Synthesis, spectroscopic and structural studies of 4-Amino-3-(ethyl)-5-(4- chlorophenyl)-4H-1,2,4-triazole and 4-Amino-3-cyclopropyl-5-oxo-4,5-dihydro-1,2, 4-triazole-1-yl-acetic acid ethyl ester

Article abstract of DOI:10.1016/j.molstruc.2014.03.022

The title compounds of 4-Amino-3-(ethyl)-5-(4-chlorophenyl)-4H-1,2,4- triazole (I, C₁₀H₁₁ClN₄) and 4-Amino-3-cyclopropyl-5-oxo-4,5-dihydro-1,2,4-triazol-1-yl-acetic acid ethyl ester (II, C₉H₁₄N₄O₃), have been determined using X-ray diffraction techniques and characterized by IR, ¹H NMR and ¹³C NMR. X-ray study shows that the title compounds both have strong intermolecular N-H?N hydrogen bonds. The molecules of I are linked into a two-dimensional framework structure by N-H?N and C-H?N hydrogen bonds which produce R₂ ²(8)R₄⁴(14)R₄⁴(15) chain of rings, while in II, the combination of N-H?N, N-H?O and C-H?O hydrogen bonds along [1 0 0] generates a chain of edge-fused R ₂²(10)R₂²(16)R₄ ²(14) R₄⁴(14) rings.

Full text of DOI:10.1016/j.molstruc.2014.03.022

Journal of Molecular Structure 1067 (2014) 83–87
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis, spectroscopic and structural studies of 4-Amino-3-(ethyl)-5-
(4-chlorophenyl)-4H-1,2,4-triazole and 4-Amino-3-cyclopropyl-5-oxo-
4,5-dihydro-1,2,4-triazole-1-yl-acetic acid ethyl ester
b
b
c
d
Onur Sßahin a, , Cihan Kantar , Selami Sßasßmaz , Nurhan Gümrükçüog˘lu , Orhan Büyükgüngör
⇑
a Scientific and Technological Research Application and Research Center, Sinop University, 57010 Sinop, Turkey
b Deparment of Chemistry, Faculty of Arts and Sciences, Recep Tayyip Erdog˘an University, 53150 Rize, Turkey
c Vocational School of Health Services, Karadeniz Technical University, 61080 Trabzon, Turkey
d Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
h i g h l i g h t s
ꢀ
ꢀ
ꢀ
We report the synthesis of two new triazole derivatives.
The crystallographic calculations were performed by X-ray diffraction technique.
The compounds have been characterized by IR, 1H NMR and 13C NMR.
a r t i c l e i n f o
a b s t r a c t
Article history:
The title compounds of 4-Amino-3-(ethyl)-5-(4-chlorophenyl)-4H-1,2,4-triazole (I, C10H11ClN4) and
4-Amino-3-cyclopropyl-5-oxo-4,5-dihydro-1,2,4-triazol-1-yl-acetic acid ethyl ester (II, C9H14N4O3), have
been determined using X-ray diffraction techniques and characterized by IR, 1H NMR and 13C NMR. X-ray
study shows that the title compounds both have strong intermolecular NAHÁ Á ÁN hydrogen bonds. The
molecules of I are linked into a two-dimensional framework structure by NAHÁ Á ÁN and CAHÁ Á ÁN hydro-
gen bonds which produce R22(8)R44(14)R44(15) chain of rings, while in II, the combination of NAHÁ Á ÁN,
Received 31 December 2013
Received in revised form 13 March 2014
Accepted 13 March 2014
Available online 20 March 2014
Keywords:
Synthesis
Crystal structures
Triazole
NAHÁ Á ÁO and CAHÁ Á ÁO hydrogen bonds along [100] generates
a
chain of edge-fused
R22(10)R22(16)R42(14) R44(14) rings.
Ó 2014 Elsevier B.V. All rights reserved.
Hydrogen bonds
Introduction
Experimental
The derivatives of 1,2,4-triazole have been used as starting
materials for the synthesis of many heterocycles [1–4]. Triazole
compounds have many applications in medicine and were re-
ported to exhibit various pharmacological activities such as antivi-
ral, antimicrobial, analgesic, anti-inflammatory, anticancer and
antioxidant properties [5–8]. Some of them are also known to ex-
hibit analgesic, anticonvulsant, tranquilizing, antidepressant, anx-
iolytic [9–12] or even antitumour activities [13] and are applied
in therapy (e.g. Alprazolam, Estazolam, Triazolam and Adinazolam)
[14]. In the present paper, we wish to report the synthesis, spectro-
scopic and structural studies of the two new triazole compounds
(I and II) (see Table 1).
