Theoretical and experimental assesment of structural, spectroscopic, electronic and nonlinear optical properties of two aroylhydrazone derivative

Article abstract of DOI:10.1016/j.molstruc.2020.128982

Two aroylhydrazone, N'-(pyridine-4-ylmethylene)nicotic acid hydrazide (1) and N'-(pyridine-3-ylmethylene)nicotic acid hydrazide (2), were synthesized and their structures were determined by single-crystal X-ray diffraction analysis. The X-ray analysis indicated that the compound 1 was crystallized in triclinic crystal system with P -1space group a = 8.7899 (2) ?, b = 10.8983 (3) ?, c = 11.7726 (3) ?, α= 89.952 (3)°, β = 88.684 (3)°, γ= 75.293 (2)°, V = 1090.50 (5) ?³ and Z = 4 and compound 2 was crystallized in monoclinic crystal system with P2₁/c space group, a = 11.9239 (3) ?, b = 8.6495 (2) ?, c = 11.1021 (3) ?, α= 90 (3)°, β = 111.664 (3) (3)°, γ= 90°, V = 1064.14 (5) ?³ and Z = 4. Intermolecular interactions of the compounds were determined by Hirhfeld Surface Analysis. The H ··· H interactions with 37.9percent (for compound 1) and 37.5percent (for compound 2) contributions are the most important interactions to the overall crystal packings. FT-IR, Raman, ¹H and ¹³C NMR and UV–Vis spectroscopy methods were used for spectroscopic characterization of the compounds. The spectroscopic properties of the compounds were calculated theoretically by using Density Functional Theory (DFT) with B3LYP and ab initio Hartree-Fock (HF) methods at different basis sets. A correlation was found between the theoretical and experimental values for the spectroscopic results. Moreover, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), electric dipole moment (μ), polarizability (α) and hyperpolarizability (β) of the compounds were computed both DFT/B3LYP/6–311++G(d,p) and ab initio HF/6–311++G(d,p) methods. The calculated first hyperpolarizability value at the DFT/B3LYP/6–31++G (d,p) level of compound 1 with dimer structure is 18.14 times larger than urea, the standard nonlinear optical material. So, this value implies that compound 1 considered have potential candidates for designing high quality nonlinear optical materials. The energy gap (ΔE_gap) and Molecular Electrostatic Potential (MEP) of the compounds were investigated. The structural and vibration frequency values calculated theoretically were compared with the experimental values.

Full text of DOI:10.1016/j.molstruc.2020.128982

Journal of Molecular Structure 1223 (2020) 128982
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
Theoretical and experimental assesment of structural, spectroscopic,
electronic and nonlinear optical properties of two aroylhydrazone
derivative
Füreya Elif Öztürkkan Özbeka,∗, Güventürk Ug˘urlub,∗, Erbay Kalayc, Hacali Necefog˘lud,e
,
Tuncer Hökelekf
a Department of Chemical Engineering, Kafkas University, 36100 Kars, Turkey
b Department of Physic, Kafkas University, 36100 Kars, Turkey
c Kars Vocational School, Kafkas University, 36100 Kars, Turkey
d Department of Chemistry, Kafkas University, 36100 Kars, Turkey
e International Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan
f Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Two aroylhydrazone, N’-(pyridine-4-ylmethylene)nicotic acid hydrazide (1) and N’-(pyridine-3-
ylmethylene)nicotic acid hydrazide (2), were synthesized and their structures were determined by
single-crystal X-ray diffraction analysis. The X-ray analysis indicated that the compound 1 was crystal-
Received 8 June 2020
Revised 25 July 2020
Accepted 26 July 2020
Available online 30 July 2020
˚
˚
lized in triclinic crystal system with P -1 space group a = 8.7899 (2) A, b = 10.8983 (3) A, c = 11.7726
3
˚
˚
(3) A, α= 89.952 (3)°, β = 88.684 (3)°, γ = 75.293 (2)°, V = 1090.50 (5) A and Z = 4 and compound
˚
2 was crystallized in monoclinic crystal system with P21/c space group, a = 11.9239 (3) A, b = 8.6495
Keywords:
3
˚
˚
˚
Aroylhydrazones
(2) A, c = 11.1021 (3) A, α= 90 (3)°, β = 111.664 (3) (3)°, γ = 90°, V = 1064.14 (5) A and Z = 4.
Intermolecular interactions of the compounds were determined by Hirhfeld Surface Analysis. The H ···
H interactions with 37.9% (for compound 1) and 37.5% (for compound 2) contributions are the most
important interactions to the overall crystal packings. FT-IR, Raman, 1H and 13 C NMR and UV–Vis spec-
troscopy methods were used for spectroscopic characterization of the compounds. The spectroscopic
properties of the compounds were calculated theoretically by using Density Functional Theory (DFT) with
B3LYP and ab initio Hartree-Fock (HF) methods at different basis sets. A correlation was found between
the theoretical and experimental values for the spectroscopic results. Moreover, the highest occupied
molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), electric dipole moment
(μ), polarizability (α) and hyperpolarizability (β) of the compounds were computed both DFT/B3LYP/6–
311++G(d,p) and ab initio HF/6–311++G(d,p) methods. The calculated first hyperpolarizability value
at the DFT/B3LYP/6–31++G (d,p) level of compound 1 with dimer structure is 18.14 times larger than
urea, the standard nonlinear optical material. So, this value implies that compound 1 considered have
potential candidates for designing high quality nonlinear optical materials. The energy gap (ꢀEgap) and
Molecular Electrostatic Potential (MEP) of the compounds were investigated. The structural and vibration
frequency values calculated theoretically were compared with the experimental values.
Single crystal XRD
Hirshfeld surface analysis
Spectroscopic characterization
Molecular electrostatic potential
Energy gap
© 2020 Elsevier B.V. All rights reserved.
