Synthesis, characterization and computational studies of 4-[(Pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid

Article abstract of DOI:10.1016/j.molstruc.2020.128247

A new hydrazone derivative compound, 4-[(Pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid, C₁₅H₁₁N₃O, was obtained and characterized by ¹H NMR, ¹³C NMR and UV–Vis, FT-IR and FT-Raman spectroscopy techniques. Molecular geometry, vibrational wavenumbers, frontier molecular orbital and non-linear optical (NLO) property of the title compound were calculated using ab initio Hartree-Fock (HF) and Density Functional Theory (DFT), employing B3LYP functional at 6–311++G (d,p) basis set. ¹H and ¹³C NMR chemical shifts were calculated by using the gauge in dependent atomic orbital (GIAO) method at the HF and B3LYP methods with different basis sets. In addition, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were obtained from DFT LSDA methods with 6–311++G (d,p) basis set. The NLO behaviour of the title compound has been studied by determining the electric dipole moment (μ) and hyperpolarizability (β) using both B3LYP/6–311++G (d,p) and HF/6–311++G (d,p) methods. The energy gaps s(ΔE_gap=E_LUMO?E_HOMO) of title molecule were calculated at 4.15, 2.77 and 9.81 eV with DFT-B3LYP/6–311++ G (d,p), DFT-LSDA/6–311++ G (d,p) and HF/6–311++ G (d,p) level of theory, respectively. The calculated experimentally energy gap was found as 2.827 eV.

Full text of DOI:10.1016/j.molstruc.2020.128247

Journal of Molecular Structure 1215 (2020) 128247
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, characterization and computational studies of 4-[(Pyridine-
3-carbonyl)-hydrazonomethyl]-benzoic acid
a
,
*
b,
**
c
d, e
€
€
ꢀ
ꢀ
Füreya Elif Oztürkkan Ozbek , Güventürk Ugurlu
, Erbay Kalay , Hacali Necefoglu
a Kafkas University, Department of Chemical Engineering, 36100, Kars, Turkey
b Kafkas University, Department of Physics, 36100, Kars, Turkey
c Kafkas University, Kars Vocational College, 36100, Kars, Turkey
d Kafkas University, Department of Chemistry, 36100, Kars, Turkey
e Baku State University, International Scientific Research Centre, 1148, Baku, Azerbaija
a r t i c l e i n f o
a b s t r a c t
Article history:
A
new hydrazone derivative compound, 4-[(Pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid,
C15H11N3O, was obtained and characterized by 1H NMR, 13C NMR and UVeVis, FT-IR and FT-Raman
spectroscopy techniques. Molecular geometry, vibrational wavenumbers, frontier molecular orbital
and non-linear optical (NLO) property of the title compound were calculated using ab initio Hartree-Fock
(HF) and Density Functional Theory (DFT), employing B3LYP functional at 6e311þþG (d,p) basis set. 1H
and 13C NMR chemical shifts were calculated by using the gauge in dependent atomic orbital (GIAO)
method at the HF and B3LYP methods with different basis sets. In addition, the highest occupied mo-
lecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were obtained from DFT
LSDA methods with 6e311þþG (d,p) basis set. The NLO behaviour of the title compound has been
Received 24 January 2020
Received in revised form
8 April 2020
Accepted 11 April 2020
Available online xxx
Keywords:
Aroylhydrazones
Nicotinohydrazides
Molecular geometry
Hyperpolarizability
NLO
studied by determining the electric dipole moment (
m
) and hyperpolarizability (
b) using both B3LYP/6
e311þþG (d,p) and HF/6e311þþG (d,p) methods. The energy gaps sð
DEgap ¼ ELUMO ꢀEHOMOÞ of title
molecule were calculated at 4.15, 2.77 and 9.81 eV with DFT-B3LYP/6e311þþ G (d,p), DFT-LSDA/6
e311þþ G (d,p) and HF/6e311þþ G (d,p) level of theory, respectively. The calculated experimentally
energy gap was found as 2.827 eV.
© 2020 Elsevier B.V. All rights reserved.
1. Introduction
[10], Cu(II) and spectrofluorimetric determination of Al(III) [11,12].
Some aromatic hydrazones derived from nicotinic acid hydrazide
Nicotinic acid derivatives are very important in biological ac-
tivities such as anti-parkinsonian, anti-tubercular, antihelmintic,
antifungicidal, antitumor and anti-bacterial activities [1e3]. Nico-
tinic acid hydrazides give the significant effect on toxicity to the
insects [4]. The chemistry aroylhydrazones derived from nicotinic
acid hydrazide have been intensively studied due to their biological
and physico-chemical properties and applications. Nicotinohy-
drazides posses antimycobacterial, antiviral, antimicrobial [5],
antituberculosis [6], anticonvulsant [7], anti-inflammatory and
analgestic [8,9], insecticidal [4] activities. Recent studies have
shown that nicotinohydrazides could be potentially used as
analytical reagents for spectrophotometric determination of V(V)
are potential fluorimetric pH sensors [13]. The efficiency of 1-(4-
propylbenzylidene)nicotinohydrazide has been studied as corro-
sion inhibitor of mild steel [14].