Synthesis
Synthesis of Ethyl N-(4-chlorobenzoyl)propanhydrazonoate (3)
To the solution of ethyl iminoethylester hydrochloride (1) in
absolute ethanol (10 mmol) was added the solution of 4-choloro-
benzoicacid hydrazide (10 mmol) in absolute ethanol and the mix-
ture was stirred at 0–5 °C for 6 h. Then the precipitated
ammonium chloride was filtered off. After the solvent was evapo-
rated at 35–40 °C under reduced pressure, a white solid appeared.
This crude product was recrystallized from benzene–petroleum
ether (1:2) to afford compound 3. (Yield: 52%). mp 113–114 °C; IR
(KBr) cmÀ1: 3270 ( C@N); 1H NMR
mNH), 1668 (mC@O), 1621 (m
(DMSO-d6) d ppm 1.28 (t, 3H, CH3, J = 5.08 Hz), 1.40 (t, 3H,
OCH2ACH3, J = 6.96 Hz), 2.48 (q, 2H, CH2, J = 5.08 Hz), 4.22 (q, 2H,
OCH2, J = 6.96 Hz), [ar-H:7.56 (d, 2H, J = 7.20 Hz), 8.06 (d, 2H,
J = 7.20 Hz)], 10.28 (s, 1H, NH); 13C NMR (DMSO-d6) d ppm:
⇑
Corresponding author. Tel.: +90 03682715644.
E-mail address: onurs@sinop.edu.tr (O. Sßahin).
http://dx.doi.org/10.1016/j.molstruc.2014.03.022
0022-2860/Ó 2014 Elsevier B.V. All rights reserved.

84
O. Sßahin et al. / Journal of Molecular Structure 1067 (2014) 83–87
Table 1
(mNH2), 1652 (m
C@N); 1H NMR (DMSO-d6) d ppm 1.38 (t, 3H,
Parameters for data collection and structure refinement of I and II.
CH3, J = 5.08 Hz), 2.80 (q, 2H, CH2, J = 5.08 Hz), 5.22 (s, 2H, NH2);
[ar-H: 7.46 (d, 2H, J = 7.20 Hz), 8.55 (d, 2H, J = 7.20 Hz)], 13C NMR
(DMSO-d6) d ppm 155.00 (triazole C5), 153.00 (triazole C3), ar-C:
[149.90 (2CH), 136.05 (C), 134.00 (2CH), 129.32 (C)], 20.83 (CH2),
12.68 (CH3). MS: m/z 222.78 (M+1).
Crystal data
I
II
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
10H11N4Cl
C9H14N4O3
226.24
triclinic
PÀ1
222.68
orthorhombic
Pbca
7.9240 (5)
26.785 (2)
10.3141 (7)
90.00
90.00
90.00
2189.1 (3)
8
1.351
6.2727 (4)
8.6161 (6)
10.9899 (8)
80.210 (6)
83.224 (5)
73.387 (6)
559.37 (7)
2
b (Å)
c (Å)
Synthesis of 4-Amino-3-cyclopropyl-5-oxo-4,5-dihydro-1,2,4-triazol-
1-yl-acetic acid ethyl ester (II)
a
(°)
The corresponding 3-cyclopropyl-4-amino-5-oxo-4,5-dihydro-
1,2,4-triazol (2) (0.01 mol) was refluxed with equivalent amount
of sodium metal in absolute ethanol for 2 h. Then, ethylbromoace-
tate (0.01 mol) was added and the mixture was refluxed for addi-
tional 5 h. After evaporation at 35–40° in a vacuum, the resulting
solid was recrystallized from an ethanol. Single crystals of
compound (II) (Scheme 1) were obtained from ethyl acetate at
room temperature by slow evaporation. (Yield: 61.20%). mp
b (°)
c
(°)
V (Å3)
Z
Dc (g cmÀ3
l
)
1.343
0.10
1.9–28.0
9294
2545
0.099
1.06
0.046/0.105
0.27/À0.19
(mmÀ1
)
0.32
h range (°)
Measured refls.
Independent refls.