1. Introduction
compounds with biological prospects such as anticancer, antibac-
terial, antioxidant, and anti-HIV activities [1–4]. Interest in these
In recent years, hydrazone ligands have increasingly attracted
attention due to various features and extensive applications. Aroyl-
hydrazones and their metal complexes are an excellent class of
ligands is due to the fact that the aromatic ring within them is
a component of many biological systems. Aroylhydrazones have
many interesting features structurally as well, with their degree
of rigidity, the conjugated π system, and the protonated or de-
protonated region in the NH group [5,6]. Aroylhydrazones which
contain protonated or deprotonated potential donor atoms such
as amido nitrogen and oxygen atoms and imino-nitrogen atoms
∗
Corresponding authors.
E-mail addresses: elif@kafkas.edu.tr (F.E. Öztürkkan Özbek),
gugurlu@kafkas.edu.tr (G. Ug˘urlu).
https://doi.org/10.1016/j.molstruc.2020.128982
0022-2860/© 2020 Elsevier B.V. All rights reserved.

2
F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
are ideal ligands commonly used in coordination chemistry. These
relative to tetramethylsilane (TMS) and dimethylsulfoxide (DMSO–
d6), which were used as internal standards. Chemical shifts (δ)
are given in ppm, and coupling constants (J) are given in Hertz.
The following abbreviations are used for multiplicities: s = singlet,
d = doublet, t = triplet, q = quartet, dd = doublet of doublets and
m = multiplet. Pyridine-3-carbohydrazide was prepared according
to the literature [22].
–
=
compounds containing the –C(O)-NH N C- moiety are also iden-
tified as one of the versatile compounds that can make inter-
molecules hydrogen bonds. When evaluated in terms of functional
groups, aroylhydrazones are unique ligands because they have a
=
–
trinuclear azomethine group (-C N NH -) that provides structure
=
diversity, a C N double bond that can form configuration iso-
merism, and -C(=O)-HN- group that can form an intermolecular
=
–
hydrogen bond (C OꢀH N) that provides stability to the structure.
Due to the physicochemical properties exhibited by the contribu-
tion of these structural characteristics, aroylhydrazone compounds
are considered as interesting materials in industrial, pharmacolog-
ical, and medicinal chemistry fields [7–11].
2.2. General procedure for the synthesis of compounds (1 and 2)
General procedure for the synthesis of compounds 1 and 2
was given in Scheme 1. The pyridine-3-carbohydrazide (1.25 g,
9.12 mmol) was placed in a round necked-flask and dissolved in
absolute ethanol (50 mL). To this mixture, the corresponding aro-
matic aldehyde (0.976 g, 9.12 mmol, 4-formyl pyridine for 1, 3-
formyl pyridine for 2) and five drops of glacial acetic acid as the
catalyst was added. The reaction mixture was stirred under reflux
for 5 h. The desired compound was monitored by TLC analysis. Af-
ter the reaction was complete, the reaction mixture was concen-
trated in vacuo. The residue was recrystallized from ethanol to give
product.
Computational chemistry is important in studying the prop-
erties of materials. Computational chemistry is fairly cheap, fast
compared to an experiment, and environmentally safe. Even if it
does not replace experiments, theoretical computation is so reli-
able in some ways that it is used today even before experimen-
tal processes are started [12]. Nowadays with the improvement of
computer technology and the development of efficient computa-
tional methods, it is possible to perform detailed physicochemi-
cal measurements and quantum chemical calculations for organic
molecules, at least in the gas phase, even on personal comput-
ers. By computer calculations, it is possible to calculate molecu-
lar properties such as energies and thermodynamic data, geome-
tries, charge distributions, vibrations, magnetic resonance parame-
ters, and reaction pathways [13]. Density functional theory (DFT)
and ab initio Hartree-Fock (HF) are widely used methods in com-
putational chemistry. In particular, the results obtained from DFT
methods for molecular geometry, FT-IR, FT-Raman, UV–Vis, NMR
spectra, etc. are highly compatible [14–16]. Although there are nu-
merous studies on the synthesis, crystal structure and applications
of aroylhydrazones and their metal complexes, studies on com-
paring experimental data with computerized methods are limited
[17–24]. Synthesis, physical and antituberculosis properties of N’-
(pyridin-4-ylmethylene)nicotic acid hydrazide (1) and N’-(pyridin-
3-ylmethylene)nicotic acid hydrazide (2) were reported in a pre-
vious study by Kakimoto and Yamamato [25]. In this study, two
aroylhydrazones, N’-(pyridine-4-ylmethylene)nicotic acid hydrazide
(1) and N’-(pyridine-3-ylmethylene)nicotic acid hydrazide (2), were
synthesized through condensation of the corresponding aldehyde
with nicotinic hydrazide, and their structures were determined
by single-crystal X-ray diffraction method, and their spectroscopic
properties were studied by FT-IR, FT-Raman, 1H NMR and 13C
NMR and UV–Vis spectroscopy. Intermolecular interactions of com-
pounds were determined by the Hirshfeld surface analysis method.
Also, the structure parameters, vibrational frequencies of FT-IR and
Raman spectra of the compounds, 1H and 13C NMR chemical shifts,
HOMO, LUMO, ꢀEgap, MEP, μ, α and β values of the compounds
have been computed by using DFT/B3LYP and HF with different ba-
sis sets.
N’-(pyridine-4-ylmethylene)nicotic acid hydrazide
(1)
It was obtained as white solid, yield: 74%, m.p: 197–198 °C. IR
(cm−1) 3237, 3051, 3023, 2968, 2830, 1693, 1650, 1589, 1559, 1484,
.
