Synthesis, crystal structure, spectroscopic characterization and nonlinear optical properties of (Z)-N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-yloxy) acetohydrazide

Article abstract of DOI:10.1016/j.molstruc.2019.05.074

New organic compound of (Z) -N'- (2, 4-dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide (DBQA) was synthesized for the first time and its structural characterization was performed by single crystal X-ray diffraction method. The compound crystallizes in the triclinic system with space group P-1. The spectroscopic characterization was also performed by the applying of FT-IR, UV–Vis, ¹H and ¹³C NMR spectroscopies. In order to support experimental results, density functional theory (DFT) calculations have been performed using B3LYP functionnal with 6–311++G(d, p) basis set. All of the obtained theoretical results are in a perfect agreement with the experimental ones. Furthermore, nonlinear optical (NLO) behavior of DBQA has been investigated by determining of electric dipole moment (μ), polarizability (α) and hyperpolarizability (β) using the same basis set. Finally, the molecular electrostatic potential (MEP) surface of DBQA molecule was simulated and discussed.

Full text of DOI:10.1016/j.molstruc.2019.05.074

Accepted Manuscript
Synthesis, crystal structure, spectroscopic characterization and nonlinear optical
properties of (Z)-N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-yloxy) acetohydrazide
N. Boukabcha, A. Djafri, Y. Megrouss, Ö. Tamer, D. Avcı, M. Tuna, N. Dege, A.
Chouaih, Y. Atalay, A. Djafri, F. Hamzaoui
PII:
S0022-2860(19)30644-1
10.1016/j.molstruc.2019.05.074
MOLSTR 26581
DOI:
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Accepted Date:
16 April 2018
18 May 2019
Please cite this article as: N. Boukabcha, A. Djafri, Y. Megrouss, Ö. Tamer, D. Avcı, M. Tuna, N.
Dege, A. Chouaih, Y. Atalay, A. Djafri, F. Hamzaoui, Synthesis, crystal structure, spectroscopic
characterization and nonlinear optical properties of (Z)-N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-
yloxy) acetohydrazide, Journal of Molecular Structure (2019), doi: 10.1016/j.molstruc.2019.05.074
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Graphical abstract

ACCEPTED MANUSCRIPT
Synthesis, crystal structure, spectroscopic characterization and nonlinear optical
properties of (Z)-N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-yloxy) acetohydrazide
1
*
1,2
1
3
3
3
4
N. Boukabcha , A. Djafri, Y. Megrouss , Ö.Tamer , D. Avcı, M.Tuna, N. Dege, A.
1
3
5
6
Chouaih, Y. Atalay, A. Djafri, F. Hamzaoui
1Laboratory of Technology and Solid Properties (LTPS), Abdelhamid Ibn Badis University of
Mostaganem, BP 227 Mostaganem 27000, Algeria,
2Centre de Recherche Scientifique et Technique en Analyses Physico-chimiques (CRAPC),
BP 384-Bou-Ismail-RP 42004, Tipaza, Algeria,
3Department of Physics, Department of Chemistry. Sakarya University, 54187 Sakarya,
Turkey,
4Department of Physics, Ondokuz Mayis University Samsun, 54187 Samsun, Turkey,
5Laboratoire de Synthèse Organique Appliquée (LSOA), Université d’Oran 1 - Ahmed Ben
Bella, 31000 Oran, Algérie,
6LPFM Académie de Montpellier – France.
Abstract
New organic compound of (Z) -N'- (2, 4-dinitrobenzylidene) -2- (quinolin-8-yloxy)
acetohydrazide (DBQA) was synthesized for the first time and its structural characterization
was performed by single crystal X-ray diffraction method. The compound crystallizes in the
triclinic system with space group P-1. The spectroscopic characterization was also performed
1
13
by the applying of FT-IR, UV-Vis, H and C NMR spectroscopies. In order to support
experimental results, density functional theory (DFT) calculations have been performed using
B3LYP functionnal with 6-311++G(d, p) basis set. All of the obtained theoretical results are
in a perfect agreement with the experimental ones. Furthermore, nonlinear optical (NLO)
behavior of DBQA has been investigated by determining of electric dipole moment (µ),
polarizability (α) and hyperpolarizability (β) using the same basis set. Finally, the molecular
electrostatic potential (MEP) surface of DBQA molecule was simulated and discussed.
Keywords: Crystal Structure; Quinoline; FT-IR; NMR; DFT
*
Corresponding author
n.boukabcha@gmail.com (N.Boukabcha)
1

