Synthesis and crystal structure of 4-phenyl-3-(pyridin-4-yl)-1H-1,2,4- triazole-5(4H)-thione

Article abstract of DOI:10.14233/ajchem.2014.16183

A triazole derivative i.e., 4-phenyl-3-(pyridin-4-yl)-1H-1,2,4-triazole- 5(4H)-thione was synthesized and its structure was studied by X-ray diffraction. The crystals are orthorhombic, space group pbcn with a = 11.337 (2), b = 12.789 (3), c = 17.625 (4) ?

Full text of DOI:10.14233/ajchem.2014.16183

Asian Journal of Chemistry; Vol. 26, No. 7 (2014), 2083-2085
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.16183
Synthesis and Crystal Structure of 4-Phenyl-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione
1
1
WEI GAO , FENG-PENG GUO2,* and JING YANG
1School of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou 450046, P.R. China
2College of Basic Medicine, Henan University of Traditional Chinese Medicine, Zhengzhou 450046, P.R. China
*Corresponding author: E-mail: weigao415@aliyun.com
Received: 12 August 2013;
Accepted: 20 November 2013;
Published online: 22 March 2014;
AJC-14966
A triazole derivative i.e., 4-phenyl-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione was synthesized and its structure was studied by
X-ray diffraction. The crystals are orthorhombic, space group pbcn with a = 11.337 (2), b = 12.789 (3), c = 17.625 (4) Å, α = 90.00, β =
90, γ = 90°, V = 2555.4 (9) Å3, Z = 8, F(000) = 1056, Dc = 1.322 g/cm3, µ = 0.240 cm-1, the final R = 0.0528 and wR = 0.1429. A total of
19773 reflections were collected, of which 2254 were independent (Rint = 0.043).
Keywords: Synthesis, Heterocycle, Crystal structure, Triazole.
(3) Å, c = 17.625 (4) Å, α = 90°, β = 90°, γ = 90°, V = 2555.4
(9) Å3, Dc = 1.322 g/cm3. The absorption coefficient µ = 0.240
mm-1 and Z = 8. The structure was solved by direct methods
with SHELXS-975 and refined by the full-matrix least squares
method on F2 data using SHELXL-976. The empirical absor-
ption corrections were applied to all intensity data. H atom of
N-H was initially located in a difference Fourier map and were
refined with the restraint Uiso (H) = 1.2 Ueq(N). Other H atoms
were positioned geometrically and refined using a riding
model, with d(C···H) = 0.93-0.97 Å and Uiso (H) = 1.2 Ueq
(C) or 1.5 Ueq (Cmethyl). The final full-matrix least squares
refinement gave R = 0.0528 and wR = 0.1429.
INTRODUCTION
In recent years, sulfur and nitrogen linked heterocyclic
compounds have received special attention due to their pesti-
cidal importance1. 1,2,4-Triazole moiety has been claimed to
have beneficial medicinal and agricultural applications2.
Because of its good bioactivity and usefulness as intermediates
in organic synthesis, the 1,2,4-triazole has been widely studied3.
Meanwhile, some triazole and nicotine structure are also exhi-
bited good biological activity4. As a continuation of our work,
a triazole derivative have been synthesized and its structure
was confirmed by X-ray crystallography. In this paper, we
report the synthesis and crystal structure of the 4-phenyl-3-
(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione.
RESULTS AND DISCUSSION
EXPERIMENTAL
Structure of the title complex: The title compound was
confirmed by single crystal X-ray diffraction analysis. Crysta-
llographic and refinement parameters are given in Table-1.
The selected bond lengths and bond angles listed in Tables 2-
4, respectively. The structure was solved by direct methods.
Anisotropic displacement parameters were applied to all
nonhydrogen atoms in full-matrix least-square refinements
based on F2. The hydrogen atoms were set in calculated posi-
tions with a common fixed isotropic thermal parameter.
The molecular structure and the packing view of the title
compound are shown in Figs. 1 and 2, respectively.
Synthesis: Compound nicotine acylhydrazine reacting
with 1.5 g of isothiocyanate gave compound thiurea after 3h
refluxing in alcohol. Compound thiourea was refluxed with
2 N NaOH for 3 h and was neutralized by diluted hydrochloric
acid to give title compound. The yields of this step were quanti-
tative. The compound was recrystallized by DMF, to give
colorless prism.
The crystal of title compound with dimensions of 0.18
mm × 0.16 mm × 0.10 mm was mounted on a Rigaku Saturn
CCD area-detector diffractometer with a graphite-monochro-
mated MoKα radiation (γ = 0.71073 Å) by using a phi and
scan modes at 293 (2) K in the range of 2.31° ≤ θ ≤ 25.02°.
The crystal belongs to monoclinic system with space group
P21/c and crystal parameters of a = 11.337 (2) Å, b = 12.789
The title compound crystallizes in the orthorhombic space
group pbcn. The unit cell contains one molecule of C13H10N4S.
As can be seen in Fig. 1, the H atom of the NH group is trans-
ferred to the thio group of triazole ring. The dihedral angles

