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

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.

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 = 525.53

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.195

S = 1.07

4940 reflections

329 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack, (1983 ▶), 2108 Friedel pairs

Flack parameter: 0.35 (19)

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.

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

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

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

C22H27N3O10S	F(000) = 1104
Mr = 525.53	Dx = 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

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

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(Fo2) + (0.1108P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
4940 reflections	Δρmax = 0.30 e Å−3
329 parameters	Δρmin = −0.27 e Å−3
0 restraints	Absolute structure: Flack, (1983), 2108 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.35 (19)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) .