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1
. Itroduction
The (Z) -N'- (2,4- dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide (DBQA) is a
heterocyclic aromatic organic compound having some advantages such as high degree of
nonlinearity. [1] It can also provide low aromatics that have better prospects for π-electron
delocalization across the donor–acceptor links. [2] Exactly, this composite looks like to form
push-pull structure known as Schiff bases, which are usually synthesized from the
condensation of primary amines and active carbonyl groups. Schiff bases are polyfunctionally
substituted aromatic (Quinoline) and heteroaromatic derivatives are the important class of
compounds. There has been growing interest in using organic materials for nonlinear optical
(NLO) devices [3], since they are well suited molecules in some special applications to
beused as starting materials in the synthesis of important drugs, such as antibiotics and
antiallergic, antiphlogistic, and antitumor substances [4, 5], antimalarials [6], as
pharmaceuticals [7], biologically interesting antimicrobials [8, 9], protease inhibitors [10] and
antischistosomal agents [11]. Some years ago, that interest was focused on a program aimed
at developing of new synthetic approaches to polyfunctionally substituted heterocycles [12-
1
4] using simple, inexpensive and readily available starting materials.
In a continuation of our research on the development of quinoline derivatives [15], this article
presents the detailed results of the synthesis and the structural characterization of (Z) -N'-
(2,4-dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide (DBQA) using single crystal
1
13
X-ray diffraction, FT-IR, HNMR, CNMR and UV-Vis spectroscopies. Spectroscopic data
of the title compound have been also evaluated using density functional theory (DFT) method
with B3LYP/6-311++G(d,p) basis set. The calculated geometric parameters (bond lengths and
1
3
1
bond angles), vibrational frequencies , C NMR and H NMR chemical shifts values for the
mentioned compound are compared with the experimental data. Experimental measurements
and theoretical calculations on NMR chemical shift become one of the key factors in the
molecular structure correlations design. Theoretical determination of NMR chemical shift is
quite useful both for understanding the relationship between the molecular structure and the
electronic properties of molecules. It also provides a guideline to experimentalists for the
design and synthesis of organic materials. [16] Additionally, the dipole moment,
polarisability, hyperpolarisability and the molecular electrostatic potential (MEP) map for the
title compound have been determined using B3LYP method with 6-311++G(d,p) basis set.
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2
2
. Experimental Details
.1. Synthesis
The synthesis of the title compound was performed according to scheme 1. Ethyl (quinoline-
-yloxy) acetate (2) was synthesized by condensation of 8-hydroxyquinoline (0.01mole) (1)
8
with ethyl bromoacetate (0.01mole) in dry acetone for 12h in the presence of anhydrous
K CO . A mixture of compound (2) (0.01mole) and hydrazine hydrate (0.02mole) in ethanol
2
3
was refluxed for 1h. After cooling, the resulting solid was washed, dread and recrystallized
from ethanol to afford 2-(quinolin-8-yloxy)acetohydrazide (3). To a solution of compound (3)
(0.01mole) in absolute ethanol, (2,4)-dinitrobenzaldehyde (0.01 mole) was added. After
refluxing for 12h, the formed precipitate was filtered off and recrystallized from ethanol to
give the title compound (Z) -N'- (2,4-dinitrobenzylidene) -2- (quinolin-8-yloxy)
acetohydrazide (DBQA) (4) with moderate yield 75% and melting point 211°C. Single
crystals of the title compound suitable for X-ray diffraction were obtained from ethanol
solution.
(
c)
(
a)
(b)
NO2
N
O
N
N
2
N
O
N
N
OH
4
O
O
3
O
O
1
H
NO2
C H
H N
2
2
5
O
N
H
Reagents and conditions: (a) BrCH COOC H , Acetone, reflux;
2
2
5
(
b) NH NH .H O, Ethanol, reflux;
2 2 2
(
c) (2,4)-diNO C H CHO, Ethanol, reflux.
2
6
4
Scheme 1
2
.2. Materials and Instrumentations
Electronic spectra were recorded on a Shimadzu UV-2600 Pc-spectrophotometer with quartz
cell of 1cm. Infrared spectra were recorded on a Perkin Elmer Spectrum Two FT-IR
spectrophotometer equipped with Perkin Elmer UATR-TWO diamond ATR and corrected by
1
13
applying the atr-correction function of Perkin Elmer Spectrum software. H and C NMR
spectra were recorded as CDCl and DMSO-d solutions on a Varian Mercury Plus 300 MHz
3
6
spectrometer.
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2
.3. X-ray crystallography and data collection
Single-crystal (DBQA) X-ray data were collected on a STOE IPDS II. All diffraction
measurements were performed at 295K using monochromated MoKα radiation (λ = 0.71073
Å). Data collections: X-AREA and Cell refinement: X-Red32 programs [17] were used to cell
refinement and data reduction, respectively. Shelxs [18] and Shelxl [19] programs were used
to solve and refine the structure, respectively. The structure was solved by direct methods. All
non-hydrogen atoms were refined anisotropically using all reflections with I >2σ (I).
Aromatic C-bound H atoms were positioned geometrically and refined using a riding mode.
All H atoms attached to aromatic C atoms were fixed geometrically and treated as riding with
C–H=0.930 Å and Uiso(H) =1.2Ueq(C), while the O–H bond length was taken 0.977 Å.
Crystal structure validations and geometrical calculations were performed using Platon [20]
and Mercury software [21]. The details of crystallographic data and refinement of the data
collection are given in Table 1.
3
. Computational details
The molecular structure of the title compound in the ground state is optimized by density
functional theory employing the closed-shell B3LYP method with 6–311G++(d, p) basis set
[22-24] which was adopted to calculate the molecular structure, vibrational frequencies and
energy of the optimized geometries of the title molecule (DBQA). The scaling factor of 0.96
for 6–311G++(d, p) was used to correct the well-known systematic errors caused by basis set
incompleteness, neglect of electron correlation and vibrational anharmonicity [25]. In NMR
calculations, the geometry of tetramethylsilane (TMS) is fully optimized [25]. The
calculations of geometrical parameters in the ground state were performed by using the
Gaussian 09 program [26]. The vibrational wavenumber assignments were carried out by
combining the results of the Gauss view 5.08 [27] and VEDA4 (Vibrational Energy
Distribution Analysis) programs [28]. Time-dependent density functional theory [29, 30] is
used to calculate the electronic transitions and the oscillator strengths of the molecule using
B3LYP method with 6–311G++(d. p) basis set. The dipole moment, polarizability and the
hyperpolarizability of (DBQA) have been calculated using the same level of theory. The
calculated values of the polarizability and the hyperpolarizability components from Gaussian
0
1
9 output have been converted from atomic unit (au) into electrostatic unit (esu): (α:1au=
.482 x 10–23 esu; β: 1au = 8.6393 x 10–33 esu).
4

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4
4
. Results and discussion
.1. Structure description
The single crystal X-ray diffraction structure with the atom-numbering scheme for DBQA
drawn with 50% probability thermal ellipsoids is shown in Figure 1(a). The structure is
formed by quinoline (N1/C1-C9) and dinitrophenyl groups connected by acetohydrazide
group which plays the role off a bridge, and a water molecule. As shown in Figure 1, The
molecule adopts a quite planar conformation as characterized by its low r.m.s 0.0041 Å. The
whole molecule is essentially planar, with a dihedral angle close to 5° between quinoline and
dinitrophenyl fragments. The para and ortho positions of the two nitro groups were chosen to
have a planar molecule. Selected measured bonds lengths and bonds angles together with the
calculated ones are grouped in Table 3 in accordance with the atom-numbering scheme given
in Figure 1. Geometric optimization of DBQA molecule is performed using B3LYP
functional with 6-311++G (d, p) basis set. The optimized molecular structure is shown in
Figure 1(b). The optimized parameters obtained are approximately similar to the experimental
ones except some discrepancies. As can be noticed from Table 3, some of the computed bond
lengths are slightly longer than the experimental ones. These discrepancies can be explained
by the fact that the calculations assume an isolated molecule where the intermolecular
Coulombic interaction with the neighboring molecules are absent, whereas the experimental
results correspond to interacting molecules in the crystal form. From experimental results,
N1‒C9 and N1=C1 distances are consistent with the corresponding values in similar quinoline
derivatives [15, 31]. The experimental C‒C bond lengths in the quinoline moiety are
consistent with previous studies [32, 33]. The two CN(Nitro) bond lengths are in the normal
range and correspond well to those reported in the literature [34]. The experimental and
theoretical C8–O1 bond lengths are approximately shorter than typical CO single bond
indicating the formation of p– conjugated systems [35]. On the other hand, The experimental
and theoretical values of C11O2 bond length confirm the double bond character [36]. The
N2‒N3 distance can be considered as a partially CN double bond owing to the fact that this
2
2
bond length value is shorter than Nsp Nsp single bond which suggests the existence of
delocalized double bonds [37]. The bond angles from DFT calculations are very close to the
experimental values (Table 3). The maximum difference is about 2°. From the above results,
the differences between experimental and calculated DFT bond lengths do not exceed 0.02 Å.
Some bond angles of the aromatic ring are slightly out of normal range due to the presence of
the two-nitro substituents. In summary, the optimized bond lengths and bond angles obtained
5

