5-Phenyl-1,3,4-thiadiazol-2-yl 2,3,4,6-tetra-O-acetyl-1-thio-β-D- glucopyranoside

Article abstract of DOI:10.1107/S0108270105003951

The structure of the title compound, C₂₂H₂₄N ₂O₉S₂, is described. This compound consists of a sugar ring and a heterocyclic base linked unusually by an S atom. The sugar is in a ⁴C₁

Full text of DOI:10.1107/S0108270105003951

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
5-Phenyl-1,3,4-thiadiazol-2-yl
2,3,4,6-tetra-O-acetyl-1-thio-
b-D-glucopyranoside
Zao-Zao Qiu, Xin-Ping Hui and Peng-Fei Xu*
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou
73000, People's Republic of China
Correspondence e-mail: xupf@lzu.edu.cn
Received 11 October 2004
Accepted 3 May 2005
Online 9 July 2005
Figure 1
A view of the title compound, with the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii.
The structure of the title compound, C22H24N2O9S2, is
described. This compound consists of a sugar ring and a
heterocyclic base linked unusually by an S atom. The sugar is
4
in a C1 chair conformation and forms dihedral angles of
49.54 (4) and 33.42 (5)ꢀ with the thiadiazole and phenyl rings,
respectively. The S atom occupies an equatorial position of the
The two endocyclic CÐO bonds, C1ÐO1 and C5ÐO1, are
Ê
nearly equal [1.431 (2) and 1.418 (2) A, respectively]. The
conformation about the exocyclic C1ÐC6 bond is gauche±
trans, with torsion angles O2ÐC6ÐC1ÐO1 = 59.6 (2)ꢀ and
O2ÐC6ÐC1ÐC2 = 61.0 (2)ꢀ.
Ê
sugar ring and lies 1.807 (2) A out of the corresponding mean
plane.
The heterocyclic 1,3,4-thiadiazole ring is planar to within
experimental error and the lengths of the endocyclic bonds
Comment
Ê
Ê
1,3,4-Thiadiazole derivatives display a broad spectrum of
biological activities, such as fungicidal (Zou et al., 2002),
antibacterial (Deibel et al., 2004), antidepressant (Clerici et al.,
2001) and anti-epileptic (Masereel et al., 2002). However, the
application of 1,3,4-thiadiazoles is limited because of their
poor solubility both in organic solvents and in water. In the
course of identifying new chemical structures that may serve
as leads in the design of novel antiviral agents, we were
particularly interested in the linking of thio-1,3,4-thiadiazoles
to hydrophilic moieties such as d-glucose. The present struc-
ture determination is part of an investigation into the
nucleophilic substitution of a bromosugar to a thiaheterocyclic
compound. We report here the X-ray crystal structure deter-
mination of the title compound, (I) (Fig. 1).
[C15ÐN1 = 1.299 (2) A and C16ÐN2 = 1.303 (2) A], clearly
indicate that they are double bonds. The N1ÐN2 bond length
Ê
of 1.375 (2) A is slightly shorter than the single-bond value of
Ê
1.393 (4) A in the hydrochloride of 5-(4-methoxyphenyl)-4-
phenyl-1,3,4-thiadiazolium-2-phenylaminide (Cheung et al.,
1992). The large deviation of the bond angle [S2ÐC15ÐN1 =
114.16 (13)ꢀ] in the ring from the value of 120ꢀ usually found
in trigonal±planar arrangements is common in ®ve-membered
rings (Downie et al., 1972). The phenyl ring linked to atom C16
forms a dihedral angle of 16.95 (6)ꢀ with the heterocyclic
plane.
The S atom of the thioglucosidic linkage bridges the sugar
and heterocyclic rings. The dihedral angles between the mean
plane of the sugar ring and the thiadiazole and phenyl planes
are 49.54 (4) and 33.42 (5)ꢀ, respectively. The orientation of
the thiadiazole moiety relative to the glucose ring may be
described by the torsion angles N1ÐC15ÐS1ÐC5
=
107.0 (2)ꢀ, S2ÐC15ÐS1ÐC5 = 78.1 (1)ꢀ, C15ÐS1ÐC5Ð
O1 = 67.2 (1)ꢀ and C15ÐS1ÐC5ÐC4 = 176.3 (1)ꢀ.
The 2,3,4,6-tetra-O-acetyglucopyranosyl ring of (I) assumes
Experimental
4
a C1 chair conformation, with atoms C2 and C5 displaced
from the C1/C3/C4/O1 mean plane. The mean CÐC and CÐ
5-Mecapto-2-phenyl-1,3,4-thiadiazole (0.582 g, 3 mmol), ꢀ-aceto-
bromoglucose (1.230 g, 3 mol) and KOH (0.168 g, 3 mmol) were
reacted at room temperature for 12 h. The product was obtained via
column-chromatograpic puri®cation and the crystals were recrys-
tallized by slow evaporation from petroleum ether±ethyl acetate (4:1)
Ê
O(acetyl) bond lengths of 1.519 (2) and 1.422 (2) A,
respectively, in the sugar moiety compare well with similar
averages observed in pyranose sugars (Berman et al., 1967).
Acta Cryst. (2005). C61, o475±o476
DOI: 10.1107/S0108270105003951
# 2005 International Union of Crystallography o475

