Journal of Molecular Structure 1194 (2019) 112e123

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Journal of Molecular Structure

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

Synthesis, crystal structure, spectroscopic characterization and

nonlinear optical properties of (Z)-N'-(2,4-dinitrobenzylidene)-2-
(quinolin-8-yloxy) acetohydrazide
N. Boukabcha a, *, A. Djafri a, b, Y. Megrouss a, O€ . Tamer c, D. Avcı c, M. Tuna d, N. Dege e,
A. Chouaih a, Y. Atalay c, A. Djafri f, F. Hamzaoui g
a
Laboratory of Technology and Solid Properties (LTPS), Abdelhamid Ibn Badis University of Mostaganem, BP 227, Mostaganem, 27000, Algeria
b
Centre de Recherche Scientifique et Technique en Analyses Physico-chimiques (CRAPC), BP 384-Bou-Ismail-RP 42004, Tipaza, Algeria
c
Departement of Physics, Faculty of Arts and Sciences, Sakarya University, 54187, Sakarya, Turkey
d
Department of Chemistry, Faculty of Arts and Sciences, Sakarya University, 54187, Sakarya, Turkey
e
Department of Physics, Ondokuz Mayis University Samsun, 54187, Samsun, Turkey
f
Laboratoire de Synth`ese Organique Appliqu´ee (LSOA), Universit´e d’Oran 1 - Ahmed Ben Bella, 31000, Oran, Algeria
g
LPFM Acad´emie de Montpellier, France

a r t i c l ein fo
abstract
Article history:
Received 16 April 2018 New organic compound of (Z) -N'- (2, 4-dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide
Received in revised form (DBQA) was synthesized for the first time and its structural characterization was performed by single
3 May 2019 crystal X-ray diffraction method. The compound crystallizes in the triclinic system with space group P-1.
Accepted 18 May 2019 The spectroscopic characterization was also performed by the applying of FT-IR, UVeVis, 1H and 13C
Available online 28 May 2019 NMR spectroscopies. In order to support experimental results, density functional theory (DFT)
calculations have been performed using B3LYP functionnal with 6e311þþG(d, p) basis set. All of the
Keywords: obtained theoretical results are in a perfect agreement with the experimental ones. Furthermore,
Crystal structure nonlinear optical
Quinoline (NLO) behavior of DBQA has been investigated by determining of electric dipole moment (m), polariz-
FT-IR
ability (a) and hyperpolarizability (b) using the same basis set. Finally, the molecular electrostatic po-
NMR
tential (MEP) surface of DBQA molecule was simulated and discussed.
DFT
© 2019 Elsevier B.V. All rights reserved.

1. Itroduction
molecules in some special applications to beused as starting ma-
terials in the synthesis of important drugs, such as antibiotics and
The (Z) -N'- (2,4- dinitrobenzylidene) -2- (quinolin-8-yloxy)
antiallergic, antiphlogistic, and antitumor substances [4,5], anti-
acetohydrazide (DBQA) is a heterocyclic aromatic organic com-
malarials [6], as pharmaceuticals [7], biologically interesting anti-
pound having some advantages such as high degree of nonlinearity
microbials [8,9], protease inhibitors [10] and antischistosomal
[1]. It can also provide low aromatics that have better prospects for
agents [11]. Some years ago, that interest was focused on a program
p-electron delocalization across the donoreacceptor links [2].
aimed at developing of new synthetic approaches to polyfunc-
Exactly, this composite looks like to form push-pull structure
tionally substituted heterocycles [12e14] using simple, inexpensive
known as Schiff bases, which are usually synthesized from the
and readily available starting materials.
condensation of primary amines and active carbonyl groups. Schiff
In a continuation of our research on the development of quin-
bases are polyfunctionally substituted aromatic (Quinoline) and
oline derivatives [15], this article presents the detailed results of the
heteroaromatic derivatives are the important class of compounds.
synthesis and the structural characterization of (Z) -N'- (2,4-
There has been growing interest in using organic materials for
dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide (DBQA)
nonlinear optical (NLO) devices [3], since they are well suited
using single crystal X-ray diffraction, FT-IR, 1HNMR, 13CNMR and
UVeVis spectroscopies. Spectroscopic data of the title compound
have been also evaluated using density functional theory (DFT)
* Corresponding author. method with B3LYP/6-311þþ G(d,p) basis set. The calculated geo-
E-mail address: n.boukabcha@gmail.com (N. Boukabcha).
metric parameters (bond lengths and bond angles), vibrational

