Synthesis, crystal structure and quantum chemical study on 3-phenylamino-4-phenyl-1,2,4-triazole-5-thione

Article abstract of DOI:10.3390/molecules14020608

3-Phenylamino-4-phenyl-1,2,4-triazole-5-thione was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. Density functional theory calculations of the structure, natural bond orbitais, atomic charge distributions and thermodynamic functions of the title compound were performed at B3LYP/ 6-311G** and PBE1PBE/6-311G **levels of theory, respectively. NPA atomic charge distributions indicate that the title compound can be used as a potential multidentate ligand to coordinate with various metallic ions. Calculation of the second order optical nonlinearity was also carried out. The thermodynamic properties of C_p,m⁰, S_m⁰ and 77°m were calculated and correlative equations between the thermodynamic properties and temperatures were also obtained.

Full text of DOI:10.3390/molecules14020608

Molecules 2009, 14, 608-620; doi:10.3390/molecules14020608
OPEN ACCESS
molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Synthesis, Crystal Structure and Quantum Chemical Study on
3-Phenylamino-4-Phenyl-1,2,4-Triazole-5-Thione
Hong-Yan Wang 1, Pu-Su Zhao 1,*, Rong-Qing Li 1 and Su-Min Zhou 2,*
1
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials Huaiyin Teachers College，
Huaian, Jiangsu, 223300, P. R. China; E-mails: why6952@163.com (H-Y. W.),
rongqingli333@yahoo.com (R-Q. L.)
2
Department of Chemical Engineering, Huaiyin Industry College, Huaian Jiangsu, 223001, P. R.
China; E-mail: zhaopusu@163.com (S-M. Z.)
* Author to whom correspondence should be addressed; E-mail: zhaopusu@hytc.edu.cn; Tel.: +86-
0517-83525083; Fax: +86-0517-83525083.
Received: 13 December 2008; in revised form: 15 January 2009 / Accepted: 21 January 2009 /
Published: 4 February 2009
Abstract: 3-Phenylamino-4-phenyl-1,2,4-triazole-5-thione was synthesized and
characterized by elemental analysis, IR and X-ray single crystal diffraction. Density
functional theory calculations of the structure, natural bond orbitals, atomic charge
distributions and thermodynamic functions of the title compound were performed at
B3LYP/ 6-311G** and PBE1PBE/6-311G**levels of theory, respectively. NPA atomic
charge distributions indicate that the title compound can be used as a potential multi-
dentate ligand to coordinate with various metallic ions. Calculation of the second order
optical nonlinearity was also carried out. The thermodynamic properties of C0p,m, S0 and
m
H0 were calculated and correlative equations between the thermodynamic properties and
m
temperatures were also obtained.
Keywords: Synthesis; Crystal structure; DFT; Second order optical nonlinearity.
Introduction
Compounds containing a 1H-1,2,4-triazole group and its derivatives are of great interest because
they exhibit fungicidal and plant-growth regulating activity [1-2]. They also show antibacterial activity

Molecules 2009, 14
609
against Puccinia recondite and root-growth regulation in cucumber [3]. In previous papers [4-8], we
have reported several new compounds containing the 1,2,4-triazole moiety. 1,2,4-Triazole-5-thiones
are important triazole derivatives and many mono-, di- and tri-substituted 1,2,4-triazole-5-thiones
have been reported [9-12], but, to our knowledge, no structural data obtained either by experimental or
theoretical methods have been reported so far for the title compound, 3-phenylamino-4-phenyl-1,2,4-
triazole-5-thione. Especially, there have been no reports on the bioactivities of this compound till now,
so we have synthesized the title compound and determinations of its bioactivities are currently in
progress. On the other hand, in recent years, density functional theory (DFT) has become an
increasingly useful tool for experimental studies. The success of DFT is mainly due to the fact that it
describes small molecules more reliably than Hartree-Fock theory. It is also computationally less
demanding than wave function based methods with inclusion of electron correlation [13-14]. Thus, in
order to characterize the correlation between molecular structure and macroscopic properties in the
studied compound, it seem to be essential to undertake a detailed comparative study of the isolated
molecule and the solid state unit. In this paper, a concerted approach by X-ray crystallography and
DFT calculation was used, which takes advantage of both the high interpretative power of the
theoretical studies and the precision and reliability of the experimental method. At the same time, a
comparison of some calculated results is also made with those of a similar compound, 3-benzyl-4-
phenyl-1,2,4-triazole-5-thione, which was reported earlier by this group [8].
Results and Discussion
Description of the crystal structure
The displacement ellipsoid plot with the numbering scheme for the title compound is shown in
Figure 1. Figure 2 shows a perspective view of the crystal packing in the unit cell. Selected bond
lengths and bond angles by X-ray diffractions are listed in Table 1, along with the calculated bond
parameters.
Figure 1. Molecular structure with the atomic numbering scheme for the title compound.

