One-pot synthesis and crystal structure of 4-phenyl-3-[4- chlorophenoloxymethyl]-1H-1,2,4-triazole-5(4H)-thione

Article abstract of DOI:10.1080/10426500701263547

4-Phenyl-3-[4-chlorophenoloxymethyl]-1H-1,2,4-triazole-5-thione was synthesized with one-pot method. The structure of the title compound was conformed by IR, 1H NMR, elemental analysis studies, and the crystal structure was determined by X-ray diffraction

Full text of DOI:10.1080/10426500701263547

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One-Pot Synthesis and Crystal
Structure of 4-Phenyl-3-[4-
chlorophenoloxymethyl]-1H-1,2,4-
triazole-5(4H)-thione
Tai-Bao Wei a , Jing Tang a , Hong Liu a & You-Ming
Zhang a
a College of Chemistry and Chemical Engineering,
Gansu Key Laboratory of Polymer Materials ,
Northwest Normal University , Lanzhou, Gansu, P.R.
China
Published online: 07 Jun 2007.
To cite this article: Tai-Bao Wei , Jing Tang , Hong Liu & You-Ming
Zhang (2007) One-Pot Synthesis and Crystal Structure of 4-Phenyl-3-[4-
chlorophenoloxymethyl]-1H-1,2,4-triazole-5(4H)-thione, Phosphorus,
Sulfur, and Silicon and the Related Elements, 182:7, 1581-1587, DOI:
10.1080/10426500701263547
To link to this article: http://dx.doi.org/10.1080/10426500701263547
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Phosphorus, Sulfur, and Silicon, 182:1581–1587, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701263547
One-Pot Synthesis and Crystal Structure of 4-Phenyl-3-[4-
chlorophenoloxymethyl]-1H-1,2,4-triazole-5(4H)-thione
Tai-Bao Wei
Jing Tang
Hong Liu
You-Ming Zhang
College of Chemistry and Chemical Engineering, Gansu Key Laboratory
of Polymer Materials, Northwest Normal University, Lanzhou, Gansu,
P.R. China
4-Phenyl-3-[4-chlorophenoloxymethyl]-1H-1,2,4-triazole-5-thione was synthesized
with one-pot method. The structure of the title compound was conformed by IR,
1 H NMR, elemental analysis studies, and the crystal structure was determined by
. . .
. . .
X-ray diffraction analysis. And, the intermolecular N
H
S and C
H
Cl hydro-
gen bonds link the molecules together as a tri-dimensional netlike supramolecular.
Keywords 4-Phenyl-3-[4-chlorophenoloxymethyl]-5-mercapto-1,2,4-triazole; crystal
structure; one-pot synthesis
INTRODUCTION
Substituted derivatives of triazole possess such comprehensive bio-
activities as antimicrobial,1−3 antiinflammatory,4 analgesic,5 anti-
tumorial,6 antihypertensive,7 anticonvulsant,8,9 and antiviral acti-
vities.10 The broad biological activities that the 1,2,4-triazoles shown
may be due to the presence of >N C S moiety.11,12
According to our previous work,13−15 we are interested in the syn-
thesis, biological activities, and crystal structure of triazole derivatives
with the help of the microwave technology. As a part of our work, the
4-phenyl-3-[4-chlorophenoloxymethyl]-1H-1,2,4-triazole-5-thione is an
important intermediate; however, to date, the traditional research on
Received November 11, 2006; accepted January 5, 2007
Financial support of this work by Natural Science Foundation (No. 20371040) of China,
the Natural Science Foundation (No. 031-A21-004) of Gansu province, and the Foundation
(No. 02-18) of Northwest Normal University are acknowledged.
Address correspondence to You-Ming Zhang, Department of Chemistry and Chemi-
cal Engineering, Gansu Key Lab of Polymer Materials, Northwest Normal University,
Lanzhou, 730070, Gansu, China. E-mail: zhangnwnu@126.com.
1581

1582
T.-B. Wei et al.
synthesis of 1,2,4-triazole suffered from the disadvantages, such as long
reaction time, low yield, and the inconvenience of handling. In view of
these, we communicate our work for an efficient one-pot synthesis of
substituted 1,2,4-triazoles and the crystal structure of the title com-
pound.
SCHEME 1
The reaction sequence is shown in Scheme 1. 4-chlorophenoxyacetyl
hydrazide 1 was prepared according to our previous work.13 Under mi-
crowave irradiation, 1 reacted with phenylisothiocyanate in the mixed
solution of DMF and 2 M NaOH gives the title compound. This method
has the advantages of simple operation that shortened reaction times
and gave high yield.
RESULTS AND DISCUSSION
The crystal structure of title compound atom-labelling scheme was
shown in Figure 1. The crystallographic data were summarized in
FIGURE 1 A plot of the title compound with displacement ellipsoid drawn at
the 50% probability level.