https://doi.org/10.1016/j.molstruc.2019.05.074
0022-2860/© 2019 Elsevier B.V. All rights reserved.
frequencies,13C NMR and 1H 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 relation-
ship 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 molec-
ular electrostatic potential (MEP) map for the title compound have
been determined using B3LYP method with 6e311þþG(d,p) basis
set.
2. Experimental details
2.1. Synthesis
The synthesis of the title compound was performed according
to Scheme 1. Ethyl (quinoline-8-yloxy) acetate (2) was
synthesized by condensation of 8-hydroxyquinoline (0.01 mol)
(1) with ethyl bromoacetate (0.01 mol) in dry acetone for 12 h in
the presence of anhydrous K2CO3. A mixture of compound (2)
(0.01 mol) and hy- drazine hydrate (0.02 mol) in ethanol was
refluxed for 1 h. 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) (0.01
mol) in absolute ethanol, (2,4)- dinitrobenzaldehyde (0.01 mol)
was added. After refluxing for 12 h, 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.
2.2. Materials and instrumentations
Electronic spectra were recorded on a Shimadzu UV-2600
Pc- spectrophotometer with quartz cell of 1 cm. Infrared spectra
were recorded on a Perkin Elmer Spectrum Two FT-IR
spectrophotom- eter equipped with Perkin Elmer UATR-TWO
diamond ATR and corrected by applying the atr-correction
function of Perkin Elmer Spectrum software. 1H and 13C NMR
spectra were recorded as CDCl3
and DMSO-d solutions on a Varian Mercury Plus 300 MHz
6 Number of measured, independent and 19104, 6980, 2072
spectrometer.
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 295 K using
monochromated MoKa radiation (l ¼ 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 > 2s (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 CeH 0.930 Å and
Uiso(H) 1.2Ueq(C), ¼ while the OeH 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 6e311G þþ(d, p) basis set [22e24]
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 þþ 0.96 for
6e311G (d, p) was used to correct the well-known systematic
errors caused by
Table 1
Crystal data and refinement parameters for DBQA.
Chemical formula C18H13N5O6$H2O
Molecular weight 413.35 g mol—1
Temperature 295 K
Radiation wavelength Ka(Mo) 0.71073 Å
Crystal System Triclinic
Space group P —1
a 7.3171 (16) Å
b 17.029 (4) Å
c 17.336 (5) Å
a 118.645 (17) ○
b 93.922 (19) ○
g 92.650 (18) ○
V 1883.6 (8) Å3
Z 4
Density 1.458 Mg m—3
m 0.12 mm—1
F(000) 856
Ѳ range for data correction 25.664○
h,k,l —8≤h ≤ 8, —20 ≤ k ≤ 20, —20 ≤ l ≤ 20
observed [I > 2s(I)] reflections
Rint 0.045
(Sin q/l)max 0.609 Å—1
R[F2 > 2s(F2)], wR(F2), S 0.074, 0.328, 1.055
Number of reflections 6980
Number of parametres 555
Drmax, Drmin 0.73 — 0.33 e.Å—3

(a) (b) (c)

NO2
N O
N N N O N
1 OH O 3 O 4 N
2 H
CH NO2
HN
2
2 5 N O
O O H
Reagents and conditions: (a) BrCH2COOC2H5, Acetone, reflux;
(b) NH2NH2.H2O, Ethanol, reflux;
(c) (2,4)-diNO2C6H4CHO, Ethanol, reflux.

Scheme 1.
basis set incompleteness, neglect of electron correlation and
Table 3
vibrational anharmonicity [25]. In NMR calculations, the geometry The experimental and calculated geometric parameters of DBQA.