organic compounds
(m.p. 424±426 K). 1H NMR (400 MHz, CDCl3): ꢁ 2.018 (s, 3H), 2.040
(s, 3H), 2.060 (s, 3H), 2.088 (s, 3H), 3.845±3.886 (m, 1H), 4.166 (dd, J =
2.0 and 12.8 Hz, 1H), 4.302 (dd, J = 4.8 and 12.8 Hz, 1H), 5.137±5.205
(m, 2H), 5.309 (t, J = 9.2 Hz, 1H), 5.444 (d, J = 10.4 Hz, 1H), 7.459±
7.511 (m, 3H), 7.899±7.922 (m, 2H).
structure: TEXSAN; molecular graphics: ORTEPIII (Burnett &
Johnson, 1996); software used to prepare material for publication:
PLATON (Spek, 2003).
Financial support by the Natural Science Foundation of
China (grant Nos. 20372027 and 20021001) and the Natural
Science Foundation of Gansu Province (grant No.
YS031-A21-002) is gratefully acknowledged. The collection
and processing of the X-ray data in Professor K. Tatsumi's
group by Dr T. Matsumoto (Nagoya University) is also
gratefully acknowledged.
Crystal data
C22H24N2O9S2
Mr = 524.56
Orthorhombic, P212121
Mo Kꢀ radiation
Cell parameters from 7511
re¯ections
ꢂ = 3.2±27.5ꢀ
Ê
a = 8.010 (2) A
1
Ê
b = 10.526 (2) A
ꢃ = 0.28 mm
T = 173.2 K
Ê
c = 28.685 (6) A
Ê
V = 2418.7 (9) A
3
Block, colourless
0.35 Â 0.25 Â 0.20 mm
Z = 4
Dx = 1.440 Mg m
3
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TY1004). Services for accessing these data are
described at the back of the journal.
Data collection
Rigaku/MSC Mercury CCD area-
detector diffractometer
! scans
Absorption correction: multi-scan
(TEXSAN; Molecular Structure
Corporation, 1999)
5524 independent re¯ections
5151 re¯ections with F2 > 2ꢄ(F2)
Rint = 0.037
References
ꢂmax = 27.5ꢀ
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Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak
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h = 10 ! 9
k = 11 ! 13
Tmin = 0.825, Tmax = 0.947
19569 measured re¯ections
l = 37 ! 37
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343.
Re®nement
Re®nement on F
R[F2 > 2ꢄ(F2)] = 0.033
wR(F2) = 0.046
S = 1.06
5499 re¯ections
w = 1/[ꢄ2(Fo) + 0.00063|Fo|2]
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.25 e A
3
Ê
0.24 e A
Áꢅmin
=
Absolute structure: Flack (1983),
2357 Friedel pairs
Flack parameter: 0.00 (5)
317 parameters
H-atom parameters constrained
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1590.
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1454.
All H atoms were placed in calculated positions with CÐH
Ê
distances of 0.97 A, and were included in the ®nal cycles of re®ne-
ment with Uiso(H) = 1.2Ueq(C).
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1991); cell re®nement: MSC/AFC
Diffractometer Control Software; data reduction: TEXSAN (Mole-
cular Structure Corporation, 1999); program(s) used to solve struc-
ture: SIR92 (Altomare et al., 1994); program(s) used to re®ne
ꢁ
o476 Qiu et al. C22H24N2O9S2
Acta Cryst. (2005). C61, o475±o476