Structures of aroylhydrazones derived from nicotinic acid hy-
drazide have been investigated in solid state, in solution and gas
phase by FT-IR, NMR, UVeVis, ATR and Raman spectroscopy, ESI-
MS and MS/MS analysis techniques [15e17]. The protonation con-
stants and hydrolytic stability of nicotinohydrazides have been
studied by using of spectrophotometric, HPLC and MS measure-
ments [18]. The dipole moments, polarizability and first order
hyperpolarizability of N’-(2-metyl-3-phenylallylidene)nicotinohy-
drazide and its isonicotinohydrazide analog have been computed
and calculated. The first order hyperpolarizabilities have revealed
that both hydrazides behave as interesting NLO materials [19].
The coordination abilities of transition metal complexes of
aroylhydrazones have made them attractive as ligands for the
synthesis of new coordination compounds dioxomolybdenum (VI)
* Corresponding author.
** Corresponding author.
€
€
E-mail addresses: elif@kafkas.edu.tr (F. Elif Oztürkkan Ozbek), gugurlu@kafkas.
ꢀ
edu.tr (G. Ugurlu).
https://doi.org/10.1016/j.molstruc.2020.128247
0022-2860/© 2020 Elsevier B.V. All rights reserved.

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
complexes 2-hydroxybenzaldehyde nicotinoylhydrazone and
vanadium(V) complex of N0-(3,5-dibromo-2-hydroxybenzylidene)
nicotinohydrazide are an effective catalysis for oxydation of alifatic
and aromatic olefines [20e22]. The cytotoxicity against human
lung cancer, human gastric cancer and human esophageal cancer
cell lines of (E)-N’-(1-(pyridin-2-yl)ethylidene)nicotinohydrazide
nicotinohydrazide and its Mn(II), Co(II), Cu(II), Cd(II) complexes
have been investigated [23]. The antitubercular activities of 2,6-
Pyridine-3-carbohydrazide was prepared according to the litera-
ture [6].
2.1. Synthesis of the pyridine-3-carbohydrazide
In a 100 mL round-bottom flask, methylnicotinate 1 (2.74 g,
20 mmol) was dissolved in methanol (99%, 50 mL), and hydrazine
hydrate (0.97 mL, 20 mmol) was added. The reaction mixture was
heated under reflux conditions for 2 h. Progress of the reaction was
monitored by TLC. After completion of the reaction, the mixture
was cooled to room temperature. The solvent was concentrated in
vacuo. The residue was redissolved in ethyl acetate (50 mL). Sub-
sequently, the mixture was extracted with water (2 ꢂ 30 mL). The
combined organic layers were dried over anhydrous Na2SO4,
filtered and removed under reduced pressure. The hydrazide 2 was
used in the following reaction without further purification (white
solid, yield: 79%, m. p: 161e163 ꢁC).
dihydroxybenzaldehyde
nicotinoylhydrazone,
5-chloro-2-
hydroxybenzaldehyde nicotinoylhydrazone and some transition
metal complexes of them have been evaluated against H37Rv strain
of Mycobacterium tuberculosis, in vitro [24,25]. Lead nicotinohy-
drazides have interesting structures due to the presence of tetrel
bonds [26,27].
Despite the fact that the crystalline structures of aroylhy-
drazones derived from nicotinic acid hydrazide have been investi-
gated using single crystal X-ray diffraction in recent years
[15,25,28e33], there are a few theoretical studies of them [34,35].
In addition, to the best of our knowledge, among the substances so
far studied aroylhydrazones derived from nicotinic acid hydrazide
the title compound is absent. In order to eliminate this deficiency,
we synthesized title compound and characterized by Fourier-
Transform Infrared (FT-IR) and Fourier-Transform Raman (FT-
Raman) and 1H, 13C NMR and UVeVis spectroscopy techniques. A
series of Hartree-Fock (HF) and Density Functional Theory (DFT)
calculations on the title compound were reported in this paper. The
optimized structure of 4-[(Pyridine-3-carbonyl)-hydrazono-
methyl]-benzoic acid molecule with atomic number scheme in
B3LYP/6e311þþG (d.p) level was given in Fig. 1.
