Journal of Molecular Structure 1143 (2017) 424e430

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Synthesis, experimental and theoretical characterizations of a new

Schiff base derived from 2-pyridincarboxaldehyde and its Ni (II)
complex
Mohammad Habibi a, S. Ali Beyramabadi a, *, Sadegh Allameh a, Maryam Khashi b,
Ali Morsali a, Mehdi Pordel a, Mahdi Khorsandi-Chenarboo a
a
Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran
b
Young Researchers and Elite Club, Mashhad Branch, Islamic Azad University, Mashhad, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this work, a tridentate Schiff base of 2-pyridinecarboxaldehyde and its Ni(II) complex have been newly
Received 13 November 2016 synthesized and characterized by the IR and NMR spectroscopies together with the elemental analysis. In
Received in revised form addition, optimized geometries, the Natural Bond Orbital (NBO) analyses, assignment of the IR bands and
8 April 2017
NMR chemical shifts of the synthesized compounds were computed by using density functional theory
Accepted 29 April 2017
Available online 3 May 2017
(DFT) methods. In the optimized geometry of the free ligand, the aromatic rings are not in the same
plane. But, the Ni complex is square planar, where the deprotonated Schiff base acts as a N3-tridentate
ligand. The chloro ligand occupies another coordination position of the complex. The DFT-calculated
Keywords:
2-Pyridinecarboxaldehyde
vibrational wavenumbers and NMR chemical shifts are in agreement with the experimental values,
Schiff base confirming suitability of the optimized geometries for the Schiff base and Ni(II) complex.
Ni(II) complex © 2017 Elsevier B.V. All rights reserved.
DFT
Assignment
NBO

1. Introduction
Schiff bases have many advantages between ligands in the co-
ordination chemistry. They are the condensation product of an
active carbonyl group as electrophile and an amino group as
nucleophile. Due to their structural varieties and very unique
characteristics, Schiff bases are the most versatile studied ligands in
coordination chemistry. On the other hand, these compounds are
an important class of organic ligands, because of their biological
properties [1e4].
Recently, the coordination chemistry of Schiff bases derived
from 2-pyridinecarboxaldehyde has received much attention
[5e10]. Several Schiff bases have been synthesized form conden-
sation reaction of 2-pyridinecarboxaldehyde-N-oxide with poly-
amines [11]. The 3-aminopyridine-2-carboxaldehyde
thiosemicarbazone (Triapine) and its zinc(II) complex exhibit po-
tential usage as anti-cancer chemotherapeutic agents [12]. On the
* Corresponding author.
E-mail addresses: beiramabadi6285@mshdiau.ac.ir, beiramabadi@yahoo.com
(S.A. Beyramabadi).
other hand, metal complexes show beneficial properties. The Zn(II)
and Cd(II) complexes of Schiff bases derived from 2-
Pyridinecarboxaldehyde and S-methyl- and S-benzyldithiocarba-
zates have been synthesized [13]. In another work, rhenium com-
plexes of the Schiff bases derived from 2-pyridinecarboxaldehyde
have been synthesized, which octahedral complexes that exhibited
high catalytic activity and selectivity in epoxidation of cyclohexene
[14]. The Cu(II) complexes of the Schiff bases derived from the 2-
pyridinecarboxaldehyde and the en, dien and trien amines have
been shown DNA cleavage activity [15]. Also, the copper complex of
the N,N0 -propylenebis[2-benzoylpyridineiminato] has high super
oxide dismutase activities [16].
Nickel, one of transition metals, has been found in biological
systems in trace quantities [17] and is also present in a series of
enzymes [18]. In hence, the nickel complexes have received
considerable attention owing to their effective biological impor-
tance such as antiepileptic [19] anticonvulsant agents and others
possess antibacterial [20] antifungal [21] antimicrobial [22] anti-
proliferative [23] and anticancer activity [24,25]. These findings
promoted us to synthesis and characterization of a new Schiff-base
ligand derived from 2-pyridinecarboxaldehyde (L3) and its Ni(II)

http://dx.doi.org/10.1016/j.molstruc.2017.04.114
0022-2860/© 2017 Elsevier B.V. All rights reserved.
 M. Habibi et al. / Journal of Molecular Structure 1143 (2017) 424e430 425

NH2
H
O2N N N
NiCl2.6H2O O2N N
H
Ni
O N L3 MeOH N
NH2 Cl
H
H Ethanol/AcOH
+
O2N NH2 N r.t., stir C5
N

1 2 H
N

O2N N L4
H

Scheme 1. Synthesis of the Schiff base (L3) and its Ni(II) complex (C5).

complex (Scheme 1).