Crystal Structure of Triazole-Thione
1583
TABLE I Crystal Data and Structure Refinement for C15H12ClN3OS
Empirical formula
Formula weight
Temperature
C15H12ClN3OS
317.79
293(2) K
˚
Wavelength
0.71073 A
Crystal system
Space group
Unit cell dimensions
triclinic
P1
α = 101.140(9)◦
β = 102.734(7)◦
γ = 110.388(7)◦
˚
a = 7.221(3) A
˚
˚
b = 10.251(4) A
c = 11.641(5) A
3
˚
Volume
752.7(5) A
Z
2
Density(calculated)
Absorption coefficient
F(000)
1.402 Mg/m3
–1
0.394 mm
328
Crystalsize
0.54 × 0.42 × 0.23 mm3
Theta range for data collection 2.45 to 27.01◦
Index ranges
–8< = h< = 8, –12< = k< = 12,
–14< = l< = 14
5715
Reflections collected
Independent reflections
Data/restraints/parameters
Refinement method
2884[R(int) = 0.0149]
2884/0/194
SHELXL
Final R indices[I>2sigma(I)]
R indices(all data)
R1 = 0.0390, wR2 = 0.0961
R1 = 0.0545, wR2 = 0.1070
Table I. Part of the bond lengths and bond angles,selected torsion an-
gles, and coordinates and equivalent isotropic thermal parameters for
non-hydrogen atoms in the structure of 2 were given in Table 2, Table
3, and Table 4, respectively.
As shown in Figure 1, the title compound contains a triazole ring
and two benzene rings. Just as anticipation, the three rings are re-
spectively in one plane and the triazole ring, the C4 C9 benzene ring
and the C10 C15 benzene ring have mean deviations of 0.0027, 0.0018,
˚
and 0.0019 A, respectively. The C10 C15 and C4 C9 planes form di-
hedral angles of 104.4◦ and 56.3◦, respectively, with the the triazole
ring. Finally, the dihedral angle between the benzene ring C4 C9 and
C10 C15 is 72.1◦.
There are two types hydrogen bonds in the crystal structure as shown
. . .
in Figure 2. The first one is N(2A) H(2A) S(2B), and this type of hy-
drogen bonds link the molecules together like dimers. And the second
. . .
one is C(9B) H(9B) Cl(1C). From Table 5, we can find that the hydro-
. . . . . .
gen bond N(2A) H(2A) S(2B) is stronger than C(9B) H(9B) Cl(1C)
. . .
because the hydrogen bond length of N(2A) H(2A) S(2B) is shorter
than the latter. And, it also can be seen that the crystals were linked

1584
T.-B. Wei et al.
◦
˚
TABLE II Selected Bond Lengths (A) and Bond Angles ( ) for
Compound 2
Bond lengths
C1-N2
C1-N1
C1-S1
C2-N1
C2-N3
1.3316(26)
1.3726(24)
1.6739(22)
1.3767(25)
1.2942(26)
1.4829(28)
N2-N3
Cl1-C7
N1-C10
C4-O1
C3-O1
1.3693(25)
1.7398(23)
1.4411(23)
1.3757(23)
1.4212(25)
C2-C3
Bond angles
N1-C1-N2
N1-C1-S1
N2-C1-S1
C1-N1-C2
C1-N1-C10
C2-N1-C10
C3-C2-N3
C3-C2-N1
103.07(0.17)
128.48(0.15)
128.45(0.15)
107.71(0.16)
125.88(0.16)
126.37(0.16)
123.98(0.19)
124.59(0.17)
Cl1-C7-C6
C8-C7-C6
Cl1-C7-C8
C4-O1-C3
O1-C3-C2
N3-N2-C1
C2-N3-N2
N3-C2-N1
119.78(0.18)
121.21(0.21)
119.00(0.19)
116.91(0.16)
107.79(0.17)
114.29(0.17)
103.52(0.17)
111.41(0.18)
to form a tri-dimensional netlike supramolecular through two times
molecular packing (Figure 3).
EXPERIMENTAL
All commercially available products were used without further purifi-
cation. Melting points were measured on a X-4 digital melting-point
apparatus and are uncorrected. Microwave irradiation was carried out
with a WP 750B commercial microwave oven at 2450MHz. IR spectra
were measured as KBr pellets on a Digilab FTS-3000 FT-IR spectropho-
1
tometer. H NMR and 13C NMR spectra were recorded on a Varian
TABLE III The Selected Torsion Angles
N3-C2-C3-O1
O1-C4-C5-C6
N1-C10-C15-C14
N2-C1-N1-C2
N2-C1-N1-C10
N3-C2-N1-C1
N3-C2-N1-C10
C15-C10-N1-C1
C15-C10-N1-C2
N1-C1-N2-N3
N1-C2-N3-N2
C1-N2-N3-C2
-110.26(0.23) N1-C2-C3-O1
-179.32(0.19) O1-C4-C9-C8
179.70(0.20) N1-C10-C11-C12 -179.93(0.19)
71.73(0.25)
179.50(0.20)
0.76(0.21) S1-C1-N1-C2
178.41(0.18) S1-C1-N1-C10
-0.72(0.23) C3-C2-N1-C1
-178.36(0.18) C3-C2-N1-C10
-74.20(0.27) C11-C10-N1-C1
103.02(0.24) C11-C10-N1-C2
-0.59(0.23) S1-C1-N2-N3
0.34(0.22) C3-C2-N3-N2
0.17(0.24) C5-C4-O1-C3
-178.42(0.16)
-0.77(0.30)
177.51(0.19)
-0.13(0.31)
105.73(0.23)
-77.06(0.26)
178.59(0.16)
-177.90(0.19)
-21.10(0.28)