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by using the DFT calculation method show the best agreement with the experimental values.
Based on results shown in Table 3, selected experimental torsion angles are very close to
those obtained with theoretical calculation.
Figure 1. (a) Experimental structure and (b) optimized structure using B3LYP/6-311G++ (d, p) for
DBQA.
The crystal structure consists of main molecule and H O molecule connected by hydrogen
2
bonds. The water molecule as donor is hydrogen bonded to N1 atom in quinoline ring and
also as acceptor is hydrogen bonded to H5 atom in acetohydrazide moiety. The structure also
reveals that the quinoline moieties are bonded to the solvent water molecules through O–
H···N hydrogen bonds to stabilize the packing. Description of the structure showing the
various hydrogen bonds are given in Figure 2.
In the crystal packing, in addition to the O–H···N hydrogen bonds, neighbouring molecules
are linked by strong C–H···O interactions into dimers as shown in Figure 2 (a and b) which
contributes to the supramolecular aggregation. Figure 2(a) shows some hydrogen bonds in the
DBQA crystal while Figure 2(b) represents the molecular packing in the unit cell. Hydrogen
bonds, as determined by X-ray diffraction technique, are reported in Table 2. These
intermolecular interactions participate in the cohesion and stabilization of the molecular
packing arrangements. In the crystal structure, H-bonds are formed due to the attraction
between electronegative atoms and hydrogen atoms. The supramolecular analysis of the title
compound indicates that C and Ow atoms act as donors while N and O atoms act as acceptors.
However, no significant stacking interactions occur between the aromatic rings. From the
above results, oxygen atoms of the two nitro groups form a weak interactions with hydrogen
atoms and in particularly those of quinoline unit. These interactions contribute hugely in the
nonlinear optical effect of the studied molecule.
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(b)
Figure 2. (a) Hydrogen bonding interactions and (b) Crystallographic packing diagram of DBQA.
4
.2 Thermal analysis
The DTG/DTA thermal analysis, shown in Figure 3, reveals the existence of adsorbed
atmospheric water. Indeed, it can be noticed from DTG analysis a continuous decrease of
mass loss with increasing of temperature up to 100°C, and then slow downing at 150°C. An
ignition loss of 20 % was obtained at 105°C. This fact asserts the elimination of hydrated
water. The DTA curve, shows an intense endothermic peak at 84°C, which is related to the
dehydration reaction. The oxygen atom lone pairs of the water molecules are in continuous
movement indicating that the water molecules possesses a non-zero dipole moment. This
instantaneous dipole moment leads to a dipole moment around the quinoline fragment which
explain the existence of attractive strengths between the positive pole represented by the
hydrogen atom of H2O and N1 atom of the quinoline moiety. These interactions are
represented by the OwHw2···N1 contact. Therefore, the presence of the water molecule is
very important in the stability of the crystalline architecture. The shorter hydrogen acceptor
distances in the case of the intermolecular hydrogen bonds indicate that these members of the
separated pairs are stronger than the intramolecular ones [38]. Dimerization of the monomeric
unit occurs through two pair of intermolecular bonds C1-H1···O4 (d=2.612 Å). On the other
hand, the nitrogen atom of the quinoline unit participates in the hydrogen bond and acts as a
…
doublet donor by forming a hydrogen bond N1 Hw1 (d = 1.942 Å) with the hydroxyl of
7

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H2O. Two molecules of water bind orthogonally to the two quinoline planes of the dimer, one
molecule on one side and the second on the other side [39-40]. These results are in good
agreement with IR data. IR spectra of the quinoline derivative show a broad absorption band
-1
at 3623.70-3591.70 cm attributed to OH stretching modes of coordinated water.
Figure 3. Thermogravimetric and thermodifferential analysis of compound DBQA
4
.3. Vibrational spectra (IR)
The theoretical IR spectra and FT-IR spectrum of the title compound are shown in Figure 4.
The vibrational spectra of (Z) -N'- (2,4-dinitrobenzylidene) -2- (quinolin-8-yloxy)
acetohydrazide were calculated by B3LYP method with the 6–311++G (d, p) basis set. This
compound consists of 45 atoms, which undergo 129 normal modes of vibrations. All
calculated wavenumbers were scaled by using the scaling factors of 0.96 [41]. Frequency
calculations at the same levels of theory discovers no fıctive frequencies, indicating that an
optimal geometry at the used level of approximation has been found for the title compound.
Vibrational frequencies calculated by using B3LYP with 6-311++G(d, p) basis set have been
given in Table 4, as compared with experimental corresponding data. The assignments of the
calculated fundamental vibrational modes of the title compound were performed on the basis
of potential energy distributions (PED) analysis using Gaussian 09 program and Gauss View
5
molecular visualization program [42]. Aromatic compounds commonly exhibit multiple
8

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−
1
week bands in the region of 3300–3000 cm due to aromatic C–H stretching vibrations [43].
The bands appeared at 3239 to 3066 cm−1 have been assigned to C–H ring stretching
vibrations for (DBQA). The C–H in plane and out–of–plane bending vibrations generally lie
−
1
−1
in the range of 1500–1000 cm and of 950–800 cm [44, 45], respectively. The C–H in–
−
1
plane bending vibrations are identified at 1525, 1461, 1456, 1428, 1412 and 1376cm , the
observed absorption bands in FT–IR spectrum are situated at 1504, 1469, 1452, 1435, 1412
−
1
and 1379cm .The HCCC twisting out–of–plane vibrations are identified at 1016, 997, 982,
−
1
9
62 and 892 cm , whereas the experimental absorption bands in FT–IR spectrum are
−
1
observed at 1018, 996, 981, 956 and 894 cm . The O–H stretching vibrations were observed
−
1
at 3781 and 3610 cm , confirming the presence of H O molecule in the title compound.
2
−
1
These bands have been calculated at 3881 and 3452 cm for B3LYP/6–311G++(d, p) level.
−
1
−1
The N–H stretching vibrations observed at 3250 cm has been calculated at 3248 cm . The
assignments of nitro group frequencies, basically some fundamental modes can be associated
to each NO group namely, ν : symmetric stretching ν : antisymmetric stretching δ :
2
sy
asy
sy
symmetric bending; and δ : asymmetric bending; which belongs to in plane vibrations. In
asy
addition to that τ: twisting modes of NO group would be expected to be depolarized for out–
2
of–plane vibrations. Aromatic nitro compounds have strong absorptions due to the
asymmetric and symmetric stretching, so the vibrations appear in the range 1588– 1554 and
–
1
–1
1
373–1356 cm respectively. In the present compound, the strong bands at 1527 – 1525 cm
by B3LYP/6-311G++(d, p) level are assigned to asymmetric stretching mode of NO and the
2
–
1
band at 1360 cm assigned to symmetric and asymmetrıc stretching mode of NO . Aromatic
2
nitro compounds have a band of weak–to–medium intensity in the region of 595–522 cm–1
[
43] due to the rocking deformation in plane mode of the NO group. This band was observed
2
–
1
at 505 cm . The deformation vibrations of NO contribute to several normal modes in the low
2
frequency region [42]. These bands were also found in the wavenumber region around the
–
1
characteristic position of 748 cm in FT–IR spectrum for DBQA. The C–O stretching
vibrations were observed at 1283 and 1029 cm−1 which confirms the presence in the
compound. These bands have been calculated at 1292 and 1030 cm−1 for B3LYP/6–
3
11G++(d, p) level. The carbonyl group exhibits a strong absorption band due to C=O
–
1
stretching vibration observed in the region of 1850–1550 cm . Because of its high intensity
and relatively interference free region in which it occurs, this band is easy to recognize.
Infrared spectra of DBQA molecule, consists of two major bands in carbonyl stretching
–
1
region; infrared bands at 1777 cm . Our calculated carbonyl stretching frequencies are found
–
1
very close to observed FT–IR frequencies at 1760 cm . The identification of C–N vibrations
9