2. Experimental

All of used chemicals were obtained from the Merck Company,

which were used without any further purification. The 1H NMR
(300 MHz) and 13C NMR (75 MHz) spectra were recorded on a
Bruker spectrometer in CDCl3 solution. The FT-IR spectra were
recorded on a Bruker Tensor 27 as KBr discs. A Stuart SMP3 melting
point apparatus was used for determination of the melting points
(m.p.). The elemental analysis for C, H and N were measured on a
Heraeus elemental analyzer CHNeO-Rapid. Percentage of the Ni2þ
ion was obtained by using a Hitachi 2-2000 atomic absorption
spectrophotometer.

2.1. General procedure for synthesis of 4-nitro-N2-pyridin-2-

ylmethylene-benzene-1,2-diamine (L3)

2 mmol of 2-pyridinecarboxaldehyde (0.153 g) and 1 mmol of 4-

nitro-o-phenylenediamine (0.153 g) was added to a solution of
ethanol (5 mL) and acetic acid (0.5 mL). The reaction mixture was
stirred for 5 h at room temperature. After this time, the yellow
product was filtered and washed with ethanol to give the Schiff
base (L3), which was purified in hot water (m.p.: 152  C, yield: 90%).

2.2. Preparation of the C5 complex

A solution of 1 mmol (0.242 g) of the L3 Schiff base in 3 mL

methanol was slowly added to the methanolic solution of
NiCl2$6H2O (1 mmol, 0.238 g in 2 mL). The reaction mixture was
stirred for 30 min and then was refluxed for 1 h to give the C5
complex. The complex was filtered off and washed with diethyl
ether (m.p.: 290  C, yield: 85%). The used methods are similar to the
previously reported methods for synthesis of the Schiff bases and
their complexes [26e28].

3. Theoretical characterizations

All present calculations have been performed with the Gaussian

03 software package [29] by using the B3LYP [30] functional and
the 6-31 þ G(d,p) basis set. First, all of the geometries were fully
optimized. Optimized geometries were confirmed to have no
imaginary frequency, except for transition state which has only one
imaginary frequency of the Hessian. Zero-point corrections have
been considered in the evaluation of energies. Optimized Fig. 1. Optimized geometries of the L3-1, L3-2 and TS1-2.
426 M. Habibi et al. / Journal of Molecular Structure 1143 (2017) 424e430