2.2. Synthesis of the 4-[(Pyridine-3-carbonyl)-hydrazonomethyl]-
benzoic acid
In a 100 mL round-bottom flask, pyridine-3-carbohydrazide 2
(2.00 g, 14.6 mmol) and 4-formylbenzoic acid 3 (2.19 g, 14.6 mmol)
were dissolved in methanol (60 mL) at room temperature. Then a
few drops of glacial acetic acid as a catalyst were added. This
mixture was heated under reflux for 5 h. The desired compound
was monitored by TLC analysis. The mixture cooled to room tem-
perature. Methanol was removed in vacuo and the precipitate ob-
tained was suspended in a mixture of methanol-water (1:1,
3 ꢂ 10 mL), filtered off. After FT-IR spectra and thermal analysis
results of 4-[(pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid
monohydrate were evaluated, this compound was dried in a vac-
uum oven to afford the 4-[(pyridine-3-carbonyl)-hydrazono-
methyl]-benzoic acid 4 (2.94 g, white solid, yield 75%, m. p:
317e319 ꢁC). The reactions were given in above reaction scheme.
2. Materials and methods
All starting materials and solvents were purchased from com-
mercial sources and used without further purification. Crystal
water determination and thermal analyses were performed by the
Shimadzu DTG-60H system, in a dynamic nitrogen atmosphere
(100 mL/min), at a heating rate of 10 ꢁC/min, in platinum sample
1H NMR (400 MHz, DMSO‑d6, ppm)
d 13.11 (br s, 1H, OH), 12.18
(s, 1H, NH), 9.09 (s, 1H, CH¼N), 8.79e8.78 (m, 1H), 8.51 (s, 1H), 8.28
(d, J ¼ 7.8 Hz, 1H), 8.03 (d, J ¼ 8.0 Hz, 2H, AreH), 7.87 (d, J ¼ 8.1 Hz,
2H, AreH), 7.59 (dd, J ¼ 7.5, 5.0 Hz, 1H); 13C NMR (100 MHz,
vessels with reference to a-Al2O3. Melting point was determined in
open glass capillary using a Stuart melting point SMP30 apparatus.
Infrared and Raman spectra of the compound were recorded in the
range of 4000e400 cmꢀ1 on an ALPHA-P Bruker FT-IR spectrometer
and Thermo Scientific/Nicolet IS50 Raman spectrometer from solid
sample, respectively. UVeVis spectra were recorded on a Perki-
nElmer’s LAMBDA 25 Spectrophotometer and Schimadzu 3600/UV-
VIS-NIR Spectrophotometer in DMSO. NMR Spectra were recorded
at 400 MHz (1H) and 101 MHz (13C) at 298 K using tetramethylsi-
lane (0 ppm) as the internal reference. NMR spectroscopic data
were recorded in DMSO‑d6 using as internal standards the residual
non-deuteriated signal for 1H NMR and the deuteriated solvent
DMSO‑d6, ppm)
d
167.4 (Cq, C¼O), 162.4 (Cq, C¼O), 152.9 (CH), 149.1
(CH), 147.7 (CH), 138.6 (Cq), 136.0 (CH), 132.4 (Cq), 130.3 (CH), 129.5
(Cq), 127.7 (CH), 124.1 (CH); FT-IR (Solid Sample, cmꢀ1) 3482, 3432,
3214, 3072, 2358, 2343, 1666, 1605, 1560, 1508, 1473, 1409, 1363,
1333, 1317.
2.3. Computational details
All computational studies on the title molecule were performed
by the aid of Gaussian 09 W program package and Gauss view 5.0
molecular visualization programs [36,37]. Initial geometries were
optimized at ab-initio-HartreFock (HF) [38] and Density Functional
Theory (DFT) with Becke’s three parameter hybrid functional (B3)
[39] and combined with gradient corrected correlation functional
of LeeeYangeParr (LYP) [40,41] and employing 6e311þþG (d,p)
basis set [42,43] in the gas phase. In order to obtain the best stable
structures, conformational analysis of the optimized molecule was
signal for 13C NMR spectroscopy. Chemical shifts (
d) are given in
ppm, and coupling constants (J) are given in Hertz. The following
abbreviations are used for multiplicities: s ¼ singlet, d ¼ doublet,
t ¼ triplet, q ¼ quartet, dd ¼ doublet of doublets and m ¼ multiplet.
performed as a function of dihedral angles f1 (C3eC2eC6eN2), f2
(N3eC7eC8eC13) and f3 (C10eC11eC14eO2) which were varied
between 0 and 360ꢁ in 10ꢁ steps with B3LYP/6-31G level of theory.
The global energy minimum of each potential energy curves was
referred to as zero. After optimization, vibrational frequencies,
m, a,
b
based on finite field approach, HOMO and LUMO of the title
molecule in the ground states obtained B3LYP/6e311þþG (d,p) and
HF/6e311þþG (d,p) level of theory were calculated in the same as
level of theory. The 1H and 13C NMR chemical shifts were calculated
Fig. 1. The optimized structure of the molecule and and its numbering scheme.