Rint
1.5–26.7
16,644
2193
0.073
1.04
0.056/0.125
0.13/À0.18
155–156 °C; IR(KBr) cmÀ1: 3298–3210 (
1706 (triazoleAC@O), 1611 C@N), 1215
(DMSO-d6) ppm: 1.16 (t, 3H, AOCH2CH3, J = 6.96 Hz),
m
NH2), 1750 (esterAC@O),
S
(m
(m
CAO); 1H NMR
R1/wR2
D
q
/
max Dqmin (e ÅÀ3
)
d
1.80–1.87 (m, 4H, CH2), 3.43 (m, 1H, CH), 4.10 (q, 2H, AOCH2CH3,
J = 6.96 Hz), 4.52 (s, 2H, ANCH2), 5.36 (s, 2H, ANH2); 13C NMR
(DMSO-d6) d ppm: 167.48 (exocyclicAC@O), 154.18 (triazole C5),
146.04 (triazole C3), 61.20 (AOCH2CH3), 53.18 (CH), 46.67
(ANCH2), 28.12 (CH2), 28.08 (CH2), 14.60 (AOCH2CH3). MS: m/z
226.92 (M+1).
170.00 (C@O), 160.05 (C@N), ar-C: [135.43 (C), 134.05 (C), 128.00
(2CH), 127.52 (2CH)], 53.15 (OCH2), 28.87 (CH2), 20.05 (OCH2ACH3),
13.86 (CH3).
Synthesis of 4-Amino-3-(ethyl)-5-(4-chlorophenyl)-4H-1,2,4-triazole
(I)
Instrumentation
A solution of the corresponding compound 3 (10 mmol) in
n-propanol was refluxed with hydrazine hydrate (25 mmol) for
24 h. After it was cooled to room temperature, a white solid ap-
peared. This crude product was filtered off, washed with benzene
3 times, and recrystallized from an ethanol to afford the desired
compound (I). Single crystals of compound (I) (Scheme 1) were ob-
tained from ethyl acetate at room temperature by slow evapora-
tion. (Yield: 64%). mp 191–192 °C; IR (KBr) cmÀ1: 3320–3275
Melting points were determined on a Gallenkampmelting point
apparatus and are uncorrected. 1H NMR and 13C NMR spectra were
recorded on a Varian-Mercury 200 MHz spectrometer. The IR
spectra were measured as potassium bromide pellets using a
Perkin–Elmer 1600 series FTIR spectrometer. Mass spectra were
performed on Thermo TSQ Quantum acces max. All the chemicals
were obtained from Fluka Chemie AG Buchs. Ethyl iminoethylester
O
N
NHC
NH.HCl
OC2H5
O
H3C CH2
C
H3C CH2
C
NH2 NH C
+
OC2H5
3
Cl
Cl
1
4-cholorobenzoicacid hydrazide
NH2 NH2
N
N
H3C CH2
N
NH2
Cl
I
O
C
N
OCH2CH3
N NH
N
BrCH2COOC2H5
O
CH
CH
N
O
N
NH2
NH2
2
II
Scheme 1. Synthesis of compounds I–II.

O. Sßahin et al. / Journal of Molecular Structure 1067 (2014) 83–87
85
Fig. 1. Structure I showing the atom numbering scheme.
hydrochloride (1) and 3-cyclopropil-4-amino-5-oxo-4,5-dihydro-
1,2,4-triazol (2) were obtained as reported earlier [15–17].
Crystal structure determination
Crystals of I and II suitable for data collection were selected and
data collection was performed on a STOE IPDS II diffractometer
with graphite monochromated Mo K
a radiation at 296 K. The
structures were solved by direct-methods using SHELXS-97 and re-
fined by full-matrix least-squares methods on F2 using SHELXL-97
[18] from within the WINGX [19] suite of software. All non-hydro-
gen atoms were refined with anisotropic parameters. The H atoms
of nitrogen atoms were located in difference maps and refined
freely. Hydrogen atoms bonded to carbon were placed in calcu-
lated positions (CAH = 0.93–0.98 Å) and treated using a riding
model with U = 1.2 times the U value of the parent atom for CH,
CH2 and CH3. Molecular diagrams were created using MERCURY
[20]. Geometric calculations were performed with PLATON [21].
Fig. 3. The molecule of II showing the atom labeling scheme.
rings plane are approximately planar, with maximum deviation
from the least-squares plane being 0.0074(25) Å for atom C4 and
0.0045(14) Å for atom N1. Molecules of (I) are linked into sheets
by a combination of NAHÁ Á ÁN and CAHÁ Á ÁN hydrogen bonds. Ami-
no atom N4 in the molecule at (x,y,z) acts as hydrogen-bond donor,
via atom H12, respectively, to atom N3 at (x À 1/2,y,Àz + 3/2), so
forming a C(5) zig-zag chain running parallel to the [100] direc-
tion. Similarly, amino atom N4 in the molecule at (x,y,z) acts as
hydrogen-bond donor, via atom H14, respectively, to atom N2 at
(x,Ày + 3/2,z À 1/2), so forming a C(5) chain running parallel to
the [001] direction. The combination of CAHÁ Á ÁN hydrogen bonds
and C(5) chains produce R22(8)R44(14)R44(15) chain of rings running
parallel to the [101] direction (Fig. 2).