Fig. 2. Optimized geometry of the C5 complex.
geometries were used to compute the vibrational frequencies. The
DFT-calculated vibrational-frequencies are usually higher than the
experimental ones, which were scaled using a factor of 0.9614 [31].
The 1H NMR and 13C NMR chemical shifts were predicted with
respect to tetramethylsilane (TMS), where the GIAO method was
employed [32]. All structures were visualized by employing the
Chemcraft 1.7 program [33].
4. Results & discussion
The elemental analysis results of the ligand (L3 species) (Anal.
Calc. for C12H10N4O2: C, 59.50; H, 4.16; N, 23.13. Found: C, 66.68; H,
4.98; N, 12.29%) and its nickel complex (Anal. Calc. for
C12H9ClN4NiO2: C, 42.98; H, 2.70; N, 16.71; Ni, 17.50. Found: C,
41.76; H, 3.10; N, 15.97; Ni, 16.82%.) proposed the C12H10N4O2 ¼ HL
and C12H9ClN4NiO2 ¼ [Ni(L)Cl] formulas for the L3 ligand and Ni
complex, respectively. Since, the 1:1 ratio of the L ligand and Ni2þ
metal ion are predicted in structure of the investigated complex,
which is in agreement with the proposed structure for the similar
complexes [10,13,24,25,34e37].
4.1. Geometry analysis
The L3 species could exist as two different isomers, L3-1 and L3-
2, in which the C1eN1 and C2eN2 bonds are trans and cis to each
other. Optimized geometries of them are shown in Fig. 1. The L3-1
isomer is more stable than the L3-2 one in both of the gas phase
and methanolic solution. Their energy difference in the gas and
solution phases is 10.59 and 6.90 kJ mol1, respectively. These
isomers may rapidly transform to each other by rotation of the
pyridine ring around the C1eC2 bond. Transition state for trans-
formation of the L3-1 isomer to the L3-2 isomer was named as TS1-
2, optimized geometry of which is shown in Fig. 1. The calculated
N2eC2eC1eN1 and C3eC2eC1eH3 dihedral angles are 175.80 and
176.30 for the L3-1 isomer, respectively, which are 1.24 and 1.81
for the L3-2 isomer, respectively. These dihedral angles are 84.76
and 84.24 for the TS1-2 species, respectively. The calculated bar-
rier energy for isomerization of the L3-1 isomer to the L3-2 one is
32.20 and 31.33 kJ mol1, in the gas and solution phases,
respectively.
In the structure of the C5 complex, the L3 ligand loses one of the
amine protons. Then, the protonated L3 acts as a tridentate-anionic
ligand. The N1 azomethine nitrogen, the N2 atom of the pyridine
ring and the N3 atom of the protonated amine group are three
donating atoms of the ligand, occupy three coordination positions.
Another coordination position of the square complex is occupied by
the Cl ligand. This is in good agreement with the elemental
analysis results.
Geometry of the L3 ligand and C5 complex was fully optimized.
Optimized geometry of the complex is shown in Fig. 2. Their
selected-structural parameters are listed in Table 1. The L3-1 is the
most stable isomer of the L3 ligand. Since, the reported data is
related to the L3-1 isomer. In the optimized geometry of the species
L3-1, the pyridine and benzene rings are planar; however, each of
them is in a separate plane.
In the optimized geometry of the L3-1 isomer, the calculated
N2eC2eC1eN1, C1eN1eC7eC9 and C1eN1eC7eC9 dihedral an-
gles are 175.8, 33.4 and 150.6 , respectively, which show that two
aromatic rings make approximately a 30 dihedral angle to each
other. All of these dihedral angles are 0.0 in the optimized ge-
ometry of the C5 complex, confirming planarity of the square
complex. Other dihedral angles confirm that the ligand has more
planar structure in the complex in comparison with the free ligand.
In both of the free ligand and complex, the C1¼N1 azomethine
group is roughly in the same plane with the pyridine and benzene
rings (Table 1). By coordination of the azomethine nitrogen to the
Ni(II) ion, the C1¼N1 bond length increases from 128.3 in the ligand
to 130.1 p.m. in the complex. Also, the C3eN2 bond is longer in the
optimized geometry of the complex. But, the C9eN3 bond length
decreases in the complex than the free ligand by 4 p.m. In

Table 1
Selected structural parameters of the L3-1, L3-2 and C5 species.

Bond length (ppm) L3-1 L3-2 C5 Angle ( ) L3-1 L3-2 C5 Dihedral angle ( ) L3-1 L3-2 C5