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is a very difficult task, since mixing of several bands is possible in this region. However, the
C–N stretching assignments are identified by the animation application of Gauss–View 5.0.8
graphical interface [43]. The C–N stretching absorption stays in the region 1382–1266 cm−1
for aromatic amines. The C–N stretching vibrations are found to be present at 1382 and 1307
−
1
−1
cm . In the present study, a very strong band at 1368 cm in FT-IR has been assigned to C–
N stretching vibration. The theoretically computed value of C–N stretching vibration is
−
1
−1
−1
defined as 1347 cm . The bands observed at 1652 cm and 1598 cm respectively in FT-IR
have been assigned to asymmetric and symmetric C=N stretching vibrations. The theoretically
−
1
−1
computed values of C=N stretching vibration are defined as 1652 cm and 1610 cm . The
−
1
C–C stretching vibration in general appears in the spectral range of 1650 to 1200 cm [46].
−
1
The computed vibration is assigned to C–C stretching vibration at 1647 cm using B3LYP/6–
−
1
3
11G++(d, p) which is comparable to experimental data at 1641 cm . The computed
vibrations are assigned to C–C–C in plane vibrations at 1504, 1396, 1135, 887, 842 and 621
−
1
cm using B3LYP/6–311G++(d, p) which are comparable to experimental data at 1525,
−
1
1
385, 1136, 883, 838 and 620 cm . The computed vibrations (modes 46 and 34) are assigned
−
1
to C–C–C out of plane vibrations at 666 and 471.17 cm using B3LYP/6–311G++(d, p)
−
1
which are comparable to experimental data at 663 and 471.81 cm . The asymmetric C–H
−
1
stretching mode of CH group is expected in the region around 2940 cm and the symmetric
2
−
1
around the region 2860 cm . The CH asymmetric stretching mode in DBQA is found at
2
3
059 cm−1 in FT–IR spectra. The symmetric stretching mode is also observed in FT–IR
−
1
−1
spectra at 3163 cm . The calculated wavenumbers of the above modes are 3165cm (100%)
and3066 cm−1 (58%) using B3LYP/6–311G++(d, p) respectively for CH symmetric and
2
asymmetric stretching modes. The scissoring vibrations of CH were determined at 1609,
2
−
1
1
575, 1560, 1542 cm in FT-IR spectra [47]. The theoretically computed values of CH give
2
−
1
wavenumber at 1504.56 cm by B3LYP/6–311G++(d, p) method.
1
0

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Figure 4. The comparison of FT-IR and calculated IR spectra for DBQA
4
.4. UV–Vis spectra analysis
The UV–Vis electronic spectra of DBQA were recorded within 600-200 nm range. The
oscillator strengths (f) , wavelength (λ), theoretical electronic excitation energies and spectral
assignment were calculated by the TD-B3LYP level and given in Table 5. The major
contributions of the transitions were designated with the aid of Swizard program [48].
Experimental and theoretical UV–Vis spectra of DBQA are given in Figure 5. The calculated
transition are represented by a Gaussian function 푦 = 푐푒 ―푏푥2 with the height c equal to the
−
2
oscillator strength and b equal to 0.04 nm [49-50].
According to the theoretical UV–Vis spectrum of the title compound, the electronic
absorption band calculated at 460 nm is attributed to HOMO→LUMO electronic transition
with 99% contribution. This electronic transitions is due to π →π* transition and may be
attributed to the excitation of C=O group. The electronic absorption bands observed at 237
and 312 nm have been calculated at 389 and 397 nm, respectively. Table 5 demonstrated that
the band calculated 397 nm is attributed to the combination of HOMO-1 → LUMO (81%),
HOMO-1 → LUMO +1(13%) and HOMO→LUMO+1 (4%). Similarly, the band calculated
at 389 nm is originated from the combination of HOMO→LUMO+1 (95%) and HOMO-1 →
LUMO (4%). The theoretically obtained absorption bands can be assigned as π → π* and n
→
π* transition with considerable intramolecular charge transfer originating from donor to
acceptor unit of the molecule DBQA. Additionally, one can easily say that the most likely
1
1

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transition is the band calculated at 397 nm with the oscillator strength of 0.2166. the highest
and lowest molecular orbitals (HOMO and LUMO) have been calculated and presented in
Figure 6. B3LYP results demonstrated that HOMO and LUMO energies for the title
compound are found as -8.499 and -5.612 eV, respectively. So, the energy gap between
HOMO and LUMO is obtained as 2.887 eV, indicating that DBQA is a chemically soft
molecule. This small energy gap also an indicator of high first order hyperpolarizability which
is a nonlinear optical parameter.
Figure 5. A comparison of experimental and theoretical UV-Vis spectra for DBQA
Figure 6. The frontier molecular orbitals for DBQA obtained by using B3LYP method
1
2

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4
.5. NMR spectral analysis
The isotropic chemical shifts are frequently used to predict and interpret the structure of large
molecular systems. Additionally, the combined use of NMR and theoretical methods presents
an opportunity to obtain more accurate results. The structure in the title compound (DBQA)
1
13
was confirmed with the help of H NMR and C NMR spectral study. The sample was
dissolved in CDCl and NMR spectrum was recorded using a Bruker Advance III FT-NMR
3
1
13
spectrometer and TMS as the internal standard. The H and C NMR chemical shifts for (Z)-
N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-yloxy) acetohydrazide have been calculated using
B3LYP/6-311++G(d, p) levels with GIAO approach [51–56]. The experimental and
theoretical chemical shifts are presented in Table 6. The aromatic protons of the title
compound give resonance at the region of 7.33-9.11 ppm as would be expected. These proton
signals have been also calculated at the range of 7.31-9.01 ppm, 7.43-9.14 ppm and 7.41-9.13
1
ppm in gas, water and chloroform media, respectively. The H NMR signals for CH protons
2
observed at 5.02 and 4.21 ppm have been calculated at 5.15 and 4.76 ppm, respectively. The
NH group proton gives NMR signal at downfield region due to the electronegative
characteristic of N atom. Therefore, NH group proton signal was observed 13.42 ppm and
calculated at 13.26, 13.46 and 13.41 ppm, respectively.
It is well known that the aromatic C atom give NMR signal at the range of 100-150 ppm. In
this study, aromatic C atom signals were observed at the region of 112.18-155.33 ppm. The
carbon which connect to both oxygen (O) and nitrogen (N) is higher than the other carbons
because of the electronegativity properties of oxygen and nitrogen atoms. Thefore, C1 and C8
atoms give resonance downfield region due to electronegative N and O atoms. The aromatic
carbon signals have been also calculated at the regions of 161.56-113.80 ppm in gas phase,
1
61.14-114.16 ppm in water solution and 161.38-114.25 ppm in chloroform solution. The
NMR signal for carbonyl C atom observed at 166.72 ppm was calculated at 170.98, 175.77
1
13
and 174.67 ppm, respectively. All of the H and C NMR signals have been found to be in
expected regions. Additionally, there is a good agreement between experimental and
1
13
theoretical results. All of the obtained H and C NMR chemical shifts have been found as
consistent with literature [57-61].
4
.6. Nonlinear optical properties
We have studied the type of the organic molecules because of their larger nonlinear optical
NLO) susceptibilities arising from π-electron cloud movement from donor to acceptor, fast
NLO response times, high laser harmsill and low insulation constants. Although the organic
(
1
3

ACCEPTED MANUSCRIPT
molecules have these advantages, they have several NLO hurt, too: they have generally low
thermal stability and they may undergo a facile relaxation to random orientation [62].
NLO effects arise from the interactions of electromagnetic fields in various media to produce
new fields altered in phase, frequency, amplitude or other propagation characteristics from the
incident fields [63]. NLO is at the forefront of current research because of its importance in
providing the key functions of frequency shifting, optical modulation, optical switching,
optical logic, and optical memory for the emerging technologies in areas such as
telecommunications, signal processing, and optical connectors [64, 65].
The non-linear optical response of an isolated molecule in an electric field can be represented
as a Taylor series expansion of the total dipole moment, μ , induced by the field:
tot
휇푡표푡 = 휇 + 훼 퐸 + 훽 퐸 + …
0
푖푗
푗
푖푗푘 푗푘
where α is the linear polarizability,μ is the permanent dipole moment and β are the first
0
ijk
hyperpolarizability tensor components. The isotropic (or average) linear polarizability is
defined as [66]:
1
훼푡표푡
=
(
훼 + 훼 + 훼푧푧)
푥푥
푦푦
3
The mean first-order hyperpolarizability is
1
2
2
2 2
훽푡표푡
=
(
훽 + 훽 + 훽
)
푥
푦
푧
where
훽푥 = 훽
푥푥푥
푦푦푦
+ 훽푥푦푦 + 훽푥푧푧
+ 훽푦푧푧 + 훽푦푥푥
훽푦 = 훽
훽푧 = 훽 + 훽푧푥푥 + 훽푧푦푦
푧푧푧
μ, α, and β parameters have been examined in gas phase, water, and ethanol solvents.
Since the values of the polarizabilities (훼) and hyperpolarizability (훽) of the Gaussian 09
output are reported in atomic units (a.u.), the calculated values have been converted into
2
4
−33
electrostatic units (esu) (for α; 1 au =0.1482×10− esu, for β; 1 au = 8.6393×10 esu).
The total molecular dipole moment, polarizability and first hyperpolarizability are 8.8128
Debye, 36.5  10-24 esu and 47.3  10-30 esu, respectively and are depicted in Table 7. The
first hyperpolarizability parameter of pNA and urea were reported to be 15.5×10-24 and
0
.13×10-24 esu, respectively [67-69]. B3LYP results demonstrated that DBQA molecule exists
approximately 3 and 363 times higher first hyperpolarizability parameter than pNA and urea,
respectively. This high value of the parameter may be explained by the donor and acceptor
functional substituents such as NO , C=O and aromatic rings. Another reason for the high
2
1
4