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
3
by GIAO approach by using B3LYP and HF methods with 6e311þþG
(d,p), 6-311 þ G (2d,p) and 6e311þþG (2d,p) basis sets both in the
gas phase and in DMSO. Also, EHOMO (the highest occupied mo-
lecular orbital energy) and ELUMO (the lowest unoccupied molecular
orbital energy) of title molecule were calculated at the DFT
methods; local-spin density approximation LSDA with 6e311þþG
(d,p) basis sets.
ppm values (DFT/HF) for C14 carbon atom were found as 171.8/
167.3, 171.2/166.9 and 171.8/167.0 ppm according to B3LYP/HF
6e311þþG (d,p), B3LYP/HF 6-311 þ G (2d,p) and B3LYP/HF
6e311þþG (2d,p), respectively. It was found that the results closest
to the experimental value were B3LYP/6e311þþG (d,p) when the
experimental data were compared with theoretically calculated
three different methods.
3. Results and discussion
3.2. Vibrational analysis
3.1. NMR spectra
The vibrational spectra of substituted benzene derivatives have
been greatly investigated by various spectroscopic methods, since
the single substitution can have a tendency to put greater changes
in vibrational wavenumbers of benzene [50,51]. In other words,
molecular system of benzene is greatly affected by the nature of
substituents. The number of potentially active fundamentals of
non-linear molecule which have N atoms is equal to (3N-6) apart
from three translational and three rotational degrees of freedom.
The title molecule contains 31 atoms and 87 normal vibration
modes have C1 symmetry (Supplemental Table 1).
Nuclear Magnetic Resonance Spectroscopy (NMR) is the useful
technique for understanding the relationship between the elec-
tronic features and the structure of compounds. In this study,
1
experimental H and 13C NMR spectra of the title compound were
1
measured in DMSO‑d6. The obtained experimental data for H and
13C NMR spectra were used to determine the molecular structure
and these data were compared with those obtained theoretically.
In the 1H NMR spectra, the carboxylic acid OeH proton in title
compound appeared as a singlet signal at 12.18 ppm. The NeH
proton observed as a singlet signal at 9.09 ppm. The aromatic
protons of the benzene and pyridine rings were observed among
the 8.27e8.79 ppm and at 8.04e7.58 ppm in regions of spectrum,
respectively. In 13C NMR spectra, C¼O carbon atom of carboxylic
acid (C14) showed as very sharp signal at 167.4 ppm. The signals of
aromatic carbons of pyridine ring were observed at 147.7 (C1),130.3
(C2), 136.0 (C3), 124.1 (C4), 149.1 (C5) ppm. The singlet signal for
imine carbon was seen at 152.9 ppm. The signals of aromatic car-
bons of benzene ring were observed at 138.6 (C8), 130.1 (C9), 129.5
(C10), 127.7 (C11), 132.4 (C12), 127.7 (C13) ppm. A singlet signal
belonged to C¼O carbon atom of carbonyl was showed at
162.4 ppm (Fig. 2).
In the spectra of the title compound, it was observed a medium
band at 3482 cmꢀ1 due to
n(OeH). This absorption band was ob-
tained among 3736 and 3613 cmꢀ1 with help of HF and DFT/B3LYP
methods at 6-31G (6e311þþG (d,p) bases set calculations for FT-IR,
respectively. The weak bands observed at 3400 and 3300 cmꢀ1 in
the FT-Raman spectrum are assigned to OeH stretching vibrations.
This vibrations were computed among 3645 and 3656 cmꢀ1 with
help of HF and DFT/B3LYP methods at 6-31G (6e311þþG (d,p)
bases set calculations for FT-Raman spectra, respectively. The peaks
displayed at a 3214 cmꢀ1 (for FT-IR) and 3257 cmꢀ1 (for FT-Raman),
which is attributed to the NeH stretching vibration. The vibration
frequency for NeH stretching was calculated to be 3219 cmꢀ1 and
3378 cmꢀ1 with help of HF and DFT for FT-Raman. The aromatic
CeH stretching vibrations for pyridine and benzene rings were
observed at 3072 cmꢀ1 (for FT-IR) and 3057 cmꢀ1 (for FT-Raman).