Molecules 2009, 14
Figure 2. A view of the crystal packing down the c axis for the title compound.
610
Table 1. Selected structural parameters by X-ray and theoretical calculations.
B3LYP/
6-311G**
1.6684
1.4073
1.3822
1.3924
1.3498
1.3916
1.394
PBE1PBE/
6-311G**
1.659
B3LYP/
6-311G**
1.3644
1.3034
1.3985
1.431
PBE1PBE/
6-311G**
1.3581
Bond lengths (Å)
Exp.
Bond lengths (Å)
Exp.
S(1)-C(13)
N(1)-C(6)
1.692(3)
1.424(4)
1.383(4)
1.388(4)
1.313(4)
1.362(5)
1.361(5)
1.350(6)
N(1)-C(14)
N(2)-C(14)
1.339(4)
1.301(4)
1.365(4)
1.433(4)
1.374(5)
1.374(5)
1.378(6)
1.370(4)
1.3985
1.3683
1.3844
1.3439
1.388
1.2995
N(2)-N(4)
N(3)-C(13)
1.391
N(3)-C(14)
N(3)-C(12)
1.4204
N(4)-C(13)
C(1)-C(2)
1.3882
1.3998
1.3941
1.3947
1.3846
C(3)-C(4)
C(5)-C(6)
1.3959
C(7)-C(12)
1.3904
1.3894
C(8)-C(9)
1.3907
C(9)-C(10)
1.3931
C(11)-C(12)
1.3918
Bond angle (º)
C(13)-N(3)-C(14)
C(13)-N(4)-N(2)
N(4)-C(13)-N(3)
C(5)-C(6)-N(1)
C(4)-C(3)-C(2)
C(10)-C(9)-C(8)
C(12)-C(11)-C(10)
N(4)-C(13)-S(1)
Bond angle (º)
C(14)-N(2)-N(4)
C(13)-N(3)-C(12)
C(7)-C(12)-N(3)
C(14)-N(1)-C(6)
C(2)-C(1)-C(6)
C(6)-C(5)-C(4)
C(12)-C(7)-C(8)
N(2)-C(14)-N(1)
107.6(3)
114.6(3)
103.9(3)
123.6(3)
119.0(3)
120.5(4)
119.1(4)
128.4(3)
107.7899
115.1305
102.0667
123.3155
119.0961
120.146
107.7477
115.2874
102.0046
123.3114
119.0674
120.1041
119.4273
129.0636
103.0(3)
127.4(3)
119.2(3)
127.0(3)
120.6(3)
119.0(3)
119.3(4)
127.8(3)
103.2568
125.9714
119.6807
129.0576
120.3618
119.3328
119.3845
128.1275
103.2951
125.993
119.7079
128.8431
120.3537
119.2883
119.2746
128.2003
119.4385
129.069
The molecular structure of the title compound consists of discrete [PhNHC2N3HSPh] entities. All of
the bond lengths and bond angles in the phenyl rings are in the normal range. The C=S bond length of
1.692(3) Å is comparable to that found in 3-benzyl-4-phenyl-1,2,4-triazole-5-thione [C=N 1.687(3) Å]
[8]. In the triazolyl ring, the N-N, C=N and C-N bond lengths are also in good agreement with those

Molecules 2009, 14
611
found in the above-cited structure [8]. The exocyclic sulfur atom and triazolyl ring define a plane P1.
The dihedral angles between P1 with phenylamino planar and another phenyl ring are 16.98(2) and
83.36(1)°, respectively. The dihedral angle between the phenyl ring and phenylamino planar is
80.56(3)°.
In the crystal lattice, there are two intermolecular interactions, one potentially weak intramolecular
interaction (C-H···Y, Y= N)[15-16] and some C-H···π supramolecular interactions (see Table 2) [17].
In the solid state, all above supramolecular interactions stabilize the crystal structures.
Table 2. Hydrogen bonds and C-H••• π supramolecular interactions.
D-H•••A
N(1)-H(1A)•••S(1)
Symmetry
-1/2+x,1/2-y,-1/2+z
x, 1-y, -1/2+z
D•••A (Å)
3.6963
3.2696
2.9298
3.747
∠D-H•••A (°)
159.75
N(4)-H(4A)•••S(1)
139.09
C(5)-H(5A) ••• N(2)
122.23
C(2)-H(2B)•••Cg(1) [triazolyl ring]
C(3)-H(3A)•••Cg(3)[C(7)-C(12)]
C(5)-H(5A)•••Cg(1) [triazolyl ring]
C(8)-H(8A) •••Cg(2)[C(1)-C(6)]
C(10)-H(10A)•••Cg(2)[C(1)-C(6)]
-1/2+x, 1/2-y, -1/2+z
-1/2+x ,1/2-y, -3/2+ z
x, 1-y, -1/2+ z
108.59
3.685
164.73
3.944
134.62
1/2+x, -1/2+y, 1+ z
x , y, 1+ z
4.035
142.60
3.562
148.46
Optimized geometry
DFT calculations were performed on the title compound at the B3LYP/6-311G** and PBE1PBE/6-
311G** levels of theory. Some optimized geometric parameters are also listed in Table 1. In view of
the bond lengths in Table 1, most predicted values are longer than experimental ones and the biggest
difference between the theoretical and experimental values occurs at C(9)-C(10) bond, with the
different values being 0.0431Å for B3LYP method and 0.0394 Å for PBE1PBE method. As for the
bond angles, most predicted values are corresponding with the experimental values and the biggest
difference takes place at bond angle of C(14)-N(1)-C(6), with the different values being 2.0576º for
B3LYP method and 1.8431º for PBE1PBE method. The reasons for above discrepances maybe as
follows: (1) the theoretical values belong to the isolated molecule in gas-phase and the experimental
values are attributed to the molecule in solid state. The geometry of the solid-state structures is subject
to intermolecular forces, such as van der Waals interactions and crystal packing forces, which make
most of the experimental bond lengths be shorter than the theoretical ones; (2) in the solid states, there
exists an intermolecular hydrogen-bond interaction corresponding with N(1)-H(1) bond, while in
theoretical calculations, intermolecular interactions are neglected, which, to some extent, may lead to
the bond angle of C(14)-N(1)-C(6) smaller in solid than that in calculations. Despite of some
differences, both DFT methods used here can reproduce the molecular geometry on the whole and they
are the bases for our following discussion.