ACCEPTED MANUSCRIPT
value of the first hyperpolarizability may be considered as the length of the bridge between
the end groups of molecule. The longer length of the bridge between electron donor and
acceptor groups may improve the nonlinear optical properties of DBQA molecule. The small
HOMO-LUMO energy gap also indicates that the DBQA is a good candidate to NLO
materials
4
.7. Molecular electrostatic potential (MEP)
Molecular electrostatic potential (MEP) is related to the electronic density and is a very useful
descriptor in understanding sites for electrophilic attack and nucleophilic reactions as well as
hydrogen bonding interactions [70–72]. The electrostatic potential V(r) is also well suited for
analyzing processes based on the ‘‘recognition” of one molecule by another, as in drug
receptor, and enzyme substrate interactions, because it is through their potentials that the two
species first ‘‘see” each other [73, 74]. Being a real physical property V(r) can be determined
experimentally by X-ray diffraction or by computational methods [75]. The molecular
electrostatic potential (MEP) at a point r in the space around a molecule is (in atomic units).
푍퐴
휌(푟)푑푟'
∫ 푟' ― 푟
푉(푟) =
―
∑
|
푅퐴 ― 푟
|
퐴
where Z is the charge on nucleus A located at R and (r) is the electron density. The first
A
A
term in the expression represents the effect of the nuclei and the second represents that of
electrons. The two terms have opposite signs and therefore opposite effects. V(r) is their
resultant at each point r; it is an indication of the net electrostatic effect produced at the point r
by the total charge distribution (electrons + nuclei) of the molecule. Electrostatic potential
correlates with dipole moment, electronegativity, partial charges and site of chemical
reactivity of the molecule. It provides a visual method to understand the relative polarity of a
molecule. While the negative electrostatic potential corresponds to an attraction of the proton
by the concentrated electron density in the molecule (and is colored in shades of red on the
ESP surface), the positive electrostatic potential corresponds to repulsion of the proton by
atomic nuclei in regions where low electron density exists and the nuclear charge is
incompletely shielded (and is colored in shades of blue). By definition, electron density
isosurface is a surface on which molecule’s electron density has a particular value and that
encloses a specified fraction of the molecule’s electron probability density.
The electrostatic potential plot is shown in Figure 7. To predict reactive sites for electrophilic
and nucleophilic attack for the investigated molecule, MEP was calculated at the B3LYP/6-
1
5

ACCEPTED MANUSCRIPT
3
1G++(d, p) on the basis of optimized geometry. The negative (red and yellow) regions of
MEP were related to electrophilic reactivity and the positive (blue) ones to nucleophilic
reactivity as shown in Figure 7. The MEP is best suited for identifying sites for intra- and
intermolecular interactions [76]. When an intramolecular interaction takes place the
electrostatic potential of the negative atom becomes less negative and the positive region on
the other atom becomes less positive [77-81]. According to Figure 7, the regions around NO2
and C=O groups are represented by red color, indicating that these regions are the electron-
rich parts of DBQA molecule. As for the most positive potential region of DBQA molecule,
Figure 7 displays that the region around hydrogen atom of water molecule is the electron-poor
region. The other aromatic protons have small positive charges and represented by light blue
color. In the case of a reaction, DBQA molecule can interact with other molecules through
these functional groups.
Figure. 7. Molecular electrostatic potential (MEP) surface for DBQA
5
. Conclusion
The organic compound (Z)-N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-yloxy) acetohydrazide,
was synthesized, and characterized by spectroscopic (FT-IR, NMR and UV-Vis) and
structural (XRD) techniques. The X-ray structure is a little different from its optimized
structure, and the crystal structure is stabilized by O ‒ H···N and C ‒ H···O type hydrogen
bonds. Crystal packing of the title compound is formed by intermolecular interactions. The
optimized molecular structure of (Z)-N'-(2,4-dinitrobenzylidene)-2-(quinolin-8-yloxy)
1
6

ACCEPTED MANUSCRIPT
acetohydrazide has been obtained at B3LYP level in conjunction with the 6-311++G(d, p)
basis set.
In this study, comparisons between the computed and experimental the geometric parameters
have been reported to test B3LYP levels of theory with 6-311++G(d, p) basis set., The
theoretical and experimental vibration wavenumbers for the title compound have been
obtained and discussed. The experimental results are seen to adapt to the theoretical ones.
Similarly, theoretical and experimental NMR chemical shifts for DBQA have been also
presented. Experimental results are seen to adapt to the theoretical results. Nonlinear optical
properties of DBQA have been investigated by the determination of the electric dipole
moment, polarizability and first order static hyperpolarizability. The compound exhibits
strong effective intra- and intermolecular charge transfer and shows large second-order
nonlinearity. The molecular electrostatic potential (MEP) plots for the title compound show
the distribution of charge of compounds with respect to the difference between positive and
negative charges. The negative region (red) is mainly over the N and O atomic sites, which
are caused by the contribution of lone-pair electrons of nitrogen and oxygen atom while the
positive (blue) potential sites are around the hydrogen atoms.
Supplementary Material
Crystallographic data for the structure reported in this article have been deposited with
Cambridge Crystallographic Data Center, CCDC 1870875. Copies of this information may be
obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge, CBZ IEZ, UK.
Facsimile
(44)
01223
336
033,
E-mail:
deposit@ccdc.cam.ac.uk
or
https://www.ccdc.cam.ac.uk.
References
[
1] S. Alturk, N. Boukabcha, N. Benhalima, Ö. Tamer, A. Chouaih, D. Avcı, Y. Atalay, F.
Hamzaoui, Conformational, spectroscopic and nonlinear optical investigations on 1-(4-
chlorophenyl)-3-(4-chlorophenyl)-2-propen-1-one: a DFT study. Indian Journal of Physics
9
1 (2017) 501-511.
[
2] S. H. Masraqui, R.S. Kenny, S.G. Ghadigaonkar, A. Krishnan, M. Bhat-tacharya,
Synthesis and nonlinear optical properties of some donor-acceptor oxadiazoles. Das PK
Opt Mater 27 (2004) 257–260.
1
7