The theoretically calculated value of CeH stretching vibrations
were found to be between 3059 and 2907 cmꢀ1 at HF and 3076-
2889 cmꢀ1 at DFT/B3LYP methods at 6e311þþG (d,p) bases set for
FT-IR spectra. In the FT-Raman spectra obtained from DFT and HF
methods, these vibrations were seen as weak vibrations. The bands
related to the carbonyl and carboxylic group C¼O stretching vi-
brations were observed at 1666 cmꢀ1 and 1605 cmꢀ1 (for FT-IR
spectra) and 1628 cmꢀ1 and 1611 cmꢀ1. The C¼O stretching vi-
brations (C6eO1) of carbonyl group were calculated to be
1754 cmꢀ1 at B3LYP/6e311þþG (d,p) and 1792 cmꢀ1 at HF/
6e311þþG (d,p). The C¼O stretching vibrations (C14eO2) of car-
boxylic group were found to be 1732 cmꢀ1 B3LYP/6e311þþG (d,p)
and 1766 cmꢀ1 HF/6e311þþG (d,p) for FT-IR spectra. In FT-IR
spectra of compound, the bands at 1605 and 1560 cmꢀ1 were
The isotropic chemical shift analysis allows us to identify rela-
tive ionic species and to calculate reliable magnetic properties in
nuclear magnetic resonance (NMR) spectroscopy which provide
the accurate predictions of molecular geometries, [44e46]. For this
purpose, the optimized molecular geometry of the titled compound
was obtained by using B3LYP and HF methods with 6e31G (d) basis
level in DMSO solvent. By considering the 1H and 13C NMR chemical
shift values of the molecule were calculated at the same level by
using Gauge-Independent Atomic Orbital method (Table 1). Theo-
retically and experimentally values were plotted according to
d
exp ¼ a.
d
calc.þ b, Eq. a and b constants regression coefficients
with a standard error values were found using the SigmaPlot pro-
gram. The correlation graphics and linear correlation data of the
titled compound were given Fig. 3.
Therefore the (R2) values (DFT/HF) for 1H NMR/13C NMR
chemical shifts have been found as 0.9714/0.6419, 0.9723/0.6293
and 0.9723/0.6311 for the title compound according to B3LYP/HF
6e311þþG (d,p), B3LYP/HF 6-311 þ G (2d,p) and B3LYP/HF
6e311þþG (2d,p), respectively (Fig. 2). In our study, in the 1H NMR
spectrum of corresponding compound, it was observed belong to
H7 proton signal at 12.18 ppm because acidic show feature [47e49].
However, theoretically (DFT/HF) H7 proton has been observed as
10.74/10.12, 10.82/10.17 and 10.84/10.18 according to B3LYP/HF
6e311þþG (d,p), B3LYP/HF 6-311 þ G (2d,p) and B3LYP/HF
6e311þþG (2d,p) methods, respectively (Fig. 2). It was observed
that there was a correlation between the calculated and experi-
mentally obtained values except for H7 proton. However, there was
a higher than expected difference between the calculated values
and the experimental values for H7 proton.
assigned to
y
(C¼N) and (N¼N) respectively. These peaks were
y
computed at 1643 and 1616 cmꢀ1 group at B3LYP/6e311þþG (d,p).
The C7eN1 stretching vibration was calculated to be 1269 cmꢀ1 at
B3LYP/6e311þþG (d,p) and 1215 cmꢀ1 at HF/6e311þþG (d,p) level
of theory [52,53]. In FT-Raman spectra of compound, the bands at
1571 cmꢀ1 and 1569 cmꢀ1 are assigned to
y
(C¼N) and (N¼N),
y
respectively. Similar vibrations were observed in the FT-Raman
spectra obtained with the help of HF and DFT methods.
The differences between the experimental and theoretical
values of mentioned vibrations were based on from non-covalent
interactions such as intermolecular and intramolecular hydrogen
bonds (Fig. 4 a, c, d). Unlike mentioned peaks, in the FT-IR spectra of
4-[(pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid mono-
hydrate, the OeH vibrations caused by the water molecule were
observed 3600-3300 cmꢀ1 in the region (Fig. 4-b). FT-Raman
spectra were given in Fig. 5.
In Table 1, the biggest 13C chemical shift value of the compound
observed at 167.00 ppm for the C14 carbon atom double bounded to
the oxygen in carbonyl group [48]. Theoretically, the calculated

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
Fig. 2. (a) 1H, (b) 13C NMR (DMSO‑d6) and (c) DEPT spectra of the titled compound.

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
5
Table 1
3.3. Conformational and structural analysis
The calculated and experimental 1H and 13C NMR isotropic chemical shifts of the
titled compound (with respect to TMS, all values in ppm).
In the result of conformation analysis, the plotted potential
energy curves (PECs) of the molecule as a function of dihedral an-
6-311þþG
6-311 þ G
6-311þþG
(d.p)
(2d.p)
(2d.p)
gles
f
1
(C3eC2eC6eN2),
f
2
(N3eC7eC8eC13) and
f3
Experiment.