Molecules 2009, 14
612
Natural bond orbital (NBO) analysis
The NBO occupancies based on the B3LYP/6-311G** and PBE1PBE/6-311G** optimized
structures are calculated and listed in Table 3. As seen from this data, the following four conclusions
can be drawn: (1) the N(2)-C(14) bond is a normal double–bond and, in two phenyl rings, the C–C
bonds are in typical single-double arrangements, which form the conjugate structure and support the
information in crystal structure. The similar situation can be found in the compound of 3-benzyl-4-
phenyl-1,2,4-triazole-5-thione [8]; (2) the N(3)-C(12) bond is only a single bond, which is different
from that seen in 3-benzyl-4-phenyl-1,2,4-triazole-5-thione [8], where N(3)-C(12) has some double-
bond character; (3) in B3LYP calculations, the S(1)-C(13) bond represents a double bond, which is in
good agreement with the experimental fact, while in PBE1PBE calculations, the S(1)-C(13) bond only
has single bond character; (4) except for the N(2)-N(4) bond, all of the single bonds, including the C-C
single bonds in the two phenyl rings, along with the double bond of N(2)-C(14) in PBE1PBE
calculations have smaller occupancies than those in B3LYP calculations. In a word, to some extent, for
the system studied here, apart from the bond of S(1)-C(13), NBO results obtained by B3LYP/6-
311G**and PBE1PBE/6-311G** both correspond to the experiments.
Table 3. Natural bond orbital occupancies*.
Occupancies(a.u)
Occupancies(a.u)
Bond
Bond
B3LYP/6-
PBE1PBE/6-311G**
B3LYP/6-
PBE1PBE/6-311G**
311G**
1.99384
1.98170
0.56667
1.97620
1.97569
1.98882
1.97738
1.98267
1.92656
0.39694
1.98381
1.98431
1.98196
1.97048
1.97622
1.70572
0.34018
1.97847
1.97940
311G**
1.36614
0.33789
1.97530
1.97189
1.64608
0.39220
1.97212
1.97552
1.64506
0.30839
1.97949
1.97945
1.65212
0.31849
1.97542
1.97228
1.68578
0.37620
S(1)-C(13)
S(1)-C(13)π
S(1)-C(13)π*
N(3)-C(13)
N(3)-C(14)
N(4)-C(13)
N(2)-N(4)
1.98157
C(3)-C(4)π
C(3)-C(4)π*
C(4)-C(5)
1.67131
0.33783
1.97504
1.97129
1.64588
0.39257
1.97113
1.97532
1.64350
0.30585
1.97941
1.97930
1.65422
0.31979
1.97514
1.97152
1.68803
0.38247
1.97596
1.97544
1.98854
1.97787
1.98223
1.92444
0.39702
1.98355
1.98387
1.98143
1.96976
1.97617
1.70603
0.33989
1.97838
1.97909
C(5)-C(6)
C(5)-C(6)π
C(5)-C(6)π*
C(7)-C(12)
C(7)-C(8)
N(2)-C(14)
N(2)-C(14)π
N(2)-C(14)π*
N(1)-C(14)
N(1)-C(6)
C(7)-C(8)π
C(7)-C(8)π*
C(8)-C(9)
C(9)-C(10)
C(9)-C(10)π
C(9)-C(10)π*
C(10)-C(11)
C(11)-C(12)
C(11)-C(12)π
C(11)-C(12)π*
N(3)-C(12)
C(1)-C(6)
C(1)-C(2)
C(1)-C(2)π
C(1)-C(2)π*
C(2)-C(3)
C(3)-C(4)
* anti-bond