Results and discussion
Description of the crystal structures
The molecular structure of I with the atom labeling is shown in
Fig. 1. The dihedral angle between the benzene and triazole rings is
22.66(12)°. The NAN bond distances are 1.397(3) Å and 1.412(3) Å,
respectively. These values are comparable to those observed in
other similar triazole complexes [22–27]. The benzene and triazole
The molecular structure of II with the atom labeling is shown in
Fig. 3. The dihedral angle between the cyclopropane and triazole
rings is 76.46(8)°. The C1AO1, C7AO2 and N2AC2 bond lengths
Fig. 2. The crystal structure of I showing the formation of R22(8), R44(14) and R44(15) rings along [101]. [Symmetry code as in Table 3].

86
O. Sßahin et al. / Journal of Molecular Structure 1067 (2014) 83–87
Table 2
Selected bond lengths and angles (Å, °).
I
Bond lengths (Å)
C7AN3
C8AN2
N1AN4
1.311 (3)
1.305 (3)
1.412 (3)
C7AN1
C8AN1
N2AN3
1.367 (3)
1.361 (3)
1.397 (3)
Bond angles (°)
C8AN1AC7
C7AN1AN4
C7AN3AN2
106.72 (19)
125.2 (2)
107.7 (2)
C8AN1AN4
C8AN2AN3
126.9 (2)
107.6 (2)
II
Bond lengths (Å)
C1AO1
C1AN3
C2AN3
C7AO2
N1AN2
1.2310 (14)
1.3779 (15)
1.3747 (13)
1.1861 (16)
1.3939 (14)
C1AN1
C2AN2
C6AN1
C7AO3
N3AN4
1.3533 (14)
1.2979 (14)
1.4369 (14)
1.3227 (14)
1.3980 (13)
Bond angles (°)
N1AC1AN3
C1AN1AN2
N2AN1AC6
C2AN3AC1
C1AN3AN4
102.92 (9)
112.65 (9)
121.34 (9)
109.02 (9)
126.53 (9)
N2AC2AN3
C1AN1AC6
C2AN2AN1
C2AN3AN4
110.79 (10)
125.35 (10)
104.51 (9)
124.41 (9)
atom N1. In II, molecules are linked into sheets by a combination of
NAHÁ Á ÁN, NAHÁ Á ÁO and CAHÁ Á ÁO hydrogen bonds. Amino atom N4
in the molecule at (x,y,z) acts as hydrogen-bond donor, via atom
H4D, respectively, to atom N2 at (x + 1,y,z), so forming a C(5) chain
running parallel to the [100] direction. Similarly, amino atom N4
in the molecule at (x,y,z) acts as hydrogen-bond donor, via atom
H4C, respectively, to atom O1 at (Àx + 2,Ày,Àz + 1), so forming a
centrosymmetric R22(10) ring centered at (1,0,1/2). The combina-
tion of NAHÁ Á ÁN and NAHÁ Á ÁO hydrogen bonds along [100] gener-
ates a chain of edge-fused R22(10)R44(14) rings (Fig. 4). Atom C8 in
the molecule at (x,y,z) acts as hydrogen-bond donor, via atom
H8B, respectively, to atom O1 at (Àx + 1,Ày,Àz + 2), so forming a
centrosymmetric R22(16) ring centered at (n + 1/2, 0, 1) (n = zero
or integer). Atom C6 in the molecule at (x,y,z) acts as hydrogen-
bond donor, via atom H6B, respectively, to atom O1 at (x À 1,y,z),
so forming a C(5) chain running parallel to the [100] direction. The
combination of CAHÁ Á ÁO hydrogen bonds along [100] generates a
chain of edge-fused R22(16)R24(14) rings (Fig. 5).
Table 3
Hydrogen-bond parameters (Å, °).