B3LYP
HF
B3LYP
HF
B3LYP
HF
(C10eC11eC14eO2) were given Fig. 6. During conformation anal-
ysis, all the geometrical parameters were concurrently relaxed but
C14
C6
C7
C5
C1
C8
C3
C12
C2
C10
C9
167.4
162.4
152.9
149.1
147.7
138.6
136.0
132.4
130.3
129.5
130.3
127.4
127.4
124.1
12.18
9.09
8.79
8.51
8.29
7.88
8.04
8.02
7.60
7.87
171.8
170.5
156.8
160.2
152.7
148.6
143.3
138.
137.1
137.0
136.6
135.8
129.7
129.6
10.74
9.02
8.98
8.77
8.63
8.57
8.52
8.36
7.59
7.56
167.3
169.7
156.2
162.7
155.9
149.2
150.7
140.9
133.1
140.0
135.2
134.2
130.2
126.2
10.12
9.19
9.14
7.75
9.07
8.72
8.85
8.61
7.56
7.77
171.2
169.8
155.9
158.8
151.6
147.5
141.8
137.0
136.1
135.7
135.3
134.8
128.2
127.8
10.82
9.11
9.07
8.89
8.63
8.56
8.54
8.41
7.59
7.61
166.9
169.1
155.1
161.5
154.6
147.9
149.4
139.3
131.8
138.4
133.7
133.2
128.6
124.5
10.17
9.24
9.17
7.82
9.08
8.67
8.88
8.64
7.57
7.82
171.8
170.4
156.4
159.4
152.3
148.0
142.4
137.5
136.6
136.2
135.8
135.4
128.7
128.4
10.84
9.14
9.07
8.90
8.66
8.57
8.55
8.43
7.61
7.63
167.0
169.2
155.2
161.6
154.7
148.0
149.5
139.4
131.9
138.5
133.8
133.3
128.7
124.6
10.18
9.24
9.16
7.82
9.08
8.66
8.88
8.63
7.57
7.83
dihedral angles, f1, f2 and f
3 were varied in steps of 10ꢁ ranging
from 0ꢁ to 360ꢁ. As shown in the Fig. 6, the global energy minimum
on PECs was referred to as zero. The PECs obtained at B3LYP/6e31 G
showed three minimum energy structures at the 0, 180 and 360ꢁ
and two energy barrier at the 90 and 270ꢁ. Since the potential
energy curves are symmetrical with respect to 180ꢁ, the barrier
heights obtained for each dihedral angle have the same value. The
barrier heights of
3 (C10eC11eC14eO2) dihedral angles were found to be 4.41, 8.09
and 9.02 kcal/mol, respectively.
f1 (C3eC2eC6eN2), f2 (N3eC7eC8eC13) and
f
C11
C13
C4
The molecular structure of 4-[(pyridine-3-carbonyl)-hydrazo-
nomethyl]-benzoic acid molecule was optimized using both HF and
DFT/B3LYP methods using 6-311Gþþ(d,p) basis set. The selected X-
ray (experimental) [54] and the theoretical results of structure
were given Table 3.
The carbon-carbon bond lengths were: C2eC6 1.5018 Å (B3LYP)/
1.5004 Å (HF)/(4) Å 1.497 (4) Å (XRD) and C7eC8 1.4629 Å (B3LYP)/
1.4766 Å (HF)/1.469 (4) Å (XRD). The carbon-nitrogen bond lengths
were: C1eN1 1.3349 Å (B3LYP)/1.3198 Å (HF)/1.337 (4) Å (XRD),
C5eN1 1.3357 Å (B3LYP)/1.3179 Å(HF)/1.336 (4) Å (XRD), C6eN2
1.3889 Å (B3LYP)/1.3697 Å(HF)/1.364 (4) Å (XRD) and C7¼N3,
1.2805 Å (B3LYP)/1.2519 Å (HF)/1.281 (4) Å (XRD) The nitrogen -
nitrogen bond lengths were: 1.3532 Å (B3LYP)/1.3512(HF)/1.389 (4)
Å (XRD).
H7
H1
H5
H2
H3
H13
H12
H10
H4
H9
H6
7.59
5.78
5.57
5.65
5.41
5.67
5.42
Fig. 3. The correlation graphics for 13C NMR B3LYP/HF 6e311þþG (d,p) (a), 1H NMR B3LYP/HF 6e311þþG (d,p) (b), 13C NMR B3LYP/HF 6-311 þ G (2d,p) (c), 1H NMR B3LYP/HF 6-
311 þ G (2d,p) (d), 13C NMR B3LYP/HF 6e311þþG (2d,p) (e) and 1H NMR B3LYP/HF 6e311þþG (2d,p) (f) chemical shifts of the title compound.

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
Fig. 6. Potential energy curves for the molecule with B3LYP/6-31G.
than the solid state, very little deviation should be expected.
