4)	−0.003 (2)	−0.022 (2)	−0.005 (2)
O9	0.0551 (17)	0.0317 (16)	0.0461 (18)	−0.0059 (15)	−0.0085 (15)	−0.0055 (15)
O10	0.0422 (15)	0.0364 (17)	0.0435 (18)	0.0015 (14)	−0.0017 (14)	−0.0034 (14)
N1	0.062 (3)	0.049 (3)	0.053 (3)	−0.002 (2)	−0.016 (2)	−0.009 (2)
N2	0.077 (3)	0.035 (2)	0.058 (3)	0.003 (2)	−0.029 (3)	0.000 (2)
N3	0.120 (5)	0.046 (3)	0.084 (4)	0.004 (3)	−0.046 (3)	0.003 (3)
C1	0.045 (2)	0.024 (2)	0.051 (3)	−0.0048 (19)	0.000 (2)	0.000 (2)
C2	0.050 (3)	0.030 (2)	0.050 (3)	−0.003 (2)	−0.004 (2)	0.000 (2)
C3	0.056 (3)	0.028 (2)	0.054 (3)	0.000 (2)	−0.003 (2)	−0.008 (2)
C4	0.042 (2)	0.024 (2)	0.052 (3)	0.0039 (18)	−0.005 (2)	−0.007 (2)
C5	0.044 (2)	0.023 (2)	0.043 (3)	0.0005 (19)	0.0009 (19)	−0.0030 (19)
C6	0.043 (3)	0.050 (3)	0.056 (3)	0.001 (2)	0.000 (2)	0.008 (3)
C7	0.053 (3)	0.045 (3)	0.081 (4)	−0.002 (3)	−0.005 (3)	−0.001 (3)
C8	0.058 (3)	0.084 (5)	0.095 (4)	−0.019 (3)	0.014 (3)	0.004 (4)
C9	0.083 (4)	0.055 (4)	0.070 (4)	−0.020 (3)	−0.028 (3)	−0.010 (3)
C10	0.099 (5)	0.080 (5)	0.071 (4)	−0.022 (4)	−0.034 (4)	−0.001 (3)
C11	0.060 (3)	0.058 (4)	0.045 (3)	0.028 (3)	−0.006 (3)	−0.018 (3)
C12	0.062 (3)	0.096 (5)	0.075 (4)	0.023 (3)	0.020 (3)	0.005 (4)
C13	0.076 (4)	0.039 (3)	0.058 (3)	0.024 (3)	−0.018 (3)	−0.012 (3)
C14	0.070 (4)	0.066 (4)	0.117 (6)	0.025 (3)	−0.019 (4)	−0.028 (4)
C15	0.041 (2)	0.032 (2)	0.048 (3)	0.004 (2)	−0.003 (2)	−0.007 (2)
C16	0.069 (3)	0.032 (3)	0.052 (3)	0.002 (2)	−0.013 (3)	0.003 (2)
C17	0.069 (3)	0.053 (3)	0.048 (3)	−0.002 (3)	−0.023 (2)	0.002 (3)
C18	0.054 (3)	0.030 (2)	0.048 (3)	−0.001 (2)	−0.005 (2)	−0.010 (2)
C19	0.062 (3)	0.035 (3)	0.057 (3)	0.000 (2)	−0.013 (2)	−0.004 (2)
C20	0.062 (3)	0.035 (3)	0.048 (3)	−0.008 (2)	−0.018 (2)	−0.003 (2)
C21	0.060 (3)	0.040 (3)	0.050 (3)	0.003 (2)	−0.015 (2)	−0.009 (2)
C22	0.076 (3)	0.047 (3)	0.053 (3)	−0.004 (3)	−0.016 (3)	0.007 (3)

Geometric parameters (Å, º) top

S1—C22	1.693 (6)	C4—H4	0.9800
O1—C7	1.330 (6)	C5—H5	0.9800
O1—C6	1.435 (6)	C6—H6A	0.9700
O2—C7	1.210 (7)	C6—H6B	0.9700
O3—C9	1.336 (6)	C7—C8	1.510 (8)
O3—C2	1.448 (6)	C8—H8A	0.9600
O4—C9	1.207 (7)	C8—H8B	0.9600
O5—C11	1.333 (6)	C8—H8C	0.9600
O5—C3	1.452 (6)	C9—C10	1.477 (8)
O6—C11	1.204 (7)	C10—H10A	0.9600
O7—C13	1.349 (6)	C10—H10B	0.9600
O7—C4	1.432 (6)	C10—H10C	0.9600
O8—C13	1.201 (7)	C11—C12	1.485 (8)
O9—C5	1.401 (5)	C12—H12A	0.9600
O9—C15	1.404 (5)	C12—H12B	0.9600
O10—C5	1.422 (5)	C12—H12C	0.9600
O10—C1	1.442 (5)	C13—C14	1.501 (8)
N1—C21	1.271 (6)	C14—H14A	0.9600
N1—N2	1.386 (6)	C14—H14B	0.9600
N2—C22	1.336 (7)	C14—H14C	0.9600
N2—H2N1	0.75 (5)	C15—C16	1.374 (7)
N3—C22	1.307 (7)	C15—C20	1.376 (7)
N3—H3A	0.8600	C16—C17	1.387 (7)
N3—H3B	0.8600	C16—H16	0.9300
C1—C2	1.516 (6)	C17—C18	1.380 (7)
C1—C6	1.518 (6)	C17—H17	0.9300
C1—H1	0.9800	C18—C19	1.391 (7)
C2—C3	1.512 (7)	C18—C21	1.477 (7)
C2—H2	0.9800	C19—C20	1.397 (7)
C3—C4	1.536 (6)	C19—H19	0.9300
C3—H3	0.9800	C20—H20	0.9300
C4—C5	1.517 (6)	C21—H21	0.9300