Molecules 2009, 14
613
Atomic charge distributions
Based on B3LYP/6-311G** and PBE1PBE/6-311G** optimized geometries, Natural Population
Analysis (NPA) atomic charge distributions were calculated. All of the atomic charges of non-
hydrogen atoms are listed in Table 4.
Table 4. NPA atomic charge distributions obtained at B3LYP/6-311G** and PBE1PBE/6-
311G** levels.
Charges (e)
B3LYP
Charges (e)
B3LYP
Charges (e)
B3LYP
Atom
Atom
Atom
PBE1PBE
-0.25839
-0.36728
-0.45806
-0.37514
0.23106
0.58960
-0.59554
PBE1PBE
-0.24608
-0.18736
-0.23177
-0.17946
-0.25464
0.16826
PBE1PBE
-0.18447
-0.19000
-0.19100
-0.19689
-0.22115
0.12458
S(1)
N(2)
N(3)
N(4)
C(13)
C(14)
N(1)
-0.25706
-0.37039
-0.46577
-0.37746
0.23522
0.59570
-0.59232
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
-0.23800
-0.18199
-0.22327
-0.17350
-0.24558
0.17109
C(7)
C(8)
-0.17805
-0.18504
-0.18313
-0.18927
-0.19869
0.12351
C(9)
C(10)
C(11)
C(12)
As seen from Table 4, since the nitrogen and sulfur atoms have greater electronegativity than the
carbon and hydrogen atoms, all of the N atoms and the S atom carry negative charges. Although N(1),
N(3) and N(4) have bigger negative charges, steric effects around them hinder these atoms from
coordinating further with metallic ions. On the other hand, the negative charges on N(2) and S(1) are
lesser than those on N(1), N(3) and N(4), however, the expansive environment around them make
these two atoms potential reaction sites for metallic ions, which suggest that the title compound can be
used as a terminal or multidentate ligand to coordinate with various metallic ions and thus assemble
diverse metal complexes. This is not only consistent with many experimental facts reported before [18-
19], but also supports one of our original aims for the synthesis.
Calculation of nonlinear optical properties
On the basis of the MNDO Hamiltonian and PM3 parametrization with the MOPAC program
package, the molecular hyperpolarizability value, βμ, the vector components along the dipole moment
direction, of the title compound were calculated to be 7.166×10-30 esu, which is greater than those for
urea (0.14×10-30 esu calculated using the same method) [20] and para-nitroaniline (PNA) (6.801×10-
30 esu calculated using the same method). The βμ, value of the title compound is also larger than those
of similar compounds 4-phenyl-3-[(1,2,4-triazol-1-yl)methyl]-triazole-5-thione (4.397×10-30esu) [21]
and 3-benzyl-4-phenyl-1,2,4-triazole-5-thione (4.025×10-30 esu) [8]. Based on the optimized
geometry at the B3LYP/6-311G** level of theory, the dipole moment of the title compound was
calculated, which was 5.2638 Debye. Using the TD-DFT method, the electronic spectra of the title
compound were predicted and two transition bands were obtained, one being at 246.92 nm, with an
oscillator strength f = 0.3151 and another at 229.23 nm, with oscillator strength f = 0.2900. Both
electronic transition bands are in the ultraviolet region, showing the good transparency of the title