1414, 1354 cm−1 1H NMR (400 MHz, DMSO–d6, ppm) δ 12.28 (s,
1H, NH), 9.11 (s, 1H, pyr CH), 8.77 (d, J = 3.4 Hz, 1H, pyr CH), 8.65–
=
8.64 (m, 2H, pyr CH), 8.45 (s, 1H, N CH), 8.28 (d, J = 7.4 Hz, 1H,
pyr CH), 7.67 (d, J = 3.9 Hz, 2H, pyr CH), 7.56 (dd, J = 7.4, 5.0 Hz,
1H, pyr CH); 13C NMR (100 MHz, DMSO–d6, ppm) δ 162.0 (Cq,
=
C
O), 152.4 (CH), 150.2 (CH), 148.6 (CH), 145.9 (CH), 141.2 (Cq),
135.5 (CH), 128.8 (Cq), 123.5 (CH), 121.0 (CH) (Figs. S1 and S2).
N’-(pyridine-3-ylmethylene)nicotic acid hydrazide
(2)
It was obtained as white solid, yield: 72%, m.p: 215–217 °C. IR
(cm−1) 3203, 3046, 2828, 1672, 1608, 1590, 1553, 1475, 1416, 1367,
.
1330 cm−1 1H NMR (400 MHz, DMSO–d6, ppm) δ 12.20 (s, 1H,
NH), 9.06 (s, 1H, pyr CH), 8.87 (s, 1H, pyr CH), 8.76 (d, J = 4.0 Hz,
=
1H, pyr CH), 8.62 (d, J = 4.0 Hz, 1H, pyr CH), 8.49 (s, 1H, N CH),
8.25 (d, J = 7.8 Hz, 1H, pyr CH), 8.15 (d, J = 7.8 Hz, 1H, pyr CH),
7.57 (dd, J = 7.5, 4.9 Hz, 1H, pyr CH), 7.49 (dd, J = 7.5, 4.9 Hz, 1H);
13
=
C NMR (100 MHz, DMSO–d6, ppm) δ 161.4 (Cq, C O), 151.9 (CH),
150.4 (CH), 148.4 (CH), 148.2 (CH), 145.3 (CH), 135.0 (CH), 133.1
(CH), 129.6 (Cq), 128.6 (Cq), 123.6 (CH), 123.2 (CH) (Figs. S3 and
S4).
2.3. X-ray crystallography
2. Experimental
Single-crystal X-ray diffraction analyses of compounds 1 and 2
2.1. Chemicals and instruments
were performed on a Bruker SMART BREEZE CCD diffractometer
˚
using Mo K (λ= 0.71073 A) radiation at a temperature of 296 K
α
All chemicals and solvents were purchased commercially and
used without further purification. Fourier-transform infrared (FT-
IR) spectra and Raman spectra of the compounds were recorded in
the range of 4000–400 cm−1 on an ALPHA-P Bruker FT-IR spec-
trometer with attenuated total reflection (ATR) detector and a
WITec alpha 300 R Micro-Raman spectrometer from solid sample,
respectively. UV–Vis spectra were obtained with a Perkin Elmer’s
LAMBDA 25 Spectrophotometer. 400 MHz 1H NMR spectra and
100 MHz 13C NMR spectra were acquired on Bruker Nuclear Mag-
netic Resonance (NMR) Spectroscopy. Chemical shifts are reported
[26]. Structures were solved by direct methods [27] and refined by
full-matrix least squares against F2 using all data [27]. All non-H
atoms were refined anisotropically. Atoms H2A and H6A (for NH,
in compound 1) were located in difference Fourier maps and re-
fined isotropically, while the N- and C-bound H atoms were posi-
˚
tioned geometrically at distances of 0.86 A (for NH, in compound
˚
2) and 0.93 A (aromatic and methine CH) (in compounds 1 and 2)
from the parent C atoms; a riding model was used during the re-
finement processes and the Uiso(H) values were constrained to be
1.2Ueq (carrier atom). Experimental data are given in Table 1.

F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
3
Scheme 1. General procedure for the synthesis of compounds.
Table 1
Experimental details for compounds 1 and 2.
Table 2
˚
Hydrogen-bond geometry (A, °).
Compounds
1
C
2
Compound
D-H•••A
D-H
H•••A
D•••A
D-H•••A
•••
Empirical Formula
formula weight
color/shape
12H10N4O
C12H10N4O
226.24
colourless/block
monoclinic
P 21/c
N2-H2A
N6-H6A
C14-H14
C16-H16
O2
N1
0.86(3)
0.94(3)
0.93
2.08(3)
2.09(3)
2.60
2.866 (3)
3.003 (3)
3.492 (4)
3.497 (34)
3.124 (7)
3.474 (9)
3.254(9)
151(3)
165(3)
160
i
•••
226.24
i
•••
•••
colourless/block
triclinic
P −1
1
2
N1
N8
ii
Crystal System
Space Group
0.93
2.61
159
iii
•••
N2-H2A
N4
iii
0.86
2.32
155
˚
•••
N4
C2-H2
C3-H3
0.93
2.56
166
a (A)
8.7899 (2)
10.8983 (3)
11.7726 (3)
89.952 (3)
88.684 (3
75.293 (2)
1090.50 (5)
4
11.9239 (3)
8.6495 (2)
11.1021 (3)
90
iv
•••
˚
N1
0.93
2.45
145
b (A)
˚
c (A)
Symmetry codes: (i) –x + 2, –y, −z + 1; (ii) x + 1, y, z + 1; (iii) –x + 1, y–1/2,
−z + 1/2; (iv) x, −y + 1/2, z–1/2.
α (°)
β (°)
γ (°)
111.664 (3)
90
3
˚
V (A )
1064.14 (5)
4
initio-Hartree-Fock (HF) [39] with 6–311+G for compound 1 and
6–311++G(d,p) basis sets [40,41] for compound 2 in the gas phase.