C5eN2 133.6 133.3 133.5 N2eC5eH1 116.0 115.9 115.3 N1eC1eN2eC2 175.8 1.2 0.0
C2eN2 134.7 134.8 136.7 C5eN2eC2 117.9 117.7 119.7 N2eC2eC1eH3 3.4 178.1 e
C2eC3 140.4 140.4 139.7 N2eC2eC1 114.7 119.0 114.1 C7eN1eC1eH3 4.4 2.7 180.0
C3eC4 139.2 139.4 139.7 C2eC1eH3 114.3 115.0 121.3 N1eC7eC8eH6 0.6 0.2 0.0
C2eC1 147.3 147.5 145.4 N1eC1eC2 112.6 122.9 115.4 N1eC7eC9eN3 4.8 3.8 0.0
C1eH3 109.6 109.9 108.8 C1eN1eC7 120.9 122.1 130.4 C7eC9eN3eH10 14.3 164.9 180.0
C1eN1 128.3 128.0 130.1 N1eC7eC9 116.2 115.2 11.3 N4eC10eC8eC7 179.2 179.5 180.0
C7eN1 140.4 140.0 138.8 C7eC9eN3 119.1 118.8 115.6 C8eC10eN4eO1 179.8 180.0 180.0
C7eC9 142.8 143.1 144.6 C9eN3eH10 119.0 116.4 119.6 C3eC2eC7eC8 144.0 23.5 0.0
C9eN3 136.9 136.4 132.9 C11eC9eN3 121.7 122.1 127.1 C2eC1eN1eC7 176.5 178.1 0.0
N3eH10 101.1 101.3 101.2 C9eC11eC12 121.0 120.9 120.3 C1eN1eC7eC8 33.4 27.7 0.0
C9eC11 141.0 141.2 143.3 C7eC8eC10 119.9 120.0 118.5 C3eC2eN1eC1 5.0 178.9 179.9
C10eN4 145.6 145.4 144.6 C8eC10eN4 119.2 119.2 119.1 C1eC2eC3eC4 179.8 179.9 180.0
N4eO1 123.7 123.7 123.8 C10eN4eO1 118.0 118.1 118.1 C2eC3eC4eC6 0.2 0.0 0.0
NieN1 e e 189.8 N3eNieN2 e e 167.6 C7eC8eC10eC12 0.3 0.4 0.0
NieN2 e e 197.0 N3eNieN1 e e 84.3 C1eC2eN2eNi e e 0.0
NieN3 e e 186.4 N1eNieCl e e 179.1 N2eN1eN3eNi e e 0.0
NieCl1 e e 219.4 N1eNieCl e e 97.6 N2eN1eN3eCl1 e e 0.0
 M. Habibi et al. / Journal of Molecular Structure 1143 (2017) 424e430 427

Table 2
Selected experimental and calculated IR vibrational frequencies (cm1) of the L3 ligand and its Ni(II) complex.

Experimental frequencies Calculated frequencies Vibrational assignment

Ligand Complex Ligand Complex

Frequency Intensity Frequency Intensity

(km.mol1) (km.mol1)

e 431 (w) e e 421 15 y(NieCl)

e 464 (w) e e 515 17 y(NieN1)
586 (m, sh) 573 (w) 508 42 525 12 don plane (N4eH10)
e 641 (w) e e 635 16 ysym(N2eNieN3)
774, 745 (m) 824, 740 (m) 805, 769 21, 37 799, 752 27, 51 don plane (CeH) of the aromatic rings
1089 (s) 1068 (m) 1074 57 1056 202 din plane (CeH) of the aromatic ringsþ y(C10eN4)
1143 (s) 1162 (w) 1171 86 1178 70 y(C7eN1)
1326 (vs, br) 1338 (vs) 1291 253 1349 103 y(C9eN3)
1312 611 1308 1539 y(C10eN4)
1481 (vs) 1481 (s) 1511 184 1528 398 yasym(O1eN1eO2)
1583 (vs) 1523 (m) 1574, 1563 73, 44 1581 207 y(C]N, C]C) of the aromatic rings
1588 258 1509, 1433 88, 436 y(C]C) of the benzene ring þ y(CeN) of the substitutions of the benzene ring
1647 (s) 1606 (m) 1641 80 1595 145 y(C1¼N1)
3126 (m, br) 2728 (m, br) 2963 21 3055 13 y(C1eH3)
3053e3118 3e21 3115e3079 2e9 y(CeH) of the aromatic hydrogens
3276 (m) 3106 (m) 3442 63 3479* 63 ysym(NeH) of the eNH2 group
3363 (m) 3387 (m) 3571 57 yasym(NeH) of the eNH2 group
*Stretching vibration of the N3eH10 bond.
Abbreviation: op, out-of-plane; ip, in-plane; w, weak; m, medium; s, strong; vs, very strong; br, broad.

