Synthesis and crystal structure of 2-aminoacetyl-1,3,4-thiadiazole

Article abstract of DOI:10.1007/s11176-006-0022-2

2-Aminoacetyl-1,3,4-thiadiazole was synthesized, and its structure was studied. In crystal, the thiadiazole molecules form hydrogen-bonded endless one-dimensional chains related by the glide reflection plane.

Full text of DOI:10.1007/s11176-006-0022-2

Russian Journal of General Chemistry, Vol. 75, No. 12, 2005, pp. 1962 1964. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 12, 2005,
pp. 2052 2054.
Original Russian Text Copyright
2005 by Kadirova, Nuralieva, Alieva, Talipov, Tilyakov, Parpiev.
Synthesis and Crystal Structure
of 2-Aminoacetyl-1,3,4-thiadiazole
Sh. A. Kadirova*, G. A. Nuralieva*, M. A. Alieva*,
S. A. Talipov**, Z. G. Tilyakov**, and N. A. Parpiev*
* Ulugbek National University of Uzbekistan, Tashkent, Uzbekistan
** Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, Tashkent, Uzbekistan
Received November 19, 2004
Abstract 2-Aminoacetyl-1,3,4-thiadiazole was synthesized, and its structure was studied. In crystal, the
thiadiazole molecules form hydrogen-bonded endless one-dimensional chains related by the glide reflection
plane.
Proceeding with our research into 1,3,4-thiadiazole
derivatives [1 3] we synthesized 2-aminoacetyl-1,3,4-
thiadiazole that belongs to compounds known to ex-
hibit a broad-range biological and pharmacological
activity [4]. A series of 1,3,4-thiadiazole derivatives
was synthesized and studied mostly by means of H
and IR spectroscopy [5].
The X-ray analysis showed that single crystals of
compound II belong to the orthorhombic syngony.
Figure 1 presents the molecular structure of II, and
the table lists the interatomic distances and bond
angles. Compound II (Fig. 1), like previously studied
2-amino-5-phenyl- and 2-amino-5-(m-nitrophenyl)-
1,3,4-thiadiazoles [1, 2], have the N1, N2, and S1 lone
electron pairs conjugated with the double bonds of the
thiadiazole ring, as evidenced by the N1 C1, N2 C2,
and N1 N2 bond lengths of 1.283(5), 1.302(4), and
1.387(4) , respectively. The endocyclic N C bond
lengths are intermediate between the standard single
and double bond lengths. The imino N3 C2 and
1
Here we present the results of single-crystal X-ray
analysis of 2-aminoacetyl-1,3,4-thiadiazole (II) pre-
pared by the reaction of 2-amino-1,3,4-thiazole (I)
with acetic anhydride. The synthesis of acetyl deri-
vative II was performed by the procedure in [6] by
heating compound I in acetic anhydride. Therewith,
the yield of the final product was 76%.
N3 C3 [1.372(4) and 1.362(4)
] and C3=O1
[1.218(4) ] bond lengths are normal values. In whole
the molecule is planar, which is evidenced by the fact
that the molecule in crystal is in a special position,
viz. in the glide reflection plane.
N
N
+ Ac2O
H C
C NH2
S
I
In the crystal structure of thiadiazole II, as noted
above, the molecules are in special positions, i.e. glide
reflection planes perpendicular to the y axis. The
N
N
H C
C NHAc
AcOH
S
II
N2
The IR spectrum of compound II contains charac-
N1
teristic absorption bands at 1543 [ (C=N)] and
1439 cm
N3
C2
[
as(C=N)] and =N-N=, N=C sN, C=O, and
1
C4
C S absorption bands at 1040, 1564, 1684, and
1
634 cm , respectively [7].
C3
1
The H NMR spectrum of compound II shows
C1
downfield multiplet signals centered at 9.08 ppm,
that were assigned to the thiadiazole ring proton.
Methyl protons give a broadened singlet at
2.14 ppm and the imino group, a singlet at
12.4 ppm.
O1
S1
Fig. 1. Molecular structure of compound II and atom
numbering scheme.
1070-3632/05/7512-1962 2005 Pleiades Publishing, Inc.