After optimization, vibrational frequencies, HOMO, LUMO, μ, α and
β values of the compounds were computed by using B3LYP/6–
311++G (d,p) and HF/6–311++G (d,p) level of theory. By using the
optimized parameters obtained theoretical calculations, The 1H and
13C NMR chemical shifts were calculated with the GIAO method at
the B3LYP/6–311+G (2d,p) and HF/6–311++G (d,p) level of theory.
The MEP, LUMO and HOMO surfaces of compounds were plotted
to visualize the charge distributions. The detailed vibrational as-
signments of theoretical FT-IR and Raman vibrational frequencies
calculated with the DFT/B3LYP method were evaluated by means
of vibrational energy distribution analysis (VEDA4) program [42].
Z
μ (Mo K ) (mm−1
)
−
0.09
0.10
α
3
ρ (calcd) (mg m
)
1.378
1.412
Number of Reflections Total
47,702
6363
Number of Reflections Unique
5211
1948
Rint
0.048
0.077
2θmax (°)
56.80
53.20
Tmin / Tmax
Number of Parameters
GOF
0.688 / 0.744
315
0.618 / 0.745
155
1.24
1.27
R [F2 >2σ(F2)]
0.086
0.117
wR
0.173
0.249
−3
˚
(ꢀρ)max (e A
)
0.25
0.28
−3
˚
(ꢀρ)min (e A
)
−0.28
−0.26
2.4. Computational details
3. Results and discussion
Visulization and exploration of intermolecular close contacts of
a structure is invaluable, and this can be achieved using the Hir-
shfeld surface (HS) [28–30]. HS analysis may be carried out to
investigate the locations of atoms with potential to form hydro-
gen bonds and the quantitative ratios of these interactions. In the
present study using Crystal Explorer 17.5 [31], To visualize the in-
termolecular interactions in the compounds 1 and 2, the HS were
mapped over dnorm, shape-index, curvedness and electrostatic po-
tential. The electrostatic potential for compound 2 was calculated
using TONTO [32,33] integrated into Crystal Explorer.
3.1. Single-crystal diffraction studies
The X-ray structural determinations of compounds 1 and 2 con-
firm the assignments of their structures from spectroscopic data.
Selected experimental and theoretical bond lengths and angles are
given in Supplemental Table 1. When the values obtained from
single crystal X-ray diffraction method and DFT and HF calcula-
tions were compared, it was found that the values related to bond
length and angles are compatible with each other. Hydrogen bond
geometries are given in Table 2. The molecular structures along
with the atom-numbering schemes are depicted in Fig. 1a and 1b,
while the packing diagrams are given in Figs. S5a and S5b, re-
spectively. In compound 1, the asymmetric unit contains two crys-
tallographically independent molecules, where they are linked by
All the calculations were carried out with Gaussian 09, Revi-
sion B.01 [34] program package and supported by Gauss view 5.0
molecular visualization programs [35]. The initial molecular mod-
eling of the compounds were optimized by using the density func-
tional theory [36] treated according to hybrid Becke’s three param-
eter and the Lee–Yang–Parr functional (B3LYP) [16,37,38] and ab-
–
the intramolecular N H···O hydrogen bond (Table 3 and Fig. 1a).
The dihedral angles between the planar rings [A (N1/C1–C5) and

4
F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
•••
O hydrogen bond is shown as dashed lines. b. An
–
Fig. 1. a. An ORTEP-3 [50] view of compound 1. The thermal ellipsoids are drawn at the 50% probability level. N
ORTEP-3 [50] view of compound 2. The thermal ellipsoids are drawn at the 50% probability level.
H

F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
5
Table 3
Electronic Energy, dipole moment (μ), polarizability (α) hyperpolarizability (β), the highest occupied and
lowest unoccupied molecular orbital Energies (EHOMO and ELUMO) of compound 1 and compound 2 (1a and
1b are monomer units calculated for compound 1).
DFT/B3LYP
Electronic Energy (a.u)
μ (D)
α (a.u)
β(a.u)
EHOMO (a.u)
ELUMO (a.u)
ꢀEgap (eV)
1
−1514.91984788
−757.694635451
−757.692978398
−757.693833408
11.65
4.28
6.45
4.13
394.4
194.0
193.5
194.5
782.9
261.3
392.3
236.9
−0.237931
−0.257365
−0.258263
−0.249646
−0.108979
−0.092353
−0.092502
−0.087209
3.51
4.49
4.51
4.42
1a
1b
2
HF
1
−1505.41573923
−753.047377877
−753.045787879
−753.047009248
12.67
4.59
6.81
4.44
338.9
166.6
166.5
167.1
311.0
267.2
311.0
52.4
−0.326544
−0.348039
−0.349282
−0.332221
0.011987
0.027391
0.021436
0.024224
9.21
1a
1b
2
10.22
10.09
9.70
B (N4/C8–C12)] and [C (N5/C13–C17) and D (N8/C20–C24)] are A /
B = 19.21(11)° and C / D = 7.09(9)°. In compound 2, the asym-
metric unit contains only one molecule, and the planar rings [A
(N1/C1–C5) and B (N4/C8–C12)] are oriented at a dihedral angle of
A / B = 4.26(18)°.
est atom inside and outside, respectively, enable the analysis of
the intermolecular interactions through the mapping of dnorm. The
combination of di and de in the form of two-dimensional finger-
print plots (Figs. 2 and 3) [44] provides a summary of intermolec-
ular contacts in the crystal. In the HS with the dnorm (Fig. S6a and
S6b) the white surface indicates contacts with distances equal to
the sum of van der Waals radii, and the red and blue colours indi-
cate distances shorter (in close contact) or longer (distant contact)
than the Van der Waals radii, respectively [45]. The shape-index of
the HS is a tool to visualize the π ··· π stacking by the presence of
adjacent red and blue triangles (Figs. S7a and S7b) [46]. In the HS
with curvedness (Figs. S8a and S8b) the curvature of the surface,
with flat surfaces in green and curved regions in blue, is useful for
depicting favourable stacking of the molecule in the crystal [47].