of tetramethylsilane (TMS) is fully optimized [25]. The calculations Bond Lengths (Å) XRD B3LYP
of geometrical parameters in the ground state were performed by N(1) ‒ C(1) 1.332(3) 1.329
using the Gaussian 09 program [26]. The vibrational wavenumber N(1) ‒ C(9) 1.352(17) 1.361
assignments were carried out by combining the results of the Gauss O(1) ‒ C(8) 1.333(18) 1.368
view 5.08 [27] and VEDA4 (Vibrational Energy Distribution Anal- N(2) ‒ N(3) 1.352(7) 1.350
N(3) ‒ C(12) 1.282(9) 1.284
ysis) programs [28]. Time-dependent density functional theory N(4) ‒ O(3) 1.20 (9) 1.220
[29,30] is used to calculate the electronic transitions and the N(4) ‒ O(4) 1.22 (8) 1.221
oscillator strengths of the molecule using B3LYP method with N(2) ‒ C(11) 1.356(9) 1.380
6e311Gþþ(d. p) basis set. The dipole moment, polarizability and C(3) ‒ C(2) 1.329 (15) 1.320
C(8) ‒ C(9) 1.444(12) 1.436
the hyperpolarizability of (DBQA) have been calculated using the
C(9) ‒ C(4) 1.429(11) 1.422
same level of theory. The calculated values of the polarizability and N(4) ‒ C(14) 1.498(10) 1.469
the hyperpolarizability components from Gaussian 09 output have C(5) ‒ C(6) 1.348(14) 1.370
been converted from atomic unit (au) into electrostatic unit (esu): O(1) ‒ C(10) 1.431(8) 1.425
(a:1au ¼ 1.482 × 10—23 esu; b: 1au ¼ 8.6393 × 10—33 esu). O(2) ‒ C(11) 1.234(8) 1.218
C(13) ‒ C(12) 1.460(10) 1.462
C(13) ‒ C(14) 1.409(10) 1.381
Bond Angles (○)
4. Results and discussion
C(8) ‒ O(1) ‒ C(10) 114.70(6) 119.70
C(9) ‒ N(1) ‒ C(1) 119.46(9) 118.43
4.1. Structure description N(3) ‒ N(2) ‒ C(11) 119.37(6) 120.00
N(2) ‒ N(3) ‒ C(12) 118.43(6) 116.76
O(5) ‒ N(5) ‒ O(6) 124.86(9) 125.03
The single crystal X-ray diffraction structure with the atom- numbering
O(1) ‒ C(8) ‒ C(9) 112.49(8) 112.35
scheme for DBQA drawn with 50% probability thermal C(9) ‒ C(4) ‒ C(3) 115.36(11) 117.10
ellipsoids is shown in Fig. 1(a). The structure is formed by quinoline O(2) ‒ C(11) ‒ C(10) 118.06(8) 121.60
(N1/C1-C9) and dinitrophenyl groups connected by acetohydrazide O(1) ‒ C(8) ‒ C(7) 126.09(8) 125.91
group which plays the role off a bridge, and a water molecule. As N(1) ‒ C(9) ‒ C(8) 118.33(8) 119.10
O(3) ‒ N(4) ‒ C(14) 117.00(8) 118.11