Molecules 2009, 14
614
compound. These calculations indicate that the title compound might be a good candidate as a second-
order nonlinear optical material.
Thermodynamic propertes
On the basis of B3LYP/6-311G** and PBE1PBE/6-311G** vibrational analyses and statistical
thermodynamics, the standard thermodynamic functions: heat capacity (C0p,m), entropy（S0 ）and
m
enthalpy（H0 ）of the title compound were obtained and are listed in Table 5. The scale factor for
m
frequencies was 0.96. For 3-benzyl-4-phenyl-1,2,4-triazole-5-thione, the corresponding value of C0
S0 and H0 obtained at B3LYP/6-311G** level of theory were also listed in Table 5.
,
p,m
m
m
Table 5. Thermodynamic properties for the title compound and 3-benzyl-4-phenyl-1,2,4-
triazole-5-thione [8].
3-Benzyl-4-phenyl-1,2,4-
triazole-5-thione
The title compound
B3LYP/6-311G** PBE1PBE/6-311G**
B3LYP/6-311G**
†
p,m
†
‡
†
†
‡
†
†
‡
m
T/K
C0
S0
H0
C0
S0
H0
C0
S0
H0
m
m
p,m
m
m
p,m
m
100.0 110.75
200.0 187.75
298.1 272.63
300.0 274.21
400.0 354.11
500.0 419.70
600.0 471.45
700.0 512.41
368.74
468.16
558.90
560.59
650.71
737.05
818.34
894.20
7.61
109.37
185.89
270.04
271.60
351.00
416.47
468.34
509.50
361.77
460.10
549.96
551.64
640.93
726.56
807.26
882.66
7.43
110.23
184.54
270.94
272.58
355.90
424.90
479.58
522.99
369.32
467.31
556.94
558.62
648.73
735.85
818.34
895.65
7.68
22.39
44.98
45.48
77.00
115.82
160.48
209.75
22.06
44.42
44.92
76.15
114.65
158.99
207.96
22.24
44.56
45.06
76.59
115.76
161.09
211.30
† J·mol-1·K-1; ‡ kJ·mol-1
As observed from Table 5, all the values of C0p,m, S0 and H0 increase with the increase of
m
m
temperature from 100.0 to 700.0 K, which is attributed to the enhancement of the molecular vibration
as the temperature increases. On the other hand, for the title compound, all of the values of C0p,m , S0
m
and H0 obtained by the PBE1PBE/6-311G** method are smaller than the corresponding values
m
obtained by the B3LYP/6-311G** method. Thirdly, compared with 3-benzyl-4-phenyl-1,2,4-triazole-5-
thione, the phenylamino group at the 3-position of the triazolyl ring of the title compound has a higher
molecular weight than that of the benzyl group of 3-benzyl-4-phenyl-1,2,4-triazole-5-thione, however,
the C0p,m , S0 and H0 values at each temperature obtained at the B3LYP/6-311G** level for the title
m
m
compound are not always lager than those of 3-benzyl-4-phenyl-1,2,4-triazole-5-thione [8]. The
correlation equations between these thermodynamic properties and temperatures for the title
compound, are listed in Table 6.

Molecules 2009, 14
Table 6.The correlation equations between thermodynamic properties and temperature.
615
C0p,m = 4.722 + 1.042 T – 4.443*10 -4 T 2 ( R2 = 0.9987 )
S0m = 266.297 + 1.047 T – 2.135*10 -4 T 2 ( R2 = 0.9999)
H0m = -2.665 + 5.726*10-2 T + 3.542*10-4 T 2( R2 = 0.9998 )
C0p,m = 4.434 + 1.031 T – 4.342*10 -4 T 2 ( R2 = 0.9988 )
S0m = 260.483 + 1.035 T –2.077*10 -4 T 2 ( R2 = 0.9999)
H0m =-2.649 + 5.573*10-2 T + 3.527*10-4 T 2( R2 = 0.9998 )
B3LYP/6-311G**
PBE1PBE/6-311G**
These equations could be used for the further studies on the title compound. For instance, when we
investigate the interaction between the title compound and another compound (for example DNA
molecules ), thermodynamic properties C0p,m , H0 and S0 could be obtained from these equations and
m
m
then used to calculate the change of Gibbs free energy of the reaction, which will assist us to judge the
spontaneity of the reaction.
Biological activity
The primary biological test has shown that the title compound exhibits inhibiting activity towards
some fungi, such as P. zeae, A. solani and P. piricola, with inhibition rates by the agar plate diffusion
method [22] of 24.1%，24.1% and 45.0% at 50 μg/mL, respectively.
Experimental and Theoretical Methods
General
Elemental analyses for carbon, hydrogen and nitrogen were performed on a Perkin-Elmer 240C
instrument. IR spectra (4000–400 cm−1), as KBr pellets, were recorded on a Nicolet FT-IR
spectrophotometer. All chemicals were obtained from a commercial source (J&K Chemical Ltd.,
Beijing, P.R. China) and used without further purification. 1H-NMR spectra were recorded on a Bruker
model DRX 500 spectrometer in CDCl3.
Synthesis
The title compound was synthesized in two steps as shown in Scheme 1.
Scheme 1. Synthesis of the title compound.
S
H
chloroform
reflux, 2h
H
N CONHNH2
NCS
+
N CONHNHCNHPh
intermediate
H
N
Ph
Ph
S
N
NaOH (2 mol/L)
80oC 2h
N
N
H