The electrostatic complementarity of the compound 2 is shown in
Fig. S9. The blue regions indicate the positive electrostatic potential
(hydrogen bond donors), while the red regions indicate the nega-
tive electrostatic potential (hydrogen bond acceptors) [33].
In the crystal structures of compounds 1 and 2, there are in-
–
–
termolecular N H ··· N and C H ··· N hydrogen bonds (Table 2). In
–
–
compound 1, N H ··· O and N H ··· N hydrogen bonds (Table 2)
link the molecules into centrosymmetric dimers (Fig. S5a), enclos-
4
–
ing an R4 (20) ring motif [43]. In compound 2, N H ··· N hydrogen
bonds (Table 2) link the molecules into infinite chains along the
c-axis (Fig. S5b). The π···π interactions between the A, B, C and D
rings, Cg1— Cg2i, Cg2— Cg2ii, Cg3— Cg3iii and Cg3— Cg4iv [symme-
try codes: (i) 1 – x, 1 – y, 1 – z,: (ii) 1 – x, 1 – y, – z,: (iii) 2 – x,
– y, 2 – z,: (iv) 2 – x, – y, 1 – z, where Cg1, Cg2, Cg3 and Cg4 are
the centroids of the rings A, B, C and D, respectively] (in compound
1), and the π ··· π interactions between the A and B rings, Cg1—
Cg2v [symmetry code: (v) 1 – x, – y, – z, where Cg1 and Cg2 are
the centroids of the rings A and B, respectively] (in compound 2)
may stabilize the structures with the centroid-centroid distances of
The overall two-dimensional fingerprint plots, Figs. 2a and 3a,
(for compounds 1 and 2, respectively) and those delineated into H
··· H, H ··· N / N ··· H, H ··· C / C ··· H, C ··· C, H ··· O / O ··· H, N ···
C / C ··· N, O ··· C / C ··· O, N ··· N and O ··· N / N ··· O contacts (for
compound 1) and H ··· H, H ··· N / N ··· H, H ··· C / C ··· H, H ··· O /
O ··· H, C ··· C, N ··· C / C ··· N, N ··· N, O ··· C / C ··· O and O ··· N / N
··· O contacts (for compound 2) [48] are illustrated in Fig. 2b-j and
Fig. 3b-j, respectively, together with their relative contributions to
the HS, where the significant H ··· N / N ··· H interactions are in-
dicated by the pairs of wings in the two-dimensional fingerprint
˚
˚
˚
˚
3.957(2) A, 3.671(2) A, 3.808(2) A and 3.816(2) A (in compound 1),
˚
and 3.779 (4) A (in compound 2).
The N1-C4, N1-C5, N2-N3, N2-C6 and N3-C7 bond lengths
of compounds
˚
1 and 2 were found to be 1.336 (3)/1.335
˚
˚
(8) A, 1.341 (3)/1.341 (8) A, 1.380 (3)/1.383 (7) A, 1.355
˚
˚
(3) /1.354 (7)
A
and 1.268 (3)/1.284 (7)
A
and these bond
˚
˚
lengths were calculated to be 1.3511/1.3377 A, 1.3528/1.3325 A,
˚
˚
˚
1.375/1.3552 A, 1.383/1.3897
A
and 1.2941/1.2798
˚
A
in the
˚
˚
B3LYP/6–311++g(d,p) and 1.3317/1.3211 A, 1.3343/1.3163 A,
plots with the prominent long spikes at de + di ≈ 1.2 A (for com-
˚
˚
˚
˚
1.3621/1.3545 A, 1.3613/1.3708
A
and 1.2649/1.2517
A
in the
pound 1, Fig. 2c) and de + di ≈ 1.3 A (for compound 2, Fig. 3c).
HF/6–311++g(d,p) level of theory. In addition to, C4-N1-C5,
N3-N2-C6 and N2-N3-C7 bond angles of compounds 1 and 2
were determined to be 117.3 (2)/116.2 (6)°, 120.6 (2)/119.0 (5) °
and 114.9 (2)/114.3 (5) ° and these angles were computed to
be 118.48/117.59 °, 119.02/120.94 ° and 118.34/117.53 ° in the
According to the analysis results of the crystal structures, the most
important interactions H ··· H contributing 37.9% (for compound 1)
and 37.5% (for compound 2) to the overall crystal packings, which
are reflected in Figs. 2b and 3b as widely scattered points of high
densities due to the large hydrogen contents of the molecules. The
next important interactions are H ··· N / N ··· H, H ··· C / C ··· H,
C ··· C and H ··· O / O ··· H contributing 22.1%, 13.8%, 10.6% and
8.2% (for compound 1), respectively, and H ··· N / N ··· H, H ··· C /
C ··· H, H ··· O / O ··· H and C ··· C contributing 19.6%, 13.6%, 12.1%
and 8.6% (for compound 2), respectively. The weakest intermolec-
ular contacts contributing to the cohesions of the structures are N
··· C / C ··· N, O ··· C / C ··· O, N ··· N and O ··· N / N ··· O, found
to contribute only 4.4, 1.2, 1.1 and 0.7% (for compound 1), respec-
tively, and N ··· C / C ··· N, N ··· N, O ··· C / C ··· O and O ··· N / N ···
O, found to contribute only 5.4, 1.7, 1.4 and 0.1% (for compound 2),
respectively (Fig. S10). The presence of these interactions may also
be shown by the HS mapped as a function of curvedness (Figs. S8a
and S8b). The large number of H ··· H, H ··· N /N ··· H, H ··· C /C ··· H
and H ··· O / O ··· H interactions suggest that Van der Waals inter-
B3LYP/6–311++g(d,p) and 119.19/118.01 °, 119.09/119.90
119.52/117.93
° and
°
in the HF/6–311++g(d,p) level of theory. The
calculated bond lengths and bond angles are compatible with
experimental values for both compounds.