C7—O1—C6	119.3 (4)	C7—C8—H8C	109.5
C9—O3—C2	118.3 (4)	H8A—C8—H8C	109.5
C11—O5—C3	119.4 (4)	H8B—C8—H8C	109.5
C13—O7—C4	117.1 (4)	O4—C9—O3	122.3 (5)
C5—O9—C15	117.6 (3)	O4—C9—C10	126.7 (5)
C5—O10—C1	114.0 (3)	O3—C9—C10	111.0 (5)
C21—N1—N2	114.1 (4)	C9—C10—H10A	109.5
C22—N2—N1	120.7 (5)	C9—C10—H10B	109.5
C22—N2—H2N1	121 (4)	H10A—C10—H10B	109.5
N1—N2—H2N1	117 (4)	C9—C10—H10C	109.5
C22—N3—H3A	120.0	H10A—C10—H10C	109.5
C22—N3—H3B	120.0	H10B—C10—H10C	109.5
H3A—N3—H3B	120.0	O6—C11—O5	122.3 (6)
O10—C1—C2	108.3 (4)	O6—C11—C12	125.2 (5)
O10—C1—C6	107.5 (4)	O5—C11—C12	112.5 (5)
C2—C1—C6	118.2 (4)	C11—C12—H12A	109.5
O10—C1—H1	107.5	C11—C12—H12B	109.5
C2—C1—H1	107.5	H12A—C12—H12B	109.5
C6—C1—H1	107.5	C11—C12—H12C	109.5
O3—C2—C3	111.4 (4)	H12A—C12—H12C	109.5
O3—C2—C1	106.3 (4)	H12B—C12—H12C	109.5
C3—C2—C1	110.1 (4)	O8—C13—O7	122.0 (5)
O3—C2—H2	109.7	O8—C13—C14	126.6 (5)
C3—C2—H2	109.7	O7—C13—C14	111.4 (5)
C1—C2—H2	109.7	C13—C14—H14A	109.5
O5—C3—C2	107.4 (4)	C13—C14—H14B	109.5
O5—C3—C4	106.5 (4)	H14A—C14—H14B	109.5
C2—C3—C4	108.9 (4)	C13—C14—H14C	109.5
O5—C3—H3	111.3	H14A—C14—H14C	109.5
C2—C3—H3	111.3	H14B—C14—H14C	109.5
C4—C3—H3	111.3	C16—C15—C20	121.7 (4)
O7—C4—C5	107.9 (3)	C16—C15—O9	115.3 (4)
O7—C4—C3	110.2 (4)	C20—C15—O9	123.0 (4)
C5—C4—C3	108.9 (4)	C15—C16—C17	118.8 (5)
O7—C4—H4	109.9	C15—C16—H16	120.6
C5—C4—H4	109.9	C17—C16—H16	120.6
C3—C4—H4	109.9	C18—C17—C16	121.2 (4)
O9—C5—O10	107.5 (3)	C18—C17—H17	119.4
O9—C5—C4	108.6 (3)	C16—C17—H17	119.4
O10—C5—C4	108.9 (3)	C17—C18—C19	119.0 (4)
O9—C5—H5	110.6	C17—C18—C21	118.9 (4)
O10—C5—H5	110.6	C19—C18—C21	122.1 (4)
C4—C5—H5	110.6	C18—C19—C20	120.4 (5)
O1—C6—C1	112.3 (4)	C18—C19—H19	119.8
O1—C6—H6A	109.1	C20—C19—H19	119.8
C1—C6—H6A	109.1	C15—C20—C19	118.8 (4)
O1—C6—H6B	109.1	C15—C20—H20	120.6
C1—C6—H6B	109.1	C19—C20—H20	120.6
H6A—C6—H6B	107.9	N1—C21—C18	122.0 (4)
O2—C7—O1	122.4 (5)	N1—C21—H21	119.0
O2—C7—C8	127.4 (5)	C18—C21—H21	119.0
O1—C7—C8	110.2 (5)	N3—C22—N2	118.0 (5)
C7—C8—H8A	109.5	N3—C22—S1	123.5 (5)
C7—C8—H8B	109.5	N2—C22—S1	118.5 (4)
H8A—C8—H8B	109.5