2084 Gao et al.
Asian J. Chem.
TABLE-1
CRYSTAL DATA AND STRUCTURE
REFINEMENT FOR THE TITLE COMPOUND
TABLE-4
SELECTED TORSIONAL ANGELS (°)
FOR THE TITLE COMPOUND
Items
Empirical formula
Formula weight
Crystal system
Unit cell dimensions
a (Å)
b (Å)
c (Å)
Unit cell angles (°)
Values
C13H10N4S
254.31
Bond angles
X-ray Crystal
2.3(4)
-0.9(4)
0.3(2)
-0.1(2)
171.78(19)
178.7(2)
141.3(2)
144.8(2)
C(3)-N(1)-C(2)-C(1)
N(1)-C(3)-C(4)-C(5)
N(3)-N(2)-C(6)-N(4)
C(7)-N(4)-C(6)-N(2)
C(8)-N(4)-C(6)-N(2)
C(7)-N(4)-C(6)-C(5)
C(1)-C(5)-C(6)-N(2)
C(4)-C(5)-C(6)-N(4)
Orthorhombic
11.337(2)
12.789(3)
17.625(4)
90
α
90
β
90
2555.4(9)
γ
Volume (Å3)
Z
8
293(2)
Pbcn
Temperature (K)
Space group
Wavelength (Å)
Calculated density (g/cm3)
Absorption coefficient (mm-1)
F(000)
0.71073
1.322
0.240
1056
Crystal size (mm)
Theta range for data collection (º)
Reflections collected
Independent reflections
Final R indices [I > 2σ(I)]
0.18 × 0.16 × 0.10
2.31 – 25.02
19773
2254 [R(int) = 0.0430]
R1 = 0.0528, wR2 = 0.1429
between the triazole ring and pyridine or phenyl planes are 37.2°
and 121.5°, respectively. The rings (C1, C2, C3, C4, C5, N1),
(C6, C7, N2, N3, N4) and (C8, C9, C10, C11, C12, C13) are
fairly planar with plane equation 10.755x + 3.350y + 3.121z =
5.9519 and 10.627x + (-4.453)y + (-0.193)z = -0.4902, -7.131x
+ (-2.781)y + 13.155z = 11.4557, respectively. The largest
deviation from the least squares plane is 0.0087 Å7.
Fig. 1. Molecular structure of the title compound
As shown in Fig. 2, the crystal structure is stabilized by
van der Waals' interactions.
TABLE-2
SELECTED BOND LENGTHS [Å] FOR THE TITLE COMPOUND
Bond lengths
S(1)-C(7)
N(1)-C(3)
N(1)-C(2)
N(2)-C(6)
N(2)-N(3)
N(3)-C(7)
N(4)-C(6)
N(4)-C(7)
N(4)-C(8)
C(1)-C(5)
X-ray Crystal
1.668(2)
1.331(3)
1.335(3)
1.301(3)
1.381(2)
1.346(3)
1.387(3)
1.391(3)
1.445(3)
1.385(3)
TABLE-3
SELECTED BOND ANGLES [°] FOR THE TITLE COMPOUND
Fig. 2. Two-dimensional network of the title compound
Bond angles
C(3)-N(1)-C(2)
C(6)-N(2)-N(3)
C(7)-N(3)-N(2)
C(6)-N(4)-C(7)
C(6)-N(4)-C(8)
C(7)-N(4)-C(8)
C(5)-C(1)-C(2)
N(1)-C(2)-C(1)
X-ray Crystal
117.2(2)
Supplementary material: CCDC 955581 contains the
supplementary crystallographic data for this paper. These data
can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html or from the Cambridge CrystallographicData
Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK
(Fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
104.36(17)
113.40(17)
107.31(17)
127.07(17)
125.08(17)
118.6(2)
123.5(2)