3.2. Hirshfeld surface analysis
The dnorm (Figs. S6a and S6b), shape-index (Figs. S7a and S7b),
curvedness maps (Fig. S8a and S8b) and electrostatic potential
(only for compound 2, Fig. S9) of compounds 1 and 2 were ob-
tained with the help of Hirshfeld Surface Analysis. The electrostatic
potential for compound 2 was mapped on the HS using STO-3 G
basis set at Hartree-Fock level of theory over a range −0.1148 to
0.1274 au The contact distances di and de from the HS to the near-

6
F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
Fig. 2. The full two-dimensional fingerprint plots of compound 1 showing (a) all interactions and delineated into (b) H…H, (c) H…N/N…H, (d) H…C/C…H, (e) C…C, (f)
˚
H…O/O…H, (g) N…C/C…N, (h) O…C/C…O, (i) N…N and (j) O…N/N…O. The di and de are the closest internal and external distances (in A) from given points on the
Hirshfeld surface contacts.
actions and hydrogen bonding play the major roles in the crystal
packings [49].
Also, the β values of GAUSSIAN-09 output are given in atomic
units (a.u.), the calculated hyperpolarizability value has been con-
verted into electrostatic units (esu) (β: 1 a.u.= 0.0086393 × 10−30
esu) [51]. The calculated β values of compound 1 and 2 are
6.764 × 10−30 and 2.047 esu, respectively. In the nonlinear optical
study, urea is taken as the prototypical molecule and calculated β
value at B3LYP/6–311++G(d,p) level of urea is 0.3728 × 10−30 cm5
esu−1 [52]. Thus, it was found that the calculated first hyperpolar-
izability values of compound 1 and 2 were 18.14 and 5.49 times
greater than urea, the standard nonlinear optical material. Accord-
ing to this value obtained, compound 1 is a potential material for
designing high quality nonlinear optical materials.
3.3. HOMO-LUMO and MEP analysis
The highest occupied molecular orbital and the lowest unoc-
cupied molecular orbitals are important in terms of determine
the electrical transport characteristic and calculate energies gap
(ꢀEgap=ELUMO-EHOMO) of the compounds. The energy levels of
HOMO and LUMO were computed by the methods of B3LYP/6–
311++G(d,p) of the compound 1 and compound 2 (Fig. 4). The
theoretically calculated electronic energy, HOMO, LUMO, ꢀEgap
,
A molecular electrostatic potential is the interaction of a unit
positive charge at a given point p(x, y, z) in the surroundings of
the molecule with the potential generated by the distribution of
the electrical charge cloud density of the molecule. MEP provides
important information about the electrostatic effect produced by
the total charge distributions in the molecules, so it helps to un-
derstand molecular interactions. The MEP of the compound 1 and
compound 2 obtained at the DFT/B3LYP/6–311G++ (d, p) level of
theory were given in Fig. 5. As seen in Fig. 5, for compond 1,
the negative electrostatic potential (blue colored region) formed
around O1, N2, N3, N4, and N8 atoms and positive potential (blue
colored region) formed around the hydrogen atoms attached to N8
μ, α and β values monomer and dimer of the compound 1 and
compound 2 obtained both methods were given in Table 3. As
seen in Table 3, the dipole moment, polarizability and hyperpo-
larizability values of the dimer of the compound 1, are larger
than that of the monomer units, and the value of the energy gap
(ꢀEgap) is smaller than that of the monomer units. The calculated
ꢀEgap values of compound 1 and 2 are 3.51 and 4.42 eV at with
DFT/B3LYP/6–311++G(d,p) level of theory and 9.21 and 9.70 eV at
with HF/6–311++G(d,p) level of theory, respectively. As shown in
Fig. 4, for both compounds, the HOMOs were localized over the en-
tire molecules except for pyridine ring, whereas the LUMOs were
mainly localized on the whole molecules.

F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
7
Fig. 3. The full two-dimensional fingerprint plot of compound 2, showing (a) all interactions, and delineated into (b) H…H, (c) H…N/N…H, (d) H…C/C…H, (e) H…O/O…H,
˚
(f) C…C, (g) N…C/C…N, (h) N…N, (i) O…C/C…O and (j) O…N/N…O interactions. The di and de values are the closest internal and external distances (in A) from given points
on the Hirshfeld surface contacts.
Fig. 5. 3D MEP plots on compound 1 and compound 2 according to the B3LYP/6–
311++G(d,p) results.
Fig. 4. 3D HOMO and LUMO plots on compound 1 and compound 2 (B3LYP/6–
3.4. Nuclear magnetic resonance spectra (NMR)
311++G(d,p)) results.