ACCEPTED MANUSCRIPT
[
3] N. Benhalima, N. Boukabcha, Ö. Tamer, A. Chouaih, D. Avci, Y. Atalay and F.
Hamzaoui, Solvent Effects on Molecular Structure, Vibrational Frequencies; and NLO
Properties of N-(2,3-Dichlorophenyl)-2-Nitrobenzene–Sulfonamide: a Density Functional
Theory Study . Brazilian. J. Phys. 46 (2016) 371-383.
[
4] H. Tanak, M. Yavuz . Molecular structure, spectroscopic (FT-IR and UV-Vis) and DFT
quantum-chemical studies on 2-[(2,4-Dimethylphenyl) iminomethyl]-6-methylphenol. J.
Mol. Struct. 961 (2010) 9–16.
[
5] M. M. Ghorab, M. S. Al-Said, Synthesis and Antitumor Activity of Some Novel
Hydrazide,1,2-dihydropyridine, Chromene and Benzochromene Derivatives. Journal of
Heterocyclic Chemistry. 49 (2012) 272-280.
[
6] B. F. Abdel-Wahab, R. E. Khidre, A. A. Farahat, A. S. El-Ahl . 2-Chloroquinoline-3-
aldehyde: Synthesis, Reactions and Applications, Arkivoc .1 (2012) 211- 276.
7] F. M. A. El-Taweel. Novel and Facile Synthesis of Thiophene,2H-pyran-2-one,
Benzimidazo[1,2-a]pyridine and Pyridine Derivatives, Phosphorus, Sulfur and
Silicon .179 (2011) 1276-1277.
[
[
8] E. Abd El-Rady and I. H. El-Azab. “Reactivity of β-Enaminoester of Benzo[f]
Chromene: One Pot Synthesis of Isolated Heterocycle-Fused Derivatives of
Benzo[f] Chromene. European Journal of Chemistry. 3 (2012) 81-86.
[
9] H. M. Mohamed, A. H. F. Abd El-Wahab, K. A. Ahmed, A. M. El-Agrody, A. H. Bedair,
F. A. Eid and M. M. Khafagy. Synthesis, Reactions and Antimicrobial Activities of
8
-Ethoxycoumarin, Molecules. 17 (2012) 971-988.
10] J. Tois, M. Vahermo and A. Koskinen. Novel and Convenient Synthesis of
(1H)quinolones, Tetrahedron Letter. 46 (2005) 735-737.
[
4
[
11] M. M. Abdelkhalik, A. M. Eltoukhy, S. M. Agamey and M. H. Elnagdi. Enaminones as
Building Blocks in Heterocyclic Synthesis of Nicotinic Acid: New Synthesis of
Nicotinic Acid and Thienopyridine Derivatives. Journal of Heterocyclic Chemistry. 41
(2004) 431-435.
[
12] E. S. Othman. Some Nucleophilic Cyclization Reactions with 3-[4 Benzo[1,3]
dioxolylmethylene)pyrazolyl] quino- line. Acta Chimica Slovonica. 50 (2003) 15-28.
13] F. M. A. El-Taweel.Studies with Quinolines: New Syhthetic Routes to 4H,5H,6H,9H-
Benzo[ij] pyrano[2,3-b] quinolizine-8-one,4H-pyrano[2,3-b] 2H– pyran-2-one and
Pyranopyridoquinoline Derivatives . Journal of Heterocyclic Chemistry. 42 (2005)
[
9
43-946.
1
8

ACCEPTED MANUSCRIPT
[
14] F. M. A. El-Taweel, A. A. Elagamey . New and Facile Synthesis of Substituted Pyrrole,
Pyridine, Pyrazolo[4,3-b] Pyridine, Pyrano[3,2-c] Quinoline, Napthopyran,
Naphthodipyran and Coumarin Derivatives . International Journal of Organic
Chemistry. 3 (2013) 58-70.
[
[
[
15] R.I. Bahoussi, A. Djafri, A. Chouaih, A. Djafri, F. Hamzaoui. Crystal structure and
Hirshfeld surface analysis of ethyl 2-{[4-ethyl-5-(quinolin-8-yloxymethyl)-4H-1,2,4-
triazol-3-yl]sulfanyl}acetate Acta Cryst E 73 (2017) 173–176.
16] A Souldozi, A. Ramazani. The reaction of (N-isocyanimino)triphenylphosphorane with
benzoic acid derivatives: a novel synthesis of 2-aryl-1,3,4-oxadiazole derivatives.
Tetrahedron Lett 48 (2007) 1549–1551.
17] Stoe & CieX-AREA (Version 1.18) and X-RED32 (Version 1.04), Stoe & Cie,
Darmstadt, Germany, (2002).
[
18] G.M. Sheldrick. A Short History of SHELX. Acta Cryst A 64 (2008) 112–122.
19] G.M. Sheldrick. Crystal structure refinement with SHELXL. Acta Cryst A 71 (2015) 3–
[
8
.
[
20] A. L. Spek. Structure validation in chemical crystallography. Acta Cryst D 65 (2009)
48–155.
1
[
21] C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor, M.
Towler, Mercury: visualisation and analysis of crystal structures . J. Appl. Cryst. 39
(2006) . 453-457.
[
[
[
22] C. Lee, W. Yang, R.G. Parr. Development of the Colle-Salvetti correlation energy
formula into a functional of the electron density. Phys. Rev. B 37 (1988) 785–789.
23] A. D. Becke. Density-functional thermochemistry. III. The role of exact exchange, J.
Chem. Phys. 98 (1993) 5648–5652.
24] P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch . Ab initio calculation of
vibrational absorption and circular dichrosim spectra using density functional force
fields, J. Phys. Chem. 98 (1994) 11623–11627.
[
25] D. Avcı , Y. Atalay . Effects of different GIAO and CSGT models and basis sets on 2-
aryl-1,3,4-oxadiazole derivatives . Struct Chem 20 (2009) 185–201.
[
26] Frisch M J, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR,
Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J,
Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H,
Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y,
Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C,
1
9

ACCEPTED MANUSCRIPT
Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C,
Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ,
Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck
AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S,
Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL,
Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill
PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA Gaussian 09, Revision
B01, Gaussian Inc., Pittsburgh PA, 2010.
[
27] E. Frisch, H. P. Hratchian, R. D. Dennington II, T.A. Keith, John Millam, B. Nielsen,
A.J. Holder, J. Hiscocks. Gaussian, Syntheses, structural elucidation, thermal properties,
theoretical quantum chemical studies (DFT) and biological studies of barbituric–
hydrazone complexes Inc. GaussView Version 5.0.8, (2009).
[
28] M. H. Jamroz, Vibrational Energy Distribution Analysis: VEDA 4 Program, Warsaw,
Poland (2004).
[
29] R.E. Stratmann, G.E. Scuseria, M.J. Frisch. An efficient implementation of time
dependent density-functional theory for the calculation of excitation energies of large
molecules, J. Chem. Phys. 109 (1998) 8218–8224.
[
30] E. Cances, B. Mennucci, J. Tomasi. A new integral equation formalism for the
polarizable continuum model: theoretical background and applications to isotropic and
anisotropic dielectrics, J. Chem. Phys. 107 (1997) 3032–3041.
[
31] S. Sarveswari, A. Srikanth, N. Arul Murugan, V. Vijayakumar, Jerry P. Jasinski, Hanna
C. Beauchesne, Ethan E. Jarvis, Synthesis, characterization of (3E)-1-(6-chloro-2-
methyl-4-phenyl quinolin-3-Yl)-3-aryl prop-2-en-1-ones through IR, NMR, single
crystal X-ray diffraction and insights into their electronic structure using DFT
calculations, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
1
36 (2015), 1010–1017.
[
32] M. Suresh, M. Syed Ali Padusha, S. Bharanidharan, H. Saleem, A. Dhandapani, S.
Manivarman, Synthesis, spectral characterization and density functional theory
exploration of 1-(quinolin-3-yl)piperidin-2-ol, Spectrochimica Acta Part A: Molecular
and Biomolecular Spectroscopy 144 (2015) 243-257.
[
33] T. Ren, J. Wang, G. Li, H. Cheng, Y. Li, Synthesis of quinoline derivatives containing
pyrazole group and investigation of their crystal structure and spectroscopic properties
in relation to acidity and alkalinity of mediums, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy 129 (2014) 7–13.
2
0