shown in Fig. 1, The molecule adopts a quite planar conformation as
C(14) ‒ N(4) ‒ O(4) 119.42(9) 117.37
characterized by its low r.m.s 0.0041 Å. The whole molecule is O(2) ‒ C(11) ‒ N(2) 124.05(7) 125.90
○
essentially planar, with a dihedral angle close to 5 between N(2) ‒ C(11) ‒ C(10) 118.10(8) 118.09
quinoline and dinitrophenyl fragments. The para and ortho posi- N(4) ‒ C(14) ‒ C(13) 121.91(8) 122.21
tions of the two nitro groups were chosen to have a planar mole- N(3) ‒ C(12) ‒ C(13) 119.21(7) 118.79
N(1) ‒ C(1) ‒ C(2) 123.09(11) 123.70
cule. Selected measured bonds lengths and bonds angles together
N(4) ‒ C(14) ‒ C(15) 114.22(8) 114.13
with the calculated ones are grouped in Table 3 in accordance with C(15) ‒ C(16) ‒C(17) 123.50(8) 121.58
the atom-numbering scheme given in Fig. 1. Geometric optimiza- Torsion angle (○)
tion of DBQA molecule is performed using B3LYP functional with C(10) ‒ O(1) ‒ C(8) ‒ C(7) —1.0 4.9
6e311 þþ
G (d, p) basis set. The optimized molecular structure is N(3) ‒ N(2) ‒ C(11) ‒ O(2) —4.1 5.8
N(2) ‒ N(3) ‒ C(12) ‒ C(13) 177.1 179.1
shown in Fig. 1(b). The optimized parameters obtained are C(1) ‒ N(1) ‒ C(9) ‒ C(4) 0.7 3.9
approximately similar to the experimental ones except some dis- O(1) ‒ C(8) ‒ C(9) ‒ N(1) —2.9 —1.0
crepancies. As can be noticed from Table 3, some of the computed O(1) ‒ C(8) ‒ C(9) ‒ C(4) 177.2 179.1
bond lengths are slightly longer than the experimental ones. These C(11) ‒ N(2) ‒ N(3) ‒ C(12) 179.8 179.0
C(9) ‒ C(8) ‒ C(7) ‒ C(6) —1.1 —1.8
discrepancies can be explained by the fact that the calculations
N(1) ‒ C(9) ‒ C(4) ‒ C(5) —176.9 —175.6
assume an isolated molecule where the intermolecular Coulombic N(1) ‒ C(9) ‒ C(4) ‒ C(3) —0.5 2.38
C(8) ‒ C(9) ‒ C(4) ‒ C(3) 179.4 178.5
O(4) ‒ N(4) ‒ C(14) ‒ C(13) 167.1 —162.1
O(4) ‒ N(4) ‒ C(14) ‒ C(15) —13.4 14.1
O(1) ‒ C(10) ‒ C(11) ‒ O(2) —160.9 —168.1
O(1) ‒ C(10) ‒ C(11) ‒ N(2) 21.7 —12.4
C(12) ‒ C(13) ‒ C(14) ‒ N(4) 12.7 8.2
C(12) ‒ C(13) ‒ C(14) ‒ C(15) —174.1 —176.4
C(18) ‒ C(13) ‒ C(12) ‒ N(3) 19.5 —17.5
C(12) ‒ C(13) ‒ C(18) ‒ C(17) 173.4 168.1
Fig. 1. (a) Experimental structure and (b) optimized structure using B3LYP/6-311G þþ C(18) ‒ C(13) ‒ C(14) ‒ N(4) —172.5 —179.2
(d, p) for DBQA.