1H and 13C NMR spectra of the compounds 1 and 2 were
recorded in DMSO–d6. The obtained these experimental data were
compared with those obtained theoretically (Figs. S11 and S12). In
1
–
and C6 atom, for compond 2, the negative electrostatic potential
(blue colored region) formed around O1, N1 and N4 atoms and
positive potential (blue colored region) formed around the hydro-
gen atoms attached to N2 and C7 atoms.
the H NMR spectra of the compounds 1 and 2, the N H pro-
ton observed as a singlet signal at 12.28 ppm and 12.20 ppm,
= –
respectively. A singlet signal belonged to N C H was showed at
8.45 ppm (for compound 1) and 8.49 ppm (for compound 2). The

8
F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
Chemical shifts in N H protons in 1H NMR of amine and amide
–
aromatic protons of the pyridine rings of compounds 1 and 2 were
observed among the 8.77–7.56 ppm and 8.77–7.47 ppm, respec-
compounds are a good example of their solvent action. However,
this situation causes some deviations in the theoretical calcula-
tions. One of the best solvents used to eliminate this is DMSO. Al-
though we used DMSO as solvent in our study, single crystal XRD
and Hirshfeld surface analysis findings showed that the synthe-
tively. When the chemical shift values
of aromatic protons for
Compound 1 were investigated in more detail, protons of H4 and
H16 are experimentally found at 8.77 ppm as a dublet with value
3.4 Hz, while the H7 and H19 aromatic protons are observed as
singlet resonance signal at 8.45 ppm. These protons were theo-
retically calculated at the interval of 8.22–9.48 ppm at B3LYP/6–
311+g (2d,p) level and 8.63–8.9.77 ppm at HF/6–311++g(d,p) level,
respectively. From the symmetry in the structure of compound 1,
H22, H23, H10 and H11 are identical protons. These protons give a
resonance signal at 8.65 ppm. They were theoretically detected at
the interval of 8.78–9.42 ppm at B3LYP/6–311+g (2d,p) level and
9.12–9.79 ppm at HF/6–311++g(d,p) level. The H9, H12, H21 and
H24 which have the same chemical environment are observed as
a dublet signal at 7.67 ppm with a value of 3.9 Hz within the
most upfield aromatic proton region. The H3 proton was exper-
imentally detected as doublets of doublet at 7.56 ppm with the
value of coupling constants 5.0 Hz and 7.4 Hz splitting by the
H2 and H4 protons and its calculated resonance signal is theo-
retically obtained at 9.12 ppm and 9.29 ppm at B3LYP/6–311+g
(2d,p) and 9.91 ppm and 9.77 ppm HF/6–311++g(d,p) level, re-
spectively . Similarly, when they aromatic proton resonances of
compound 2 were also evaluated, the H5 and H9 protons reso-
nance signals observed at 8.87 ppm and 9.06 ppm as a singlet,
while they were theoretically calculated at 9.63 ppm and 8.81 ppm
at B3LYP/6–311+g (2d,p) level and 9.84 ppm and 8.83 ppm at
HF/6–311++g(d,p) level, respectively. The H4 and H10 protons are
experimentally recorded as a dublet 8.76 ppm and 8.62 ppm with
the coupling constant 4.0 Hz. The calculated values of these pro-
tons are found at 9.10 ppm and 8.94 ppm B3LYP/6–311+g (2d,p)
level and 9.14 ppm and 8.99 ppm at HF/6–311++g(d,p) level re-
spectively. H12 proton resonate as dublet at 8.25 ppm with a value
of coupling constant 7.8 Hz splitting by H11 proton. In addition of
this, H2 proton observed at 8.15 ppm as a dublet signal with a
value of 7.8 Hz of coupling constant. The H11 proton, which in-
teracted with the H10 and H12 protons, resonates as a doublets
of doublet at 7.49 ppm. Finally, H3 aromatic proton was experi-
mentally recorded as a doublets of doublet at 7.57 ppm with the
value 4.9 Hz and 7.5 Hz of coupling constant. These protons were
theoretically detected at 7.47 ppm at B3LYP/6–311+g (2d,p) level
and 7.53 ppm at HF/6–311++g(d,p) level for the H11 proton and
–
–
–
sized compounds have N H ··· O, C H ··· N and N H ··· N hydrogen
bonds and Van der Waals interactions. Therefore, in the theoret-
–
ical calculations, some chemical shifts were detected in the N H
protons [56–58]. It was determined that the data closest to the ex-
perimental data were those obtained with B3LYP/6–31+G(d) (for
1H NMR) and B3LYP/6–31G(d) (for 13C NMR) methods.
3.5. Vibrational analysis and UV studies
In the FT-IR spectra of the compound 1 and 2, it was showed
a medium vibration at 3237 cm−1 and 3203 cm−1 related to the
–
ν(N H) streching vibration, respectively. These absorption bands
were computed at 3290 cm−1 (for DFT) and 3438 cm−1 (for HF) for
1 and 3345 cm−1 (DFT) and 3451 cm−1 (HF) for 2. Both experimen-
–
tally and theoretically, aromatic C H vibrations were observed in
the range of 3000–3050 cm−1. The C O and C N vibrations were
observed at 1693 cm−1 and 1650 cm−1 for 1 and 1672 cm−1 and
1608 cm−1 for 2, respectively. These vibrations were calculated to
be 1588 cm−1 and 1579 cm−1 for 1 and 1651 cm−1 and 1641 cm−1
for 2 with help of DFT and HF methods at 6–31 G, respectively.
=
=
–
The υ(N N) streching vibrations for 1 and 2 were observed at 1589
cm−1 and 1590 cm−1, respectively. In FT-IR spectra obtained from
DFT and HF calculations of compound 1 and 2, the bands at 1530
cm−1 and 1584 cm−1 for 1 and 1574 cm−1 and 1604 cm−1 for 2
–
were assigned to υ(N N), respectively (Figs S13 and S14).