complexation, the eNH2 amine group loses a proton, firstly, which
increases electron density in the C9eN3 bond region. Then, the N3
nitrogen coordinates to the metal ion.
The complex has a square planar geometry. All of the two aro-
matic rings with their substitutions, two chelating rings, all of the
donating atoms of the ligands as well as the Ni atom lie in a same
plane (Table 1). The calculated structural parameters for the L3
Schiff base ligand and its Ni(II) complex are in agreement with the
reported data for the similar compounds [13,24,25,34e37], con-
firming suitability of the optimized geometries for the investigated
compounds.
C5 complex (Table 2).
For comparison, the IR spectra of the L3 Schiff base and its Ni (II)
complex (C5) are shown in Fig. 3. The FT-IR spectrum of the L3
showed the absorption peaks at 1647 cm1 and 3276-3362 cm1 for
the azomethine and eNH2 groups, respectively. On the other hand,
the FT-IR spectrum of the complex (b) did not show the absorption
peaks of eNH2 group. Also, shift of the symmetrical stretching
modes of azomethine groups to 1606 cm1 confirm coordination of
the ligand via the eNH amine group and the azomethine nitrogen.
4.3. NMR analysis

4.2. Vibrational spectroscopy The 1H NMR spectrum of the ligand in CDCl3 showed one single
peak at 5.13 ppm for the eNH2 group. The aromatic protons of the
Herein, the IR spectra of the L3 ligand and its Ni(II) complex benzene and pyridine rings were observed at 8.05e8.80 ppm
were analyzed by comparing their DFT-computed and experi- (Fig. 4, spectrum c). These results confirmed the structure of the L3
mental vibrational modes. In Table 2 selected vibrational fre- Schiff base. On the other hand, the existence of the eNO2 group as
quencies of the investigated compounds are gathered. an electron accepting group in the para position of the eNH2 group
An important diagnostic for coordination mode of the Schiff
bases to metals is the energy value of an intensive band in the 1660-
1500 cm1 region of the IR spectra [10,13,24,25,34,38e48]. The
symmetrical stretching modes of C1¼N1 bond are attributed to a
strong band at 1647 cm1 of the IR spectrum of the L3 ligand, which
band that shifts to lower frequency (1606 cm1) in the IR spectrum
of the complex. This shift to lower energy approves that the L3
ligand is coordinated to the Ni2þ ion through the azomethine ni-
trogen (N1 atom) [10,24,25,34,38e48].
In the 3600-2000 cm1 spectral region of the IR spectra, over-
lapping of the OeH, NeH and CeH stretching vibrations causes to
band broadening [10,24,25,34,38e48]. Deconvolution of this
spectral region of the L3 Schiff base and the C5 complex has been
given in Table 2. In this region, the most intensive band is related to
the stretching vibrations of the NeH bonds of the amine group.
For complexation, the L3 ligand is deprotonated, firstly, which
loses the H9 proton of the eNH2 group. Deprotonation of the amine
nitrogen increases the electron density in the bonding region of the
C9eN3 bond, which increases strength of the C9eN3 bond. Since, in
comparison with the free L3 ligand, the stretching vibration of the
C9eN3 bond shifts to the higher frequencies in the spectrum of the Fig. 3. The FTIR spectra of the L3 ligand (a) and the C5 complex (b).
428 M. Habibi et al. / Journal of Molecular Structure 1143 (2017) 424e430

numbered as in Figs. 1 and 2. The DFT-calculated chemical shifts are

in agreement with the experimental results. The only exception is
the H10 proton of the amine substitution, where the calculated
chemical shift is considerably lower than its experimental value.
Obviously, the solvent molecules and other species in the solvent
interact with the eNH proton. On the other hand, the experimental
values are obtained from CDCl3 solutions, while the calculated
values are correspond to the isolated molecule.
In addition to the elemental analysis, the DFT-calculated vibra-
tional frequencies and chemical shifts are good in agreement with
the corresponding experimental values, confirming validity of the
proposed structures for the investigated compounds. The obtained
results could be beneficial in identification of the similar com-
Fig. 4. The 1H NMR spectra of the L3 ligand (c) and the C5 complex (d).
pounds, too.