Table 2
Geometries of intermolecular interactions obtained from structural analysis of
DBQA. interaction with the neighboring molecules are absent, whereas the
○
experimental results correspond to interacting molecules in the
DeH ….
A D e H (Å) D e A (Å) H e A(Å) De H…A( )
crystal form. From experimental results, N1‒C9 and N1¼ C1 dis-
Ow Hw2 …. N1(i) 0.977 2.754 (12) 1.929 162.32 tances are consistent with the corresponding values in similar
Ow Hw1 …. N2(i) 0.977 2.894 (11) 2.220 136.02
C10 H10A …. O8(ii) 0.938 3.374 (9) 2.449 158.86
quinoline derivatives [15,31]. The experimental C‒C bond lengths
C7 H7 …. O2(iii) 0.938 3.309 (9) 2.448 153.97 in the quinoline moiety are consistent with previous studies
—
C5 H5 …. O5(iv) 0.938 3.462 (12) 2.783 129.31 [32,33]. The two C N(Nitro) bond lengths are in the normal range and
C1 H1 …. O4(v) 0.938 3.477 (12) 2.612 162.22 correspond well to those reported in the literature [34]. The
Symmetry codes: (i) x,y,z; (ii) -xþ1,-y,-zþ1; (iii) -x,-y-1,-z; (iv) x-1,þy-1,þz-1; (v) experimental and theoretical C8eO1 bond lengths are approxi-
-xþ1,-y,-z. mately shorter than typical C—O single bond indicating the
formation of pep 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
— istence of adsorbed atmospheric water. Indeed, it can be noticed
fact that this bond length value is shorter than Nsp2 Nsp2 single
—
bond which suggests the existence of delocalized double bonds
[37]. The bond angles from DFT calculations are very close to
the experi-
mental 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 opti-
mized bond lengths and bond angles obtained by using the DFT
calculation method show the best agreement with the experi-
mental values. Based on results shown in Table 3, selected experi-
mental torsion angles are very close to those obtained with
theoretical calculation.
The crystal structure consists of main molecule and H2O
mole- cule connected by hydrogen 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 OeH/N
hydrogen bonds to sta- bilize the packing. Description of the
structure showing the various hydrogen bonds are given in Fig.
2.
In the crystal packing, in addition to the OeH/N hydrogen
bonds, neighbouring molecules are linked by strong CeH/O in-
teractions into dimers as shown in Fig. 2 (a and b) which contrib-
utes to the supramolecular aggregation. Fig. 2(a) shows some
hydrogen bonds in the DBQA crystal while Fig. 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 stabi-
lization 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 signif-
icant 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.
Fig. 2. (a) Hydrogen bonding interactions and (b) Crystallographic packing diagram of DBQA.
4.2. Thermal analysis
The DTG/DTA thermal analysis, shown in Fig. 3, reveals the ex-
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 dehy-
dration reaction. The oxygen atom lone pairs of the water mole-
cules 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 be-
tween the positive pole represented by the hydrogen atom of
H2O and N1 atom of the quinoline moiety. These interactions
are rep- resented by— the Ow Hw2$$$N1 contact. Therefore, the
presence of the water molecule is very important in the stability
of the crys- talline 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 intra- molecular ones [38]. Dimerization of the
monomeric unit occurs through two pair of intermolecular¼
bonds C1-H1/O4 (d 2.612 Å). On the other hand, the nitrogen
atom of the quinoline unit par- ticipates in the hydrogen bond
and acts as a doublet donor by forming ¼ a hydrogen bond N1 …
Hw1 (d 1.942 Å) with the hy- droxyl of 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 at 3623.70e3591.70 cm—1 attributed to OH stretching
modes of coordinated water.
4.3. Vibrational spectra (IR)
The theoretical IR spectra and FT-IR spectrum of the title com-
pound are shown in Fig. 4. The vibrational spectra of (Z) -N'- (2,4-
dinitrobenzylidene) -2- (quinolin-8-yloxy) acetohydrazide were
calculated by B3LYP method with the 6e311þþG (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
(b)
 Fig. 3. Thermogravimetric and thermodifferential analysis of compound DBQA.
been found for the title compound. Vibrational frequencies calcu-
lated by using B3LYP with 6e311 G(d, p) basis set have been
given in Table 4, as compared with þþ experimental corresponding
data. The assignments of the calculated fundamental vibrational
modes of the title compound were performed on the basis of po-
tential energy distributions (PED) analysis using Gaussian 09 pro-
gram and Gauss View 5 molecular visualization program [42].
Aromatic compounds commonly exhibit multiple week bands in
the region of 3300e3000 cm—1 due to aromatic CeH stretching
vibrations [43]. The bands appeared at 3239 to 3066 cm —1 have
been assigned to CeH ring stretching vibrations for (DBQA). The
CeH in plane and outeofeplane bending vibrations generally lie in