DAHÁ Á ÁA
I
DAH
HÁ Á ÁA
DÁ Á ÁA
DAHÁ Á ÁA
N4AH12Á Á ÁN3i
N4AH14Á Á ÁN2ii
C9AH9AÁ Á ÁN2i
0.94 (4)
0.88 (3)
0.97
2.44 (4)
2.25 (3)
2.58
3.114 (4)
3.118 (4)
3.351 (3)
129 (3)
169 (3)
136
II
N4AH4DÁ Á ÁN2i
N4AH4CÁ Á ÁO1ii
C3AH3Á Á ÁO2iii
C6AH6BÁ Á ÁO1iv
C8AH8BÁ Á ÁO1v
0.91 (2)
0.95 (2)
0.98
0.97
0.97
2.355 (19)
2.02 (2)
2.45
2.56
2.59
3.1000 (14)
2.9538 (16)
3.2382 (16)
3.5084 (15)
3.4387 (18)
139.6 (16)
167.2 (16)
138
166
146
Symmetry codes: (i) x À 1/2, y, Àz + 3/2; (ii) x, Ày + 3/2, z À 1/2 for I; (i) x + 1, y, z;
(ii) Àx + 2, Ày, Àz + 1; (iii) Àx + 1, Ày + 1, Àz + 1; (iv) xÀ1, y, z; (v) Àx + 1, Ày, Àz + 2
for II.
are indicative of significant double-bond character (Table 2). In the
cyclopropane ring, the CAC bond distances ranged between
1.476(2) and 1.5049(18) Å, while the CACAC bond angles ranged
between 58.94(9)° and 60.88(9)°. These values are comparable to
those observed in other triazole complexes with cyclopropane ring
[28,29]. The triazole ring plane is approximately planar, with max-
imum deviation from the least-squares plane being 0.0180(7) Å for
Evaluation of spectroscopic results
In this study two new compounds (I, II) were synthesized. Their
structures were established by IR, 1H NMR, 13C NMR and MS
techniques.
Fig. 4. The crystal structure of II showing the formation of an [100] chain of edge-fused R22(10) and R44(14) rings. [Symmetry code as in Table 3].

O. Sßahin et al. / Journal of Molecular Structure 1067 (2014) 83–87
87
Conclusions
Two new triazole derivatives were syhthesized and character-
ized by the IR, NMR, MS spectroscopy and X-ray diffraction method.
All spectroscopic data of compounds show good agreement with the
expected values. In addition the present study provides the bond
angles, bond lengths and other crystallographic information of syn-
thesized molecules. X-ray study shows that the compound I is ex-
tended into 2-D supramolecular network by NAHÁ Á ÁN and
CAHÁ Á ÁN hydrogen bonds while the compound II is extended into
1-D supramolecular network by NAHÁ Á ÁN, NAHÁ Á ÁO and CAHÁ Á ÁO
hydrogen bonds.
Supplementary data
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Centre, CCDC
929139 for compound I and 929140 for compound II. Copies of this
information may be obtained free of charge from the Director,
CCDC 12 Union Road, Cambridge CB2 1EZ, UK. (Fax: +44 1223
336 033 or e-mail: deposit@ccdc.cam.ac.uk).
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[100] generated by CAHÁ Á ÁO hydrogen bonds. [Symmetry code as in Table 3].
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In the first part of the study, compound 3 was synthesized from
the reaction of corresponding iminoester hydrochloride 1 with acyl
hydrazine which was obtained by a published method [1]. The
formed acylhydrazone’s structure was established by IR, 1H NMR
and 13C NMR technigues. Compound I was obtained by treatment
of compound 3 with hydrazine hydrate. The reaction was carried
out in 1-propanol at refluxing temperature for 24 h and the desired
3-alkyl-4-amino-5-aryl-1,2-4-triazole was yielded.
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The IR spectrum of compound 3 displayed no absorption de-
rived from ANH2 stretching. In the NMR spectra of this compound
new signal originating from the AOEt group was recorded. In the IR
spectra of compound I, the stretching band derived from the ANH2
group was present. Beside this the signal due to the ethoxy group
was absent in the NMR spectra of compound I, While the peak cor-
responding to the ANH2 group was recorded at 5.22 ppm in the 1H
NMR spectra of this compound (exchangeable with D2O).
In the second part of the study, compound II was synthesized via
the nucleophylic attack of N-1 on 5-oxo-[1,2,4] triazole ring to bro-
mine-bearing C atom of ethyl bromoacetate. This compound was
obtained by a published method [7]. In the NMR spectra of this com-
pound additional signals derived from ester group were observed at
4.52 (ANCH2), 4.10 ppm AOCH2CH3 and 1.16 ppm AOCH2CH3 ppm
integrating for two proton, two proton and three proton, respec-
tively. 13C NMR spectra of this compound, the signals belonging to
the same groups were recorded at 46.67, 61.20, 14.60 ppm,
respectively.
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High resolution MS spectra (ESI) of compounds (I–II) provided a
definitive proof for their characterization. Ionization took place in
the methanol solution. Molecular ions peaks of compounds (I–II)
were detected as expected. MS spectrum measurements confirmed
unambiguously the molecular mass of compounds (I)
(m/z = 222.78 M+1), (II) (m/z = 226.92 M+1).