C21—N1—N2—C22	−171.8 (6)	C7—O1—C6—C1	−102.7 (5)
C5—O10—C1—C2	61.6 (4)	O10—C1—C6—O1	−43.1 (5)
C5—O10—C1—C6	−169.7 (3)	C2—C1—C6—O1	79.8 (5)
C9—O3—C2—C3	84.1 (5)	C6—O1—C7—O2	12.4 (8)
C9—O3—C2—C1	−156.0 (4)	C6—O1—C7—C8	−166.7 (4)
O10—C1—C2—O3	−178.4 (3)	C2—O3—C9—O4	−9.7 (9)
C6—C1—C2—O3	59.1 (5)	C2—O3—C9—C10	173.3 (5)
O10—C1—C2—C3	−57.6 (5)	C3—O5—C11—O6	6.7 (7)
C6—C1—C2—C3	179.9 (4)	C3—O5—C11—C12	−172.2 (4)
C11—O5—C3—C2	−141.7 (4)	C4—O7—C13—O8	−1.1 (7)
C11—O5—C3—C4	101.7 (5)	C4—O7—C13—C14	−180.0 (5)
O3—C2—C3—O5	60.0 (5)	C5—O9—C15—C16	−161.2 (4)
C1—C2—C3—O5	−57.7 (5)	C5—O9—C15—C20	18.6 (6)
O3—C2—C3—C4	174.9 (4)	C20—C15—C16—C17	−0.1 (8)
C1—C2—C3—C4	57.2 (5)	O9—C15—C16—C17	179.8 (5)
C13—O7—C4—C5	154.5 (4)	C15—C16—C17—C18	0.7 (8)
C13—O7—C4—C3	−86.7 (5)	C16—C17—C18—C19	−0.9 (8)
O5—C3—C4—O7	−59.8 (4)	C16—C17—C18—C21	178.5 (5)
C2—C3—C4—O7	−175.3 (4)	C17—C18—C19—C20	0.3 (8)
O5—C3—C4—C5	58.4 (4)	C21—C18—C19—C20	−179.0 (5)
C2—C3—C4—C5	−57.2 (5)	C16—C15—C20—C19	−0.4 (8)
C15—O9—C5—O10	−79.8 (4)	O9—C15—C20—C19	179.7 (5)
C15—O9—C5—C4	162.5 (4)	C18—C19—C20—C15	0.3 (8)
C1—O10—C5—O9	180.0 (3)	N2—N1—C21—C18	178.3 (5)
C1—O10—C5—C4	−62.5 (4)	C17—C18—C21—N1	−171.7 (5)
O7—C4—C5—O9	−65.2 (4)	C19—C18—C21—N1	7.6 (8)
C3—C4—C5—O9	175.2 (4)	N1—N2—C22—N3	−3.1 (9)
O7—C4—C5—O10	178.1 (3)	N1—N2—C22—S1	174.7 (4)
C3—C4—C5—O10	58.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N1···O10ⁱ	0.75 (5)	2.33 (5)	3.076 (6)	172 (6)
N3—H3A···O8ⁱⁱ	0.86	2.60	3.229 (7)	131

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₇N₃O₁₀S
M_r	525.53
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	292
a, b, c (Å)	9.848 (3), 11.515 (3), 23.250 (4)
V (Å³)	2636.5 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.54 × 0.46 × 0.24

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.909, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	5423, 4940, 2851
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.195, 1.07
No. of reflections	4940
No. of parameters	329
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.27
Absolute structure	Flack, (1983), 2108 Friedel pairs
Absolute structure parameter	0.35 (19)

Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), 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
N2—H2N1···O10ⁱ	0.75 (5)	2.33 (5)	3.076 (6)	172 (6)
N3—H3A···O8ⁱⁱ	0.86	2.60	3.229 (7)	130.9

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

Acknowledgements

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

References

Chen, W. S., Lu, S. D. & Eberhard, B. (1981). Liebigs Ann. Chem. 10, 1893–1897. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J., White, P. S. & Enright, G. D. (1993). DIFRAC. American Crystallographic Association, Pittsburgh Meeting Abstract, PA 104. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sha, J. Z. & Mao, H. K. (1987). Chin. Pharm. Bull. 22, 21–27. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Google Scholar
Yang, H. J., Hu, C., LI, Y. & Yin, S. F. (2008). Chin. J. Org. Chem. 28, 899–902. CAS Google Scholar
Zhu, Q. L., Tang, Q., Li, Y. & Yin, S. F. (2006). Chin. J. Org. Chem. 26, 1264–1267. CAS Google Scholar

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Volume 65| Part 4| April 2009| Page o679

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-[4-(2,3,4,6-Tetra-O-acetyl-β-D-allo­pyranos­yl­oxy)benzyl­­idene]thio­semi­carbazide

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-[4-(2,3,4,6-Tetra-O-acetyl-β-D-allopyranosyloxy)benzylidene]thiosemicarbazide