the range of 1500e1000 cm—1and of 950e800 cm—1 [44,45],
respectively. The CeH ineplane bending vibrations are identified at
1525, 1461, 1456, 1428, 1412 and 1376 cm—1, the observed absorp-
tion bands in FTeIR spectrum are situated at 1504, 1469, 1452,
1435,
Fig. 4. The comparison of FT-IR and calculated IR spectra for DBQA.
1412 and 1379 cm—1. The HCCC twisting outeofeplane vibrations
are identified at 1016, 997, 982, 962 and 892 cm—1, whereas the
experimental absorption bands in FTeIR spectrum are observed at
1018, 996, 981, 956 and 894 cm—1. The OeH stretching vibrations
were observed at 3781 and 3610 cm—1, confirming the presence of
H2O molecule in the title compound. These bands have been
calculated at 3881 and 3452 cm —1 for B3LYP/6e311G þþ(d, p) level.
The NeH stretching vibrations observed at 3250 cm —1has been
calculated at 3248 cm—1. The assignments of nitro group fre-
quencies, basically some fundamental modes can be associated to
each NO2 group namely, nsy: symmetric stretching nasy: antisym-
metric stretching dsy: symmetric bending; and dasy: asymmetric
bending; which belongs to in plane vibrations. In addition to that
T: twisting modes of NO2 group would be expected to be
depolarized for outeofeplane vibrations. Aromatic nitro
compounds have strong absorptions due to the asymmetric and
symmetric stretch- ing, so the vibrations appear in the
range 1588e1554 and 1373e1356 cm—1 respectively. In the
present compound, the strong bands at 1527e1525 cm—1 by
B3LYP/6-311Gþþ(d, p) level are assigned to asymmetric
stretching mode of NO2 and the band at 1360 cm—1 assigned to
symmetric and asymmetrıc stretching mode of NO2. Aromatic
nitro compounds have a band of weak- etoemedium
intensity in the region of 595e522 cm—1 [43] due to the rocking
deformation in plane mode of the NO2 group. This band was
observed at 505 cm—1. The deformation vibrations of NO2
contribute to several normal modes in the low frequency
region [42]. These bands were also found in the wavenumber
region around the characteristic position of 748 cm—1 in FTeIR
spectrum for DBQA. The CeO stretching vibrations were
observed at 1283 and 1029 cm—1 which confirms the presence
in the compound.þþ These bands have been calculated at 1292
and 1030 cm—1 for B3LYP/6e311G
¼ (d, p) level. The carbonyl
group exhibits a strong absorption band due to C O stretching
vibration observed in the region of 1850e1550 cm—1. Because of
its high intensity and rela- tively 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
region; infrared bands at 1777 cm—1.
Our calculated carbonyl stretching frequencies are found very close Additionally, one can easily
to observed FTeIR frequencies at 1760 cm—1. The identification of
CeN vibrations is a very difficult task, since mixing of several bands
is possible in this region. However, the CeN stretching assignments
are identified by the animation application of GausseView 5.0.8
graphical interface [43]. The CeN stretching absorption stays in the
region 1382e1266 cm—1 for aromatic amines. The CeN stretching
vibrations are found to be present at 1382 and 1307 cm—1. In the
present study, a very strong band at 1368 cm—1 in FT-IR has been
assigned to CeN stretching vibration. The theoretically computed
value of CeN stretching vibration is defined as 1347 cm—1. The
bands observed at 1652 cm—1 and 1598 cm—1 respectively in FT-IR
have been assigned to asymmetric and symmetric C N stretching
vibrations. The theoretically computed values of C¼N stretching
vibration are defined as 1652 cm—1 and 1610 cm¼—1. The CeC
stretching vibration in general appears in the spectral range of
1650 to 1200 cm—1 [46]. The computed vibration is assigned to CeC
stretching vibration at 1647 cm—1 using B3LYP/6e311G (d, p)
which is comparable to experimental data at 1641 cm þþ—1
. The
computed vibrations are assigned to CeCeC in plane vibrations at
1504, 1396, 1135, 887, 842 and 621 cm—1 using B3LYP/6e311G (d,
p) which are comparable to experimental data at 1525, þþ 1385,
1136, 883, 838 and 620 cm—1. The computed vibrations (modes
46 and
34) are assigned to CeCeC out of plane vibrations at 666 and
471.17 cm—1 using B3LYP/6e311Gþþ (d, p) which are comparable to
experimental data at 663 and 471.81 cm—1. The asymmetric CeH
stretching mode of CH2 group is expected in the region around
2940 cm—1 and the symmetric around the region 2860 cm—1. The
CH2 asymmetric stretching mode in DBQA is found at 3059 cm—
1
in FTeIR spectra. The symmetric stretching mode is also
observed in FTeIR spectra at 3163 cm—1. The calculated
wavenumbers of the above modes are 3165 cm—1 (100%)
and3066 cm—1 (58%) using B3LYP/6e311Gþþ(d, p) respectively
for CH2 symmetric and asymmetric stretching modes. The
scissoring vibrations of CH2 were determined at 1609, 1575,
1560, 1542 cm—1 in FT-IR spectra [47]. The theoretically
computed values of CH2 give wavenumber at 1504.56 cm—1 by
B3LYP/6e311Gþþ(d, p) method.