Vol. 26, No. 7 (2014)
Synthesis and Crystal Structure of 4-Phenyl-3-(pyridin-4-yl)-1H-1,2,4-triazole-5(4H)-thione 2085
(c) P.H. Zhao, M. Zhang and G.Z. Zhao, Asian J. Chem., 25, 5068
ACKNOWLEDGEMENTS
(2013); (d) S.Ö. Yildirim, M. Akkurt, A. Çetin, A. Cansiz, M. Sekerci
and C. Kazak, Acta Crystallogr. Sect. E Struct. Rep. Online, 61, o619
(2005).
We gratefully acknowledge financial support from the
Doctoral Research Fund of Henan University of Traditional
Chinese Medicine.
5. G.M. Sheldrick, SHELXS97, A Program for Crystal Structure Solution;
University of Göttingen: Germany (1997).
6. G.M. Sheldrick, SHELXL97, A Program for Crystal Structure Refinement;
University of Göttingen: Germany (1997).
REFERENCES
7. (a) X.F. Liu, Inorg. Chim. Acta, 378, 338 (2011); (b) X.F. Liu and X.Y.
Yu, Acta Crystallogr., E67, m1552 (2011); (c) X.F. Liu, X.W. Xiao
and L.J. Shen, Transition Met. Chem., 36, 465 (2011); (d) X.F. Liu and
B.S. Yin, J. Coord. Chem., 63, 4061 (2010); (e) X.F. Liu, Z.Q. Jiang
and Z.J. Jia, Polyhedron, 33, 166 (2012); (f) X.F. Liu, X.W. Xiao, L.J.
Shen, J.H. Fang, J.R. Wang, H.Q. Gao and X.H. Liu, Chinese J. Struct.
Chem., 30, 1016 (2011); (g) X.F. Liu, X.W. Xiao and L.J. Shen, J.
Coord. Chem., 64, 1023 (2011); (h) X.F. Liu, X.W. Xiao and X.H. Liu,
Chinese J. Struct. Chem., 30, 1437 (2011); (i) X.F. Liu and B.S. Yin, Z.
Anorg. Allg. Chem., 637, 377 (2011); (j) X.F. Liu and X.W. Xiao, J.
Organomet. Chem., 696, 2767 (2011); (k) X.F. Liu, W.H. Xu and H.
Li, Acta Crystallogr. Sect. E Struct. Rep. Online, 67, o370 (2011); (l)
L.J. Luo, X.F. Liu and H.Q. Gao, J. Coord. Chem., 66, 1077 (2013);
(m) X.F. Liu and H.Q. Gao, J. Clust. Sci., 25, 367 (2014).
1. (a) X.H. Liu, C.X. Tan and J.Q. Weng, Phosphorus Sulfur Silicon Rel.
Elem., 186, 552 (2011); (b) X.H. Liu, C.X. Tan and J.Q. Weng, Phos-
phorus Sulfur Silicon Rel. Elem., 186, 558 (2011); (c) P.Q. Chen, C.X.
Tan, J.Q. Weng and X.H. Liu, Asian J. Chem., 24, 2808 (2012); (d)
Y.L. Xue, Y.G. Zhang and X.H. Liu, Asian J. Chem., 24, 3016 (2012).
2. (a)Y.L. Xue,Y.G. Zhang and X.H. Liu, Asian J. Chem., 24, 1571 (2012);
(b) X.F. Liu and X.H. Liu, Acta Crysallogrt. E, 67, o202 (2011); (c)
X.H. Liu, L. Pan, C.X. Tan, J.Q. Weng, B.L. Wang and Z.M. Li, Pestic.
Biochem. Physiol., 101, 143 (2011).
3. (a) X.H. Liu, J.Q. Weng, C.X. Tan, H.J. Liu, Acta Crystallogr., E67,
o1940 (2011); (b) X.H. Liu, J.Q. Weng, C.X. Tan, L. Pan, B.L. Wang
and Z.M. Li, Asian J. Chem., 23, 4031 (2011); (c) H.J. Liu, J.Q. Weng,
C.X. Tan, X.H. Liu, Acta Crystallogr., E67, o1940 (2011).
4. (a) X.H. Liu, C.X. Tan and J.Q. Weng, Asian J. Chem., 23, 4064 (2011);
(b)Y.L. Xue,Y.G. Zhang and X.H. Liu, Asian J. Chem., 24, 5087 (2012);