In the FT-Raman spectra of the compound 1 and 2, the weak
bands observed at 3250 cm−1 and 3240 cm−1 were assigned to
–
N H stretching vibrations, respectively. These vibrations were com-
puted as 3645 cm−1 and 3656 cm−1 with help of DFT and HF
methods for FT-Raman spectra, respectively. Similar to FT-IR spec-
–
tra, aromatic C H vibrations were also seen in the region of 3050–
3000 cm−1 in FT-Raman spectra. The υ(C O), υ(C N) and υ(N N)
vibrations were observed at 1604 cm−1, 1589 cm−1 and 1544 cm−1
for 1, respectively. The theoretically calculated values of these
stretching vibrations were found to be 1604 cm−1, 1574 cm−1 and
1499 cm−1 at DFT method and 1710 cm−1, 1664 cm−1 and 1589
cm−1 at HF method. These vibrations for 2 were showed at 1629
cm−1, 1589 cm−1 and 1550 cm−1, respectively. The theoretically
obtained values of these stretching vibrations were found to be
1682 cm−1, 1603 cm−1 and 1537 cm−1 at DFT method and 1735
cm−1, 1709 cm−1 and 1603 cm−1 at HF method. Characteristic
=
=
–
7.37 ppm at B3LYP/6–311+g (2d,p) level and 7.36 ppm at HF/6–
13
=
311++g(d,p) level for the H3. In C NMR spectra, the C O carbon
signal for compound 1 and 2 was seen at 162 ppm and 161 ppm,
respectively within downfield region of the 13C NMR spectrum as
expected. The aromatic carbon signals of compound 1 and 2 ap-
peared at 152–123 ppm and 151–123 ppm, respectively [53–55].
The optimized molecular geometries of the compound 1 and 2
were determined by using DFT and HF methods with 6–31 G (d)
basis level in DMSO solvent. Correlation graphs and linear correla-
tion data obtained from 1H and 13C NMR experimental and theo-
retical spectra of Compounds 1 and 2 are given in Fig. S1-S4. The
chemical shifts from 1H NMR spectra obtained from experimen-
tal and B3LYP/6–31+G(d) and HF/6–31G+(d) methods were plot-
ted. The chemical shifts from 13C NMR spectra obtained from ex-
perimental and B3LYP/6–31G(d) and HF/6–31G(d) methods were
plotted (Figs. S12). The R2 values DFT/HF methods for 1H NMR /
13C NMR chemical shifts have been found as 0.7957/0.9733 and
0.5393/0.9288 for the compound 1, respectively. Similarly, the R2
values DFT/HF methods for 1H NMR/13C NMR chemical shifts have
been found as 0.853/0.9672 and 0.6921/0.9309 for the compound
2, respectively. There is a correlation between the experimentally
=
=
=
C
O, C C, and C N vibrations were observed in 1688 cm−1, 1602
cm−1, and 1581 cm−1, respectively, compared to similar reference
acyl hydrazone compounds. In addition, all other observed vibra-
tions were determined to be compatible with the literature [54,59–
61]. The observed with respect to the starting compounds confirm
that two new compounds are synthesized. In the infrared spec-
=
trum, it was observed that the C N stretch of the related aldehyde
–
and the N H stretch bands of the acyl hydrazide was replaced by
=
the new C N stretch band in the product formed as a result of the
condensation reaction of these two reagents. In addition, it was de-
termined that the calculations obtained theoretically regarding the
vibrations were compatible with the experimental data (Figs S15
and S16). The differences between the experimental and theoreti-
cal values of the above-mentioned vibrations can be attributed to
non-covalent interactions such as intermolecular and intermolecu-
lar hydrogen bonds and Van der Waals interactions.
–
and theoretically obtained chemical shifts except for N H proton.
UV–Vis measurements of the compounds were recorded in
DMSO. The n→π∗ or π→π∗transitions resulting from the pres-
–
–
O H and N H protons are known to be significantly affected by
the solvent due to hydrogen bond and van der Waals interactions.
=
=
ence of pyridine ring, C O, C N were observed at 489 (1) and 386

F.E. Öztürkkan Özbek, G. Ug˘urlu and E. Kalay et al. / Journal of Molecular Structure 1223 (2020) 128982
9
(2) nm. The electronic energy excited states of compound 1 and
2 were calculated at TD-DFT/LSDA level with 6–31++G (d,p) and
6–311++G (d,p) in DMSO, respectively. The experimental and the-
oretical visible absorption maxima of the compound 1 and 2 are
given in Fig. S17. These values at TD-DFT/LSDA/6–31++G (d,p) and
TD-DFT/LSDA 6–311++G (d,p) level of theory were computed to be
452 and 393 nm, respectively. It was determined that the experi-
mental and theoretical data of observed spectroscopic vibrations
and electronic transitions are generally compatible.
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–
–
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–
–
–
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–
N H ··· N hydrogen bonds provide stability to the crystal structure
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tecture. H ··· H, H ··· N / N ··· H, H ··· C / C ··· H, C ··· C, H ···
•
••
O / O ··· H, N
C / C ··· N, O ··· C / C ··· O, N ··· N and O ···
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Declaration of Competing Interest
The authors declare that they have no known competing finan-
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CRediT authorship contribution statement
Füreya Elif Öztürkkan Özbek: Investigation, Writing - review
& editing. Güventürk Ug˘urlu: Investigation, Writing - review &
editing. Erbay Kalay: Investigation, Writing - review & editing.
Hacali Necefog˘lu: Investigation, Writing - review & editing. Tuncer
Hökelek: Investigation, Writing - review & editing.
[22] F. Elif Öztürkkan Özbek, G. Ug˘urlu, E. Kalay, H. Necefog˘lu, Synthesis, characteri-
zation and computational studies of 4-[(Pyridine-3-carbonyl)-hydrazonomethyl]-
benzoic acid, J. Mol. Struct. 1215 (2020) 128247, doi:10.1016/j.molstruc.2020.
128247.
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DFT, NBO, and QTAIM analysis, Int. J. Quantum Chem. 116 (2016) 27–34,
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