3.4. Electronic properties, HOMO-LUMO and MEP analysis
The UVeVis spectra of the title compound were recorded in
DMSO at room temperature. The experimental and theoretical
electronic spectra of the title compound were given in Fig. S1. In the
electronic spectra, n/
p* and
p/p* transitions are due to the
presence of Q bands. The n/p* or p/p* transitions of the func-
tional groups such as the benzene ring, pyridine ring, C¼O, C¼N
were observed at 322 nm. This value was calculated to be 315 nm
for the B3LYP/6-31G level [55].
Fig. 4. Theoretical and experimental FT-IR Spectra of the titled compound (a) Theo-
retical FT-IR from HF/6e311þþG (d,p) (with scalling factor); b) Theoretical FT-IR
B3LTY/6e311þþG (d,p) (with scalling factor); c) Experimental FT-IR spectra of 4-
[(Pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid monohydrate; d) Experimental
FT-IR spectra of 4-[(Pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid.
The band gap, a fundamental physical feature of the molecules,
can be described as minimum photon energy necessary to excite an
electron from HOMO to LUMO. We determined the band gap of 4-
[(pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid molecule
obtained through the UV-3600 Plus UV-VIS-NIR Spectrophotom-
eter with ISR-603 Integrating Sphere Attachment and carry out an
ab-initio HF and DFT with B3LYP and LSDA level using 6e311þþG
(d.p) basis set. The iso-density plots of the HOMO and LUMO
computed by the methods of B3LYP/6e311þþG (d,p) of the studied
compounds were shown in Fig. 7.
The carbon-oxygen bond lengths were: C6¼O11.2117 Å (B3LYP)/
1.1875 Å (HF)/1.225 (3) Å (XRD), C14 ¼ O2 1.2089 Å (B3LYP)/1.1847 Å
(HF) and C14eO3 1.3587 Å (B3LYP)/1.3288 Å (HF). The optimized
parameters at both methods differ slightly from the XRD values and
since the theoretical studies are performed on the gas phase rather
Also, the theoretically calculated electronic energy, dipole
moment polarizability and hyperpolarizability values of the mole-
cule and the HOMO and LUMO values obtained both theoretically
and experimentally were given in Table 4.
The reflectance spectra obtained from UVeViseNIR Spectro-
photometer were converted into equivalent absorption spectra by
means of Kubelka-Munk function (Fig. 8). Kubelka-Munk method is
based on following equation [56,57].
K
S
FðRÞ ¼ ð1 ꢀ RÞ2∕2R ¼
Molecular Electrostatic Potential (MEP) gives important infor-
mation about interactions ligand-substrate interactions and local
reactivity of molecule. The MEP of the molecule computed at the
DFT/B3LYP/6-311Gþþ (d, p) level of theory were given in Fig. 9.
The red and blue color regions on MEP surface represent
nucleophilic and electrophilic site, respectively. With respect to the
surface of MEP, the negative potential preferred site for electro-
philic attack is formed around the oxygen atom of the carbonyl
groups and nitrogen atom of imine group and pyridine ring. The
Fig. 5. FT-Raman Spectra of the title compund

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
7
Table 3
The selected experimental and calculated sructure parameters of the molecule.
Bond Length (Å)
X-ray [54]
HF
B3LYP
Bond angle (o)
X-ray [54]
HF
B3LYP
C1eN1
C2eC6
C5eN1
C6eN2
C6eO1
C7eC8
C7eN3
C11eC14
C14eO2
C14eO3
N2eN3
1.337 (4)
1.497 (4)
1.336 (4)
1.364 (4)
1.225 (3)
1.469 (4)
1.281 (4)
e
1.3198
1.5004
1.3179
1.3697
1.1875
1.4766
1.2519
1.4882
1.1847
1.3288
1.3512
1.3349
1.5018
1.3357
1.3889
1.2117
1.4629
1.2805
1.4854
1.2089
1.3587
1.3532
C1eC2eC6
C3eC2eC6
C2eC6eO1
N2eC6eO1
C8eC7eN3
C7eC8eC9
C7eC8eC13
C6eN2eN3
C7eN3eN2
C2eC6eO1
O2eC14eO3
116.9 (3)
119.3 (3)
120.8 (3)
122.9 (3)
121.0 (3)
120.0 (3)
121.6 (3)
119.0 (2)
115.8 (3)
120.8 (3)
e
124.08
118.16
121.65
123.71
121.63
118.95
121.52
120.13
117.93
121.65
122.09
124.23
118.01
122.33
123.39
121.72
119.10
121.79
120.94
117.47
122.33
121.96
e
e
1.389 (4)
Dihedral angle (o)
Dihedral angle (o)
C1eC2eC6eN2
C1eC2eC6eO1
C3eC2eC6eN2
C2eC6eN2eN3
N3eC7eC8eC9
ꢀ23.0 (5)
154.3 (3)
163.7 (3)
168.6 (3)
ꢀ179.3 (3)
28.09
28.01
N3eC7eC8eC13
C6eN2eN3eC7
C10eC11eC14eO3
C12eC11eC14eO2
C12eC11eC14eO3
ꢀ1.1 (5)
ꢀ0.24
ꢀ0.29
ꢀ152.38
ꢀ154.24
ꢀ179.33
179.77
ꢀ152.71
ꢀ154.68
ꢀ177.56
179.67
178.8 (3)
ꢀ172.27
ꢀ0.77
ꢀ175.92
ꢀ0.01
e
e
e
ꢀ0.70
ꢀ0.01
179.98
179.94
3.5. Thermal analysis
The obtained water molecule of 4-[(Pyridine-3-carbonyl)-
hydrazonomethyl]-benzoic acid monohydrate removed in the
temperature range of 50e200 ꢁC that is accompanied by an endo-
thermic peak on 160 ꢁC (exp. 6.42%, calc. 6.27%). After this weight
loss, the anhydrous compound is thermally stable up to 280 ꢁC. The
obtained title compound began to decompose at this temperature
and the obtained compound was completely decomposed (exp.