ACCEPTED MANUSCRIPT
[
[
[
[
34] N. Benhalima, K. Toubal, A. Chouaih, G. Chita, S. Maggi, A. Djafri, F. Hamzaoui,
Synthesis and Molecular Structure Investigation by DFT and X-Ray Diffraction of
ARNO. Journal of Chemical Crystallography 41 (2011) 1729-1736.
35] Ö. Tamer, D. Avcı, Y. Atalay, calculations of electronic structure and nonlinear optical
parameters of 4-methoxybenzaldehyde-n-methyl-4-stilbazolium tosylate, Journal of
Applied Spectroscopy, 80 (2014) 971-982.
36] S. Guner, Y. Atalay, A. Dolma, Experimental and theoretical study of 4-
cyanobenzaldehyde isonicotinoyl-hydrazone monohydrate, Journal of Molecular
Structure 984 (2010) 389–395.
37] A. Eşme, S. Güneşdoğdu Sağdınç, Molecular structures, spectroscopic (FT–IR, NMR,
UV) studies, NBO analysis and NLO properties for tautomeric forms of 1,3-dimethyl-5-
(phenylazo)-6-aminouracil by density functional method, Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy 188 (2018) 443-455.
…
[
38] C. Ceccarelli, G. A. Jeffrey and R. Taylor, A survey of O-H O hydrogen bond
geometries determined by neutron diffraction. Journal of Molecular Structure 70 (1981)
2
55–271.
[
39] Yong-chu Liu, Zheng-yin Yang, Crystal structures, antioxidation and DNA binding
properties of Yb(III) complexes with Schiff-base ligands derived from 8-
hydroxyquinoline-2-carbaldehyde and four aroylhydrazines, Bimetals 22 (2009) 733-
7
51.
[
40] Yong-chu Liu, Zheng-yin Yang, Crystal structures, antioxidation and DNA binding
properties of Eu(III) complexes with Schiff-base ligands derived from 8-
hydroxyquinoline-2-carboxyaldehyde and three aroylhydrazines Journal of Inorganic
Biochemistry 103 (2009) 1014-1022.
[
[
[
41] J.B. Foresman, Exploring chemistry with electronic structure methods, in A guide to
using Gaussian, ed. by E. Frisch (Gaussian Inc, Pittsburg, 1996).
42] M. Silverstein, G. C. Basseler, C. Morill. Spectrometric Identification of Organic
Compounds, Wiley, New York, 1981.
43] V. Krishna Kumar, S. Dheivamalar, R. John Xavier, V. Balachandran, Analysis of
vibrational spectra of 4-amino-2,6-dichloropyridine and 2-chloro-3,5-dinitropyridine
based on density functional theory calculations, Spectrochim. Acta A 65 (2006) 147–154.
44] J.B. Lambert, H.F. Shurvell, L. Verbit, Cooks RG, Stout GH Organic Structural
Analysis, Macmillan Publ., New York, 1976.
[
[
45] P.S. Kalsi. Spectroscopy of Organic Compounds, Academic Press, New York, 2002.
2
1

ACCEPTED MANUSCRIPT
[
46] M. Ramalingam, V. Sethuraman, N. Sundaraganesan, Molecular structure, vibrational
spectroscopic, first order hyperpolarizability and HOMO–LUMO studies of 7-amino-8-
oxo-3- vinyl-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid, Spectrochim. Acta
A 78 (2011) 660–669.
[
47] N. Dege, N. Şenyüz, H. Batı , N. Günay , D. Avcı , Ö. Tamer , Y. Atalay. The synthesis,
characterization and theoretical study on nicotinic acid [1-(2,3-dihydroxyphenyl)
methylidene] hydrazide Spectrochim. Acta A 120 (2014) 323–331.
[48] S.I. Gorelsky, Swizard Program Revision 4.5, University of Ottawa, Ottawa, Canada,
2
010.
[49] N.B. Colt up, L.H. Daly, S.E. Wiberley, Introduction to Infrared and Raman
Spectroscopy, Academic Press, New York, 1990.
[50] C. James, A. AmalRaj, R. Reghunathan, I. Hubert Joe, V.S. JayaKumar, J. Raman
Spectroscopic investigation on the efficient organic nonlinear crystals . Spectrosc. 37
(2006) 1381–1392.
[
51] R.J. Ditchfield. Molecular Orbital Theory of Magnetic Shielding and Magnetic
Susceptibility. Chem Phys 56 (1972) 5688–569.
[
52] K. Wolinski, J.F. Hinton, P. Pulay, Efficient implementation of the gauge-independent
atomic orbital method for NMR chemical shift calculations. J Am Chem Soc 112 (1990)
8
251–8260.
[
[
[
[
[
53] J. Gauss, Effects of Electron Correlation in the Calculation of Nuclear Magnetic
Resonance Chemical Shifts .J Chem Phys 99 (1993) 3629–3643.
54] R Ditchfield. Self-consistent perturbation theory of diamagnetism: I. A gauge-invariant
LCAO method for NMR chemical shifts. Mol Phys 27 (1974) 789–807.
55] T. A. Keith, R.F.W. Bader. Calculation of magnetic response properties using atoms in
molecules .Chem Phys Lett 94 (1992) 1–8.
56] T.A. Keith, R.F.W. Bader Calculation of magnetic response properties using a
continuous set of gauge transformations. Chem Phys Lett 210 (1993) 223–231.
57] T. A. Keith, R.F.W. Bader. Topological analysis of magnetically induced molecular
current distributions . J Chem Phys 99 (1993) 3669–3682.
[58] R. F. W Bader, T. A. Keith.Properties of atoms in molecules: Magnetic susceptibilities. J
Chem Phys 99 (1993) 3683–3693.
2
2