4.4. UVeVis spectra analysis

The UVeVis electronic spectra of DBQA were recorded within

600-200 nm range. The oscillator strengths (f), wavelength ( l),
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 UVeVis
spectra of DBQA are given in Fig. 5. The calculated transition are
2
represented by a Gaussian function y ce—bx¼ with the height c equal
to the oscillator strength and b equal to 0.04 nm—2 [49,50].
According to the theoretical UVeVis 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 p /p*
transition and may be attributed to the ¼ excitation of C O
group. The elec- tronic 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 þ (81%),
HOMO-1 / LUMO 1(13%) and
HOMO/LUMO þ1 (4%). Similarly, the band calculated at 389 nm is
originated from the combination of HOMO/LUMO þ 1 (95%)
and HOMO-1 / LUMO (4%). The theoretically obtained
absorption bands can be assigned as p / p* and n / p*
transition with considerable intramolecular charge transfer
originating from donor to acceptor unit of the molecule DBQA.
say that the most likely transition is the band calculated at 397 nm frequency shifting,
with the oscillator strength of 0.2166. the highest and lowest mo-
lecular orbitals (HOMO and LUMO) have been calculated and pre-
sented in Fig. 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 ob- tained 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.

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
op- portunity to obtain more accurate results. The structure in the
title compound (DBQA) was confirmed with the help of 1H NMR
and 13C NMR spectral study. The sample was dissolved in CDCl3
and NMR spectrum was recorded using a Bruker Advance III FT-
NMR spec- trometer and TMS as the internal standard. The 1H
and 13C 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 [51e56]. The experi- þþ
mental and theoretical chemical shifts are presented in Table 6.
The aromatic protons of the title compound give resonance at
the re- gion of 7.33e9.11 ppm as would be expected. These
proton signals have been also calculated at the range of
7.31e9.01 ppm, 7.43e9.14 ppm and 7.41e9.13 ppm in gas, water
and chloroform media, respectively. The 1H NMR signals for
CH2 protons 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. There- fore, NH group
proton signal was observed 13.42 ppm and calcu- lated 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 100e150 ppm. In this study, aromatic C atom
signals were observed at the region of 112.18e155.33 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 aro- matic carbon signals have been also
calculated at the regions of 161.56e113.80 ppm in gas phase,
161.14e114.16 ppm in water so- lution and 161.38e114.25 ppm in
chloroform solution. The NMR signal for carbonyl C atom
observed at 166.72 ppm was calculated at 170.98, 175.77 and
174.67 ppm, respectively. All of the 1H and 13C NMR signals have
been found to be in expected regions. Addi- tionally, there is a
good agreement between experimental and theoretical results.
All of the obtained 1H and 13C NMR chemical shifts have been
found as consistent with literature [57e61].

4.6. Nonlinear optical properties

We have studied the type of the organic molecules because of

their larger nonlinear optical (NLO) susceptibilities arising from
p- electron cloud movement from donor to acceptor, fast NLO
response times, high laser harmsill and low insulation constants.
Although the organic 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
Table 4
The observed (FTeIR) and calculated vibrational frequencies (cm—1), IR intensity (km mol—1) and probable assignments of

DBQA. FTeIR B3LYP/6e311þþG(d,p) Assignments with PED>10%

No
(cm—1) Scaled freq (cm—1) IIR

129 3881.80 3881.57 74.70 n OH (99%)