Molecules 2009, 14
616
First, equimolar amounts of phenylaminoformyl hydrazide and phenyl isothiocyanate were mixed
in chloroform with refluxed to give, after 2 h, white solids which were recrystallized from a mixture of
DMF-C2H5OH-water to afford afforded the intermediate, of which 5 mmol was added to 2 mol/L
NaOH solution (15 mL) and stirred until the intermediate dissolved. Then, the mixture was heated at
80oC for 2 h and then cooled to room temperature. After the mixture was adjusted to pH = 7 using 10%
hydrochloric acid, a great deal of white solid was observed. The title compound was obtained by
o
recrystallization the white solid from the mixture of DMF and C2H5OH. Yield 95%. Mp.178-179 C.
IR: ν 3487 (m), 3067 (m), 1604 (vs), 1554 (s), 1525 (s), 1469 (m), 1446 (s), 1340 (m), 1325 (m), 1237
(m), 1207 (m), 1162 (vs), 1083 (m), 1048 (m), 1029 (m), 1011 (w), 996 (m), 872 (s), 842 (vs), 745 (s),
1
699 (s), 637 (m), 560 (m) cm−1. H-NMR: 4.0 (s, 1H, -HN-Ph), 6.43-6.67 and 7.0-7.04 (m, 11H, two
C6H5- and C2N3SH-); Found: C, 62.41; H, 4.38; N, 20.72%.Calc. for C14H12N4S: C, 62.66, H, 4.51, N,
20.88%.
Crystallographic study
The selected crystal of the title compound was mounted on an Enraf-Nonius CAD4 diffractometer.
Reflection data were measured at 20°C using graphite monochromated Mo-Kα (λ = 0.71073 Å )
radiation and a ω-2θ scan mode. The correction for Lp factors and empirical absorption were applied
to the data. The structures were solved by direct methods and refined by full-matrix least-squares
method on Fobs2 using the SHELXTL software package [23]. All non-H atoms were anisotropically
refined. The hydrogen atom positions were fixed geometrically at calculated distances and allowed to
ride on the parent C atoms. The final least-square cycle gave R = 0.0463, wR2 = 0.0980. Atomic
scattering factors and anomalous dispersion corrections were taken from International Table for X-ray
Crystallography [24]. A summary of the key crystallographic information is given in Table 7.
CCDC-649123 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(0)1222-
336033; email: deposit@ccdc.cam.ac.uk].
Table 7. Summary of crystallographic results for the title compound.
Empirical formula
Formula weight
C14H12N4S
268.34
Temperature
293(2) K
Wavelength
0.71073 Å
Crystal system, space group
Unit cell dimensions
Monoclinic, Cc
a = 15.232(3) Å, b = 11.758(2) Å, c = 8.6025(17) Å,
β = 121.66(3)°
Volume
1311.5(5) Å3
Z, Calculated density
Absorption coefficient
F(000)
4, 1.359 Mg/m3
0.238 mm-1
560
θ range for data collection
Limiting indices
2.34 to 25.99°
-18≤ h ≤ 18, -9 ≤ k ≤ 14, -10≤ l ≤10

Molecules 2009, 14
617
Table 7. Cont.
Reflections collected / unique
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
2794 / 2221 [Rint = 0.0223 ]
Full-matrix least-squares on F2
2221 / 2 / 172
1.075
Final R indices [I>2σ (I)]
R indices (all data)
Largest diff. peak and hole
R1 = 0.0463, wR2 = 0.0980
R1 = 0.0492, wR2 = 0.1006
0.203and -0.232e. Å-3
Computational methods
In order to find out which method is more suitable to the system studied here, two density
functional theory (DFT ) calculations at the B3LYP/6-311G** and PBE1PBE/6-311G** [25-26] levels
of theory by the Berny method [26] were performed with the Gaussian 03 software package [28].
Vibrational frequencies calculated ascertain the structure was stable (no imaginary frequencies). Based
on the statistical thermodynamics and vibrational analyses, the thermodynamic properties of the title
compound at different temperatures were calculated. Natural Bond Orbital (NBO) analyses and the
time–dependent density functional theory (TD-DFT) [29-32] calculations of electronic absorption
spectra were also performed on the optimized structure. On the basis of the MNDO Hamiltonian [33]
and PM3 parametrization [34] with the MOPAC [35] program package, the molecular
hyperpolarizability value was also calculated. All calculations were performed on a DELL PE 2850
server and a Pentium IV computer using the default convergence criteria.
Acknowledgments
This work was supported by Natural Science Foundation of the Department of Education of Jiangsu
Province P. R. China (06KJD150033), Huaian Science & Technology Bureau, Jiangsu Province, P. R.
China (HAG07025) and Fund of Huanyin Teachers College (07HSBS004, 08HSJSK003,
JSKC08047).
References and Notes
1. Xu, L.Z; Jian, F.F.; Qin, Y.Q.; Jiao, K. Structure and Biological Activities of 3-Phenyl-2-[1-
benzoyl-1-(1,2,4-trizol-1-yl)] Methenyl Thiazolidine. Chem. Res. Chin. Univ. 2004, 20, 305-307.
2. Genin, M.J.; Allwine, D.A.; Anderson, D.J.; Barbachyn, M.R.; Emmert, D.E.; Garmon, S.A.;
Graber, D R.; Grega, K.C.; Hester, J.B.; Hutchinson, D.K.; Morris, J.; Reischer, R.J.; Ford, C.W.;
Zurenko, G.E.; Hamel, J.C.; Schaadt, R.D.; Stapert, D.; Yagi, B.H. Substituent Effects on the
Antibacterial Activity of Nitrogen−Carbon-Linked (Azolylphenyl)oxazolidinones with Expanded
Activity Against the Fastidious Gram-Negative Organisms Haemophilus influenzae and
Moraxella catarrhalis. J. Med. Chem. 2000, 43, 953-970.
3. Banting, L.; Nicholls, P.J.; Shaw, M.A.; Smith, H.J. Progress in Medicinal Chemistry; Elsevier
Science: Amsterdam, The Netherlands, 1989.