4.4. NBO analysis

The 3D-distribution map for the highest-occupied-molecular

orbital (HOMO) and the lowest-unoccupied-molecular orbital
(LUMO) of the L3 and C5 species are shown in Fig. 6. As seen, the
HOMO orbital of the L3 is localized on the benzene ring and its
substitutions. But the LUMO orbital is mainly localized on the

13
Fig. 5. The C NMR spectra of the L3 ligand (e) and the C5 complex (f).

is an important reason for decrease in activity of the eNH2 group as

a nucleophile. The 1H NMR spectrum of the complex in CDCl3
showed a chemical shift of eNH group at 13.81 ppm, where the
aromatic protons of pyridine ring were observed at 8.35e8.46 ppm
(Fig. 4, spectrum d). The 13C NMR spectra of both of the L3 ligand
and C5 complex (Fig. 5) showed 12 carbons, which is accordance
with their proposed structures.
The experimental and DFT-calculated NMR chemical shifts (d) of
the L3-1 (more stable isomer of the L3 Schiff base) and the C5
complex are gathered in Table 3, where the atom positions are
Fig. 6. The HOMO and LUMO frontier orbitals of the L3 ligand and C5 complex.

Table 3
Experimental and theoretical 1H NMR and 13
C NMR chemical shifts of the L3 and C5 species in CDCl3 solution, d [ppm].

Atom position L3 C5 Atom position L3 C5

Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo.

H1 8.78 9.19 8.78 9.23 C1 160.04 156.27 143.44 136.54

H2 7.46 7.64 7.76 7.51 C2 154.57 153.45 147.80 156.85
H3 8.80 9.11 8.36 8.1 C3 122.53 115.29 117 116.14
H4 8.08 8.10 8.13 8.03 C4 133.35 129.97 126.23 136.06
H5 8.76 8.71 7.38 7.36 C5 151.56 146.83 143.92 151.39
H6 8.19 8.53 8.46 8.24 C6 125.34 118.04 122.62 120.23
H7 6.79 6.90 6.53 6.12 C7 136.43 131.49 128.80 129.33
H8 8.21 8.56 8.04 8.02 C8 113.81 109.33 111.86 112.51
H9 5.13 4.15 13.81 2.41 C9 150.02 144.95 150.17 153.34
H10 5.13 5.86 e e C10 137.25 135.86 138.37 123.11
C11 98.69 113.53 116.10 105.98
C12 113.55 121.09 118 120.38
 M. Habibi et al. / Journal of Molecular Structure 1143 (2017) 424e430
pyridine ring. Both of the HOMO and LUMO frontier orbitals are
localized on the azomethine group. Inversely, the HOMO and LUMO
frontier orbitals of the C5 species are mainly localized on the pyr-
idine and benzene rings, respectively. Since, in both of the L3 ligand
and the C5 complex, electron transition from the HOMO orbital to
the LUMO orbital is a p/p* transition.
The energy gap between the HOMO and LUMO frontier orbitals
is one of the essential characteristics of molecules, which plays a
determining role in such cases as electric properties, electronic
spectra and photochemical reactions. The value of the energy gap
between the HOMO and LUMO orbitals of the L3 and C5 species are
equal to 3.69 and 2.21 eV, respectively. These large energy gaps
demonstrate that structures of the L3 ligand and the C5 complex
are stable [39,46,47,49,50].
5. Conclusion
In this work, the 4-nitro-N2-pyridin-2-ylmethylene-benzene-
1,2-diamine (L3) Schiff base and its Ni(II) complex have been newly
synthesized and characterized. In addition, the DFT methods were
employed to achieve deeper insight into geometry and spectral
properties of the synthesized compound.
The optimized geometry of the L3 ligand isn’t planar; the aro-
matic rings make approximately a 30 dihedral angle to each other.
But, the optimized geometry of the C5 complex is exactly square
planar. By complexation, the C1¼N1 bond length of the azomethine
group is increased, while the C9eN3 bond length is decreased.
Deprotonation of the amine group leads to decrease of the ph-NH
bond length.
The L3 Schiff base coordinates to the Ni2þ ion via three nitrogen
atoms of the pyridine ring, azomethine moiety and deprotonated
eNH amine group. The fourth coordination position of the square
complex is occupied with the Cl ligand. Good consistency between
the calculated and experimental values confirms suitability of the
optimized geometries for the L3 and C5 compounds.
Shapes of the HOMO and LUMO frontier orbitals of the L3 ligand
and its complex were determined. The conjugation increases sta-
bility of the investigated compounds. High energy gaps confirm
stability of both of the investigated compounds.
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