SYNTHESIS AND CRYSTAL STRUCTURE OF 2-AMINOACETYL-1,3,4-THIADIAZOLE
1963
molecules related to each other by the glide reflection
plane is observed. Thus, these contacts make possible
formation of a layer on the reflection plane (Fig. 2).
Molecules related by the inversion center form a layer
antiparallel to the mentioned layer (Fig. 3). Therewith,
the distance between the two layers is 3.307 . The
distance between the C2 atoms of opposite molecules
is close to this value (3.365 ). These data suggest
dipole interactions between molecules of opposite
layers, which makes the crystal packing tight (packing
coefficient 0.732).
EXPERIMENTAL
The IR spectra were measured on an Avatar in-
1
1
strument at 400 4000 cm . The H NMR spectra
were obtained on XL-100 and XL-200 spectrometers
(solvent DMSO-d6, internal reference HMDS).
Fig. 2. Association of molecules II via H bonds and
shortened contacts.
The single-crystal X-ray analysis of 2-amino-
acetyl-1,3,4-thiadiazole (II) was performed on an
STOE Stadi-4 diffractometer ( MoK radiation,
z
graphite monochromator, /2 scanning, 2
560).
The C4H5N3OS crystals have orthorhombic msyaxngony.
x
Unit cell parameters: a 9.2610, b 6.6130, c 9.6350
;
0
3
V 590.1(5) 3, Z 4, dcalc 1.612 g cm , space group
Pnma. Data collection was performed at 293 2 K.
Crystal dimensions 0.2 0.2 0.4 mm, (MoK )
1
0.456 mm , and F(000) 296. Angle range 3.05
25 . The structure was solved by the direct method
using the SHELXS-97 program package [8] and re-
fined by the SHELXL-97 program package [9].
Hydrogen atoms were located geometrically and re-
fined by the rider model. The divergence factor R after
Interatomic distances and bond angles in structure II
y
Bond
d,
Bond
d,
S1 C1
1.717(3)
1.726(3)
1.493(5)
1.283(5)
1.372(4)
N3 C3
O1 C3
N1 N2
N2 C2
1.362(4)
1.218(4)
1.387(4)
1.302(4)
S1 C2
C3 C4
N1 C1
N3 C2
Angle
, deg
Angle
, deg
Fig. 3. Crystal structure of compound II.
C1S1C2
N2N1C1
N1N2C2
C2N3C3
C2N3H2
C3N3H2
S1C1N1
85.90(16)
112.0(3)
111.6(3)
124.0(3)
118.0(2)
118.0(2)
115.7(2)
O1C3N3
O1C3C4
S1C2N3
N2C2N3
S1C2N2
N3C3C4
121.0(3)
122.3(3)
124.0(2)
121.2(3)
114.8(2)
116.7(3)
molecules form endless one-dimensional chains run-
ning along the x plane, by means of the N3 H O1
bond with a length 2.848(4) and an angle of 165(3)
[N3 H 0.79(4), H O1 2.07(3) ], related to each
other by the glide reflection plane. A shortened
contact between sulfur and nitrogen [3.225(3) ] in
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

1964
KADIROVA et al.
the final step of refinement of positional and thermal
parameters was 0.0389. The molecular drawings
were performed using the XP program in SHELXTL-
Plus [10].
2. Kadirova, Sh., Abstracts of Papers, XVIII Ulusal
kimya kongresi, Kars, 2004, p. 406.
3. Kadirova, Sh., Abstracts of Papers, XVIII Ulusal
kimya kongresi, Kars, 2004, p. 407.
The structures were registered in the Cambridge
structural database.
4. Sandstrom, J., Adv. Heterocycl. Chem., 1969, vol. 9,
pp. 165, 199.
5. Eremin, K.I., Golovanov, A.V., Krutikov, V.I., and
Lavrent’ev, A.N., Zh. Obshch. Khim., 1997, vol. 67,
no. 1, p. 144.
2-Aminoacetyl-1,3,4-thiadiazole (II). A solution
of 1.01 g of 2-amino-1,3,4-thiazole (I) in 20 ml of
acetic anhydride was stirred for 1.5 h at 100 C and
then cooled to 0 C. The precipitate that formed was
filtered off and recrystallized from ethanol. Yield
76%, mp 242 244 C. The single crystals of com-
pound II for X-ray analysis were obtained by recrys-
tallization from hot ethanol.
6. Elokhina, V.N., Karnauhova, R.V., Nakhmano-
vich, A.S., Larina, L.I., and Lopyrev, V.A., Zh. Org.
Khim., 2002, vol. 38, no. 2, p. 318.
7. Nakamoto, K., Infrared and Raman Spectra of In-
organic and Coordination Compounds, New York:
Wiley, 1986. Translated under the title IK spektry
ACKNOWLEDGMENTS
neorganicheskih
i
koordinatsionnyh soedinenii,
Moscow: Mir, 1991, p. 204.
The work was financially supported by the Center
for Science and Technologies of Uzbekistan (grant
no. F-3.9).
8. Sheldrick, G.M., Acta Crystallogr., Sect. A, 1990,
vol. 46, no. 3, p. 467.
9. Sheldrick, G.M., SHELXL-97, Program for the Re-
finement of Crystal Structures, Gottingen: Univ. of
Gottingen, 1997.
REFERENCES
1. Ishanhodzhaeva, M.M., Kadyrova, Sh.A., Surazhs-
kaya, M.D., Parpiev, N.A., and Koz’min, P.A., Zh.
Org. Khim., 2001, vol. 37, no. 5, p. 759.
10. Siemens XP. Molecular Graphics Program, Ver. 5.03,
Madison: Siemens Analytical X-Ray Instruments,
1994.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005