Molecules 2009, 14
618
4. Jian, F.F.; Xu, L.Z.; Shi, J.G.; Xiao, H.L. 2-(1,3-Dithiolan-2-ylidene)-1-phenyl-2-(1,2,4-triazol-1-
yl)ethanone. Acta Cryst. 2004, E6s0, o1204-o1205.
5. Jian, F.F; Xiao, H.L; Qin, Y.Q.; Xu, L.Z. 2-Benzoyl-N-phenyl-2-(1,2,4-triazol-1-yl)thioacetamide
and 2-(4-methoxybenzoyl)-N-phenyl-2-(1,2,4-triazol-1-yl)thioacetamide. Acta Cryst. 2004, C60,
o492-o495.
6. Xu, L.Z.; Jian, F.F.; Gao, H.R.; Zhu, C.Y. Synthesis, Structure and Biological Activities of S-[α
(4-Methoxyphenylcarbonyl)-2-(1,2,4-Triazole-1-yl)]ethyl-N, N-dimethyldithiocarbamate. Chin. J.
Chem. 2003, 21, 1615-1618.
7. Jian, F.F.; Xu, L.Z.; Li, L.; Zhu, C.Y. Synthesis and crystal structure of compound: 2,2-dimethyl-
4-[1H-(1,2,4-triazoly)]- 4-[1H-benzotriazolyl]-3-butanone. Chin. J. Struct. Chem. 2004, 23. 539-
542.
8. Jian, F.F.; Bai, Z.S.; Xiao, H.L.; Li, K. 3-Benzyl-4-phenyl-1H-1,2,4-triazole-5(4H)-thione. Acta
Cryst. 2005, E61, o557-o558.
9. Gors, C.; Baert, F.; Foulon, M.; Henichart, J.P.; Houssin, R. Structure of 4-formylamino-Δ2-1,2,4-
triazoline-5-thione. Acta Crystallogr. 1979, B35, 489-491.
10. Belcher, L.K.A.; Squattrito, P.J. Structure of 4-amino-3-butyl-1,2,4-triazole-5-thione: Relation to
derivatives with H, Me, Et, and Pr in the 3-position. J. Chem. Cryst. 2006, 36, 175-180.
11. Heras, M.; Font, D.; Linden, A.; Villalgordo, J.M. Synthesis of Triazolo[1,5-a]triazin-7-one
Derivatives and Highly Functionalized [1,2,4]Triazoles. Helv. Chim. Acta. 2003, 86, 3204-3214.
12. Chen, X.D.; Wu, H.F.; Du, M. Controllable preparation of ZnII coordination polymers: unusual
solvothermal formation of a LiGe-type framework directed by in situ S–S coupling of 5-(4-
pyridyl)-1H-1,2,4-triazole-3-thiol. Chem. Commun. 2008, 1296-1298.
13. Koch, W.; Holthausen, M.C.A. A Chemistry Guide to Density Functional Theory; Wiley-VCH:
Weinheim, New York, Chichester, 2000.
14. Parr, R.R.; Yang, R.G. Density Functional Theory of Atoms and Molecules. Oxford University
Press: New York, USA, 1989, and references therein.
15. Steiner, T. C-H-O Hydrogen Bonding in Crystals. Cryst. Rev. 1996, 6, 1-51.
16. Jeffrey, G.A.; Maluszynska, H.; Mitra, J. Hydrogen bonding in nucleosides and nucleotides. Int.
J. Biol. Macromol. 1985, 7, 336-348.
17. Hunter, R.H.; Haueisen, R.H.; Irving, A. The First Water-Dependent Liquid Clathrate: X-Ray
Evidence in the Solid for a C-H···π (Heteroarene) π···H-C Interaction. Angew. Chem. Int. Ed.
Engl. 1994, 33, 566-568.
18. Jian, F.F.; Xiao, H.L.; Wang, H.X.; Sun, P.P. Structure of tetra (β-propiophenone-1,2,4,triazole-
N4) dichloro metal hexahydrate complex: [MCl2(C2H2N3CH2CH2COPh)4]·6H2O (M = Ni, Co). J.
Chem. Crystallogr. 2004, 34, 647-652.
19. Vos, G.; de Graaf, R.A.G.; Haasnoot, J.G.; van derKraan, A.M.; de Vaal, P.; Reedijk, J. Crystal
structure at 300 and 105 K, magnetic properties and Moessbauer spectra of bis(triaquatris(4-
ethyltriazole-N1)iron(II)-N2,N2',N2")iron(II) hexakis(trifluoromethanesulfonate).
A
linear,
trinuclear iron(II) compound, showing a unique high-spin-low-spin transition of the central iron
atom. Inorg. Chem. 1984, 23, 2905-2910.
20. You, X.Z. Molecular-based Materials -Opto-electronic Functional Compounds, Science and
Technology Publishing Company: Shanghai, P.R. China, 2001; p. 164.