ACCEPTED MANUSCRIPT
[
59] Ö. Tamer, D. Avcı, Ç. Arıoğlu, A. Başoğlu, Y. Atalay, A theoretical study on structural,
spectroscopic, electronic and electric properties of 4-chloro 4-nitrostilbene Indian J of
Physics 89 (2015) 1–11.
[
60] O. Tamer, D. Avcı, Y. Atalay. Synthesis, molecular structure, spectral analysis and
nonlinear optical studies on 4-(4-bromophenyl)-1-tert-butyl-3-methyl-1H-pyrazol-5-amine:
A combined experimental and DFT approach Acta Phys. Polonica A 126 (2014) 679–687.
[
61] O. Tamer, D. Avcı, Y. Atalay, The effects of electronegative substituent atoms on
structural, vibrational, electronic and NLO properties of some 4-nitrostilbene derivates
Spectrochim. Acta A 136 (2015) 644–650.
[
62] R. Rajkumar, A. Kamaraj, S. Bharanidharan, H. Saleem, K. Krishnasamy, Synthesis,
spectral characterization, single crystal X-ray diffraction and DFT studies of 4-((2,4,5-
triphenyl-1H-imidazol-1- yl)methyl) pyridine derivatives . J. Mol. Struct. 1084 (2015)
7
4–81.
[63] H. Moghanian, A. Mobinikhaledi, R. Monjezi. Synthesis, spectroscopy (vibrational,
NMR and UV–vis) studies, HOMO–LUMO and NBO analysis of 8-formyl-7-hydroxy-
4
-methylcoumarin by ab initio calculations. J. Mol. Struct 1052 (2013) 135-145.
[
64] C.E. Powel, M.G. Humphrey.Nonlinear optical properties of transition metal acetylides
and their derivatives. Coord. Chem. Rev. 248 (2004) 725–756.
[
65] X. Sun, Q.L. Hao, W.X. Wei, Z.X. Yu, D.D. Lu, X. Wang, Y.S. Wang, Experimental
and density functional studies on 4-(3,4-dihydroxybenzylideneamino) antipyrine,
and 4- (2,3,4-trihydroxybenzylideneamino)antipyrine, J. Mol. Struct. 904 (2009) 74–82
[
66] C. Andraud, T. Brotin, Garcia, F. Pelle, P. Goldner, B. Bigot, A. Collet, Theoretical and
Experimental Investigations of the Nonlinear Optical Properties of Vanillin,
Polyenovanillin, and Bisvanillin Derivatives J. Am. Chem. 116 (1994) 2094–2102.
[67] L.T. Cheng, W. Tam, S.H. Stevenson, G.R. Meredith, G. Rikken, S.R. Marder,
Experimental investigations of organic molecular nonlinear optical polarizabilities.1.
Methods and results on benzene and stilbene derivatives, J. Phys. Chem. 95 (1991)
1
0631-10643.
[
68] P. Kaatz, E.A. Donley, D.P. Shelton, A comparison of molecular hyperpolarizabilities
from gas and liquid phase measurements, J. Chem. Phys. 108 (1998) 849-856.
2
3

ACCEPTED MANUSCRIPT
[
69] C. Adant, M. Dupuis, J.L. Bredas, Ab initio study of the nonlinear optical properties of
urea: electron correlation and dispersion effects, Int. J. Quant. Chem. 56 (2004) 497-
5
07.
[
70] V.M. Geskin, C. Lambert, J.L. Bredas, Origin of High Second- and Third-Order
Nonlinear Optical Response in Ammonio/Borato Diphenylpolyene Zwitterions: the
Remarkable Role of Polarized Aromatic Groups . J. Am. Chem. 125 (2003) 15651–
1
5658.
[
71] R. Zhang, B. Du, G. Sun, Y. Sun, Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy, 75 (2010) 1115-1124.
[
72] E. Scrocco, J. Tomasi. Electronic molecular structure, reactivity and intermolecular
forces: an heuristic interpretation by means of electrostatic molecular potentials. Adv
Quantum Chem 11 (1978) 115- 193
[
73] F.J. Luque, J.M. Lopez, M. Orozco, Perspective on “Electrostatic interactions of a solute
with a continuum. A direct utilization of ab initio molecular potentials for the prevision
of solvent effects”. Theor. Chem. Ac. 103 (2000) 343 -345.
[
[
[
[
[
[
74] N. Okulik, A. H. Jubert . Theoretical analysis of the Reactive Sites of Non-steroidal
Anti- inflammatory Drugs, Internet Electron. J Mol Des 4 (2005) 17-30.
75] P. Politzer, P.R. Laurence, K. Jayasuriya, J. McKinney. in strucrure-activity correlation
in mechanism studies and predictive toxicology Environ. Health Perspect. 61 (1985) 191.
76] E. Scrocco, J. Tomasi, in Topics in Current Chemistry, 42, Verlag , Springer, Berlin,
1
973.
77] P. Politzer, D.G. Truhlar, Chemical Applications of Atomic and Molecular Electrostatic
Potentials, Plenum, New York, 1981
78] P. Politzer, M.C. Concha, J.S. Murray. Density functional study of dimers of
dimethylnitramine. Int. J. Quantum Chem. 80 (2000) 184 –192.
79] K. Toubal, N. Boukabcha, O. Tamer, N. Benhalima, S. Altürk, D. Avcı, A.Chouaih,Y.
1
13
Atalay, A. Djafri, F. Hamzaoui . Spectroscopic (FT-IR, H and C NMR)
characterization and density functional theory calculations for (Z)-5-(4-
nitrobenzyliden)-3-N(2-ethoxyphenyl)-2-thioxo-thiazolidin-4-one (ARNO) . Journal
of Molecular Structure 1147 (2017) 569-581.
[80] Ö. Tamer, S. A. Tamer, Ö. İdil, D. Avcı, H. Vural, Y. Atalay, Antimicrobial activities,
DNA interactions, spectroscopic (FT-IR and UV-Vis) characterizations, and DFT
2
4

ACCEPTED MANUSCRIPT
calculations for pyridine-2-carboxylic acid and its derivates. J. Mol. Struct, 1152 (2018)
3
99-408.
[
81] R Rahmani, N. Boukabcha, A Chouaih , F. Hamzaoui, S. Goumri-Said , On the
molecular structure, vibrational spectra, HOMO-LUMO, molecular electrostatic
potential, UV-Vis, first order hyperpolarizability, and thermodynamic investigations of
3
-(4-chlorophenyl)-1-(1yridine-3-yl) prop-2-en-1-one by quantum chemistry
calculations . Journal of Molecular Structure 1155 (2018) 484-495.
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HIGHLIGHTS


There exist weak C-H…O hydrogen bond .
The optimized geometry is computed using B3LYP method

Experimentally and Theoretically calculated by FT-IR, UV-Vis , NMR spectrum of DBQA
Spectroscopic properties of DBQA were examined and B3LYP methods.
The nonlinear optical properties have been evaluated for the different conformation.
MEP of the title compound was calculated.




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Table 1. Crystal data and refinement parameters for DBQA
Chemical formula
Molecular weight
Temperature
C H N O .H O
18 13 5 6 2
413.35 g.mol
295 K
-1
Radiation wavelength
Crystal System
Kα(Mo) 0.71073 Å
Triclinic
Space group
P -1
a
b
c
α
β
γ
V
7.3171 (16) Å
17.029 (4) Å
17.336 (5) Å
118.645 (17) °
93.922 (19) °
92.650 (18) °
3
1883.6 (8) Å
Z
4
-3
Density
μ
F(000)
1.458 Mg m
0.12 mm
856
-1
Ѳ range for data correction
25.664°
h,k,l
-8≤h≤ 8 , -20≤k≤20 , -20≤l≤20
Number of measured , independent and 19104, 6980, 2072
observed [I > 2σ(I)] reflections
Rint
Sin θ/λ)
R[F > 2σ(F )], wR(F ), S
Number of reflections
Number of parametres
Δρmax, Δρmin
0.045
0.609 Å
0.074, 0.328, 1.055
6980
555
−
1
(
max
2
2
2
−
3
0.73 − 0.33 e.Å

ACCEPTED MANUSCRIPT
Table 2.Geometries of intermolecular interactions obtained from structural analysis of DBQA.
…
.
D – H A
Ow Hw2 N1
D – H (Å) D – A (Å)
H – A(Å) D – H...A (°)
…
.
(i)
(i)
0.977
0.977
0.938
0.938
0.938
0.938
2.754 (12)
2.894 (11)
3.374 (9)
3.309 (9)
3.462 (12)
3.477 (12)
1.929
2.220
2.449
2.448
2.783
2.612
162.32
136.02
158.86
153.97
129.31
162.22
…
.
Ow Hw1 N2
C10 H10A O8
H7 O2
H5 O5
C1 H1 O4
…
.
(ii)
…
.
(iii)
C7
C5
…
.
(iv)
…
.
(v)
Symmetry codes: (i) x,y,z; (ii) -x+1,-y,-z+1; (iii) -x,-y-1,-z ; (iv) x-1,+y-1,+z-1; (v) -x+1,-y,-z