97.66%) (Fig. 10).
4. Conclusion
A novel Schiff base derivative, 4-[(pyridine-3-carbonyl)-hydra-
zonomethyl]-benzoic acid was synthesized at a high yield by an
original procedure from methyl nicotinate and hydrazine, followed
by condensation with 4-carboxybenzaldehyde. It was characterized
by 1H, 13C NMR, FT-IR, FT-Raman and UVeVis spectroscopy.
Although aroylhydrazones derived from nicotinic acid hydrazides
are widely synthesized, studies comparing experimental data used
for characterization of these compounds with those calculated
theoretically are limited. Molecular geometry, vibrational wave
numbers, frontier molecular orbital and non-linear optical (NLO)
properties of the title compound were calculated using HF and
B3LYP methods. The spectroscopic results obtained were compared
with the results obtained using these methods. When experimental
data from the 1H and 13C NMR spectroscopy were compared with
theoretically calculated values, it was found that the results closest
was obtained from the B3LYP/HF 6e311þþG (d,p) method. In
addition, LSD is considered to be the most appropriate calculation
method for HOMO-LUMO values in this study. The nonlinear optical
properties were calculated at DFT/B3LYP/6-311Gþþ (d, p) level of
theory and it was found that the hyperpolarizability of the
Fig. 7. Calculated HOMO-LUMO plots of the molecule with B3LYP/6e311þþG (d,p).
positive potential is formed around the hydrogen atom of the car-
boxylic acid and attached to nitrogen atom (NH). The dipole
moment value of title molecule has been found as 4.60 (B3LYP) and
5.09 Debye (HF). The hyperpolarizability values of the title mole-
cule are 1299.49 (B3LYP) and 494.57 a. u (HF). The hyper-
polarizability (b) values at the Gaussian 09 output are in atomic
units (a.u) and these values ꢀco33nverted into electrostatic unit (e.s.u)
(for
b
: 1 a. u ¼ 8.639 ꢂ 10
esu). Urea is one of the archetypal
molecules used in the study of the NLO property of molecular
systems. The calculated
value of urea by B3LYP/6e311þþG (d,p)
value of the
b
method is 0.3728 ꢂ 10e30 e. s.u. While comparing,
b
title molecule is 30.11 times greater than that of urea. So, the of 4-
[(pyridine-3-carbonyl)-hydrazonomethyl]-benzoic acid molecule is
suitable for NLO device applications.
Table 4
Electronic Energy, dipole moment (
m), polarizability (a) hyperpolarizability (b), EHOMO and ELUMO of the compound.
DFT/6e311þþG (d,p)
HF/6e311þþG (d,p)
LSDA/6e311þþG (d,p)
Experimental
Electronic Energy (a.u)
ꢀ930.292061803
ꢀ924.728961455
m
a
b
(D)
(a.u)
(a.u)
4.60
5.09
230,74
1299,49
192,67
494,57
EHOMO (a.u)
ELUMO (a.u)
ꢀ0.249004
ꢀ0.096358
4.15
ꢀ0.332458
0.028088
9,81
ꢀ0,248427
ꢀ0,146743
2,77
D
Eg ðeVÞ
2.827

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F. Elif Oztürkkan Ozbek et al. / Journal of Molecular Structure 1215 (2020) 128247
ꢀ
Evaluation of Results Güventürk Ugurlu.: Theoretical Calculations.
ꢀ
Erbay Kalay: Synthesis and Evaluation of Results; Hacali Necefoglu:
Writing-Reviewing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molstruc.2020.128247.
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