Molecules 2009, 14
619
21. Jian, F.F.; Zhao, P.S.; Bai, Z.S.; Cai, Z.J. Experimental and Theoretical Study on 4-Phenyl-3-
[(1,2,4-triazol-1-yl)methyl]-triazole-5-thione. Polish J. Chem. 2006, 80, 325-333.
22. Xu, L.Z.; Zhai, Z.W.; Yu, G.P.; Qin, Y.Q.; Yang, Y.X. Syntheses and Biological Activities of
Novel Benzotriazole Compounds Containing a Thioamide Group. Chem. Res. Chinese U. 2006.
22, 574-576.
23. Sheldrick, G.M. Siemens Analytical X-Ray Systems. In SHELXTL, v5 Reference Manual;
Madison: WI, USA, 1997.
24. Wilson, A.J. International Table for X-Ray Crystallography; Kluwer Academic: Dordrecht, The
Netherlands, 1992; Vol. C: Tables 6.1.1.4 (pp. 500-502) and 4.2.6.8 (pp. 219-222), respectively.
25. Perdew, J.P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys.
Rev. Lett. 1996, 77, 3865-3868.
26. Perdew, J.P.; Burke, K.; Ernzerhof, M. K+ Emission in Symmetric Heavy Ion Reactions at
Subthreshold Energies. Phys. Rev. Lett. 1997, 78, 1396-1396.
27. Peng, C.; Ayala, P.Y.; Schlegel, H.B.; Frisch, M.J. Using redundant internal coordinates to
optimize equilibrium geometries and transition states. J. Comput. Chem. 1996, 17, 49-56.
28 Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.;
Montgomery, J.A.; Vreven, Jr.T.; Kudin, K.N.; Burant, J.C.; Millam, J.M.; Iyengar, S.S.; Tomasi,
J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G.A.; Nakatsuji, H.;
Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.;
Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J.E.; Hratchian, H.P.; Cross, J.B.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R.E.; Yazyev, O.; Austin, A.J.; Cammi, R.; Pomelli, C.;
Ochterski, J.W.; Ayala, P.Y.; Morokuma, K.; Voth, G.A.; Salvador, P.; Dannenberg, J.J.;
Zakrzewski, V.G.; Dapprich, S.; Daniels, A.D.; Strain, M.C.; Farkas, O.; Malick, D.K.; Rabuck,
A.D.; Raghavachari, K.; Foresman, J.B.; Ortiz, J.V.; Cui, Q.; Baboul, A.G.; Clifford, S.;
Cioslowski, J.; Stefanov, B.B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R.L.;
Fox, D.J.; Keith, T.; Al-Laham, M.A.; Peng, C.Y.; Nanayakkara, A.; Challacombe, M.; Gill, P.M.
W.; Johnson, B.; Chen, W.; Wong, M.W.; Gonzalez. C.; Pople, J. A. Gaussian; Gaussian Inc.:
Wallingford, CT, USA, 2004.
29. Runge, E.; Gross, E.K.U. Density-Functional Theory for Time-Dependent Systems. Phys. Rev.
Lett. 1984, 52, 997-1000.
30. Petersilka, M.; Gossmann, U.J.; Gross, E.K.U. Excitation Energies from Time-Dependent
Density-Functional Theory. Phys. Rev. Lett. 1966, 76, 1212-1215.
31. Bauernschmitt, R.; Ahlrichs, R. Treatment of electronic excitations within the adiabatic
approximation of time dependent density functional theory. Chem. Phys. Lett. 1996, 256, 454-
464.
32. Jamorski, C.; Casida, M.E.; Salahub, D.R. Dynamic polarizabilities and excitation spectra from a
molecular implementation of time-dependent density-functional response theory: N2 as a case
study. J. Chem. Phys. 1996, 104, 5134-5138.
33. Dewar, M.J.S.; Thiel, W. Ground states of molecules. 38. The MNDO method. Approximations
and parameters. J. Am. Chem. Soc. 1977, 99, 4899-4907.
34. Stewart, J.J.P. Optimization of parameters for semiempirical methods I. Method. J. Comput.
Chem. 1989, 10, 209-220.

Molecules 2009, 14
620
35. Stewart, J.J.P. QCPE Program 455, 1983, Version 6.0, 1990.
Sample Availability: Samples of the title compound are available from the authors.
© 2009 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.
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