Crystal Structure of Triazole-Thione
1585
TABLE IV Final Atomic Coordinates (×105)
for All Non-Hydrogen Atoms and Equivalent
Thermal Parameters (× 105 nm2)
Atom
x
y
z
U (eq)
C1
C2
C3
Cl1
N1
N2
N3
O1
S1
26786(31)
43242(32)
58712(35)
115433(11)
42562(25)
19068(29)
28978(28)
53873(23)
19304(10)
46898(23)
33520(21)
27039(24)
−5553(9)
42697(18)
39866(20)
31549(20)
16264(16)
58280(7)
11755(18) 4199(46)
5651(17) 4182(45)
5966(20) 4786(50)
31346(9) 9332(30)
15732(14) 3971(38)
−259(16) 4594(43)
−4265(15) 4824(43)
12193(14) 5154(38)
19962(5) 5940(21)
TABLE V Data of Hydrogen Bond for 2
. . . . . . . . . . . .
A/nm D-H A/deg Symmetry code
D-H
A
D-H/nm
H
A/nm
D
. . .
N(2A)-H(2A) S(2B) 0.0828
0.2445
0.2856
0.3272
0.3756
177.61
163.2
−x, −y+1, −z
. . .
C(9B)-H(9B) Cl(1C) 0.0930
—
FIGURE 2 Two types of hydrogen bonds in the crystal structure.

1586
T.-B. Wei et al.
. . .
. . .
FIGURE 3 Intermolecular N H S and C H Cl hydrogen bonds link the
molecules together as a tri-dimensional netlike supramolecular.
Mercury plus-400 MHz spectrometer with TMS as internal standard.
X-ray intensity data was collected on Siemens P4 diffractometer with
Mo Ka radiation.
Synthesis of 4-Phenyl-3-[4-chlorophenoloxymethyl]-1H-1,2,4-
triazole-5-thione 2
4-Chlorophenoxyacetyl hydrazide (5 mmol, 0.93g) 1 and phenylisothio-
cyanate (5 mmol, 0.68 g) were dissolved in 5 mL DMF, then 10 mL
2M NaOH was added, and the mixture was reacted under the mi-
crowave irradiation (400W) for 5 min. After cooling, the solution was
acidified by 12 mL 2M HCl. The crude product was precipitated, fil-
tered, and washed with distilled water. Pure compounds were obtained
by recrystallization from the mixed solution of DMF and H2O (DMF
: H2O = 1:3). Crystal was also gained from the solution of DMF and
H2O.
2: Yield 83%, m.p. 214–216◦. IR: 3433 (NH), 1620 cm−1 (C = N). 1H
NMR (400 MHz, DMSO-d6): δ 14.115(s, 1H, NH), 4.993(s, 2H, CH2),
7.536–6.850 (m, 9H, Ar-H). 13C NMR (400 MHz, DMSO-d6): δ 168.689,
155.939, 147.823, 133.366, 129.594, 129.304, 129.266, 128.054, 125.463,
116.737, 60.419. Anal. Calcd for C15H13ON3S: C 56.69; H 3.81; N 13.22.
Found C 56.52; H 4.01; N 13.49.
It was interesting for us to find out, from the data shown above, an
unusual NMR shift of the N H (14.1 ppm) appeared in the title com-
pound. We all know that the chemical shift like this for N H hydrogens
is not always large, and the reason for this may be the N-H formed the
. . .
strong hydrogen bond, N H S.

Crystal Structure of Triazole-Thione
1587
CONCLUSION
The synthesis and 3 D catenulate supramolecular structure of the title
compound have been reported. The compound 2 is synthesized with the
method of one-pot synthesis, and this method has the advantages of
simple operation that shortened reaction times and gave high yield. In-
teresting, there is an unusual NMR shift of the N H is found. Finally,
in the crystal of compounds 2, there are two types of hydrogen bonds in
the crystal structure; and, with the help of them, the compound was as-
sembled to 3D catenulate supramolecular structure by these two types
of intermolecular hydrogen bonds.
SUPPLEMENTARY MATERIAL
Crystallographic data have been deposited to the Cambridge Crystal-
lographic Data Center, CCDC 617525 for 2. Copies of the information
may be obtained free of charge from the Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336-033; e-mail: de-
posit@ccdc.cam.ac.uk, or http://www.ccdc.ac.uk), upon request.
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