128 3610.93 3452.68 879.73. n OH (97%)
127 3250.15 3248.23 613.79 n N4H (97%)
126 3368.89 3239.66 19.63 n CH (99%) ring1
125 3225.25 3224.95 3.55 n CH (99%) ring 1
124 3202.63 3208.74 2.54 n CH (86%) ring 1þ n CH asy (13%)
123 3213.94 3208.27 1.31 n CH (90%) ring 2
122 3196.98 3196.92 13.64 n CH (10%) þ n CH (87%) ring 3
121 3185.67 3188.87 16.57 n CH (38%) ring 2þ n CH (53%) ring 2
120 3174.92 3173.10 1.84 n CH (63%) ring 2þ n CH asy (33%) ring 3
119 3169.27 3170.26 3.04 n CH (75%) ring 3þ n CH asy(12%) ring 3
118 3163.61 3165.84 14.95 n CH (100%)
117 3146.65 3145.84 13.95 n CH (97%) ring 3
116 3126.29 3115.47 8.90 n CH (57%) þ n CH asy (42%)
115 3059.00 3066.31 20.09 n CH (42%) þ n CH (58%)
114 1760.65 1777.42 352.25 n C¼O (85%)
113 1678.03 1658.95 51.62 n CC (10%) ring 2þ d HOH (34%)
112 1652.02 1652.95 17.99 n N¼C asy (16%)þ n CCasy (10%) ring 1
111 1641.28 1647.06 23.58 n CC asy (19%) ring 2þ n CC asy (12%) þ d HOH asy (28%)
110 1636.19 1637.73 50.89 n CCasy (12%) ring 1þ d HNN (12%)
109 1630.53 1633.49 18.03 n CC (19%) ring 3
108 1621.48 1624.64 232.82 d HNN (19%)
107 1609.61 1610.82 267.62 n N¼C (32%)
106 1598.86 1605.45 285.02 n N¼C asy(12%)þ n CC asy(12%)
105 1588.12 1583.69 132.16 n ON asy (36%) þ n ON (36%)
104 1554.19 1569.75 163.43 n ON asy (24%)þ n ON (20%) þ n CC (15%) ring 1
103 1548.53 1536.41 103.38 n CC asy (10%) ring 3
102 1525,91 1504.56 16.69 d HCC (36%) ring1þ d HCC (15%) þ d CCC (10%) ring1
101 1503.29 1501.52 95.13 n NC (12%) ring1þ n CCasy (10%) ring3þ d HCC (12%) ring3
þd HCC (11%) ring2
100 1469.36 1491.67 11.59 d HCH (74%)þ THCOC asy (10%)
99 1452.40 1456.92 7.84 d HCC (16%) ring3þ d HCC (13%) ring2þ d HCC (22%)
98 1435.43 1428.10 7.30 n CC asy (20%) ring 1þ n CC (28%) ring 1þ d HCC asy (14%) ring1
97 1412.81 1418.84 26.92 d HCC (33%) ring 2
96 1402.07 1405.47 100.03 d HCN (53%)
95 1385.10 1396.54 54.38 n CC (25%) ring 2þ dCCC(18%) ring 2
94 1379.45 1376.08 3.31 d HCH asy (10%) þ T HCOC asy(24%) þ T HCOC asy(29%)
93 1373.79 1370.47 201.99 n ON2 asy(33%) þ n ON1 asy(41%)
92 1356.83 1360.57 491.08 n ON2 (23%)þ n ON1 (24%)þ n ON2 asy(19%) þ n ON1 asy(24%)
91 1368.14 1347.64 59.53 n CN5ring3 (15%)þ n CC ring3 (16%)þ n CC asy ring 2 (10%)
90 1345.52 1344.81 13.56 n CC asy ring 1 (17%)þ n CC ring 1 (11%)þ n CC asy ring 2 (10%)
89 1305.93 1298.21 160.62 d HCC (11%) þ d HCO (25%)
88 1283.31 1292.70 94.92 n OC (11%)þ d HCO (29%)
87 1272.00 1274.61 159.54 d HCO (11%)
86 1266.35 1267.91 3.10 n CN ring3 (28%)þ d HCC asy ring3 (21%)þ d HCC ring3 (11%)
85 1260.56 1259.12 229.78 n NN (13%)þ d HCH asy (11%)
84 1249.38 1237.81 12.31 n CC asy ring 2 (19%)þ d HCC asy ring3 (10%)þ d HCC ring2 (10%)þ
83 1232.98 1227.51 192.74 n CN4 asy (12%)þ n CC (11%)
82 1204.71 1201.54 192.81 d HCC asy ring1 (13%)þ d HCC ring3 (26%)
81 1182.09 1175.67 28.68 n NN (35%)þ d HCC asy (13%)þ d HCC (16%)
80 1159.47 1160.91 5.02 n CC asy ring 3(13%)þ d HCC asy ring3 (27%)þ d HCC asy ring 2(21%)þ
79 1142.50 1150.21 273.52 n NN (11%)þ d HCC asy ring1 (12%)
78 1136.85 1135.01 66.23 n CN5 ring3 (12%)þ d CCC (11%)
77 1125.54 1132.66 236.99 n OC (18%)þ d CCC asy ring2(10%)þ d HCC asy (11%)
76 1102.92 1102.04 9.14 n CC ring 3(15%)þ n CC ring 2(35%)þ d HCC (14%) þ d HCC asy ring2 (10%)
75 1080.30 1078.00 58.31 d CC$C asy ring1(10%)þ d HCC (13%) þ d HCC asy ring 1 (25%)
74 1052.59 1059.08 4.36 n CC ring 2(10%)þ n CC ring 3(43%)
73 1029.97 1030.61 5.26 n OC (25%)þ THCOC asy (10%)
72 1018.66 1016.89 0.63 THCCC ring1(41%)þ THCCN asy ring1(45%)
71 1013.00 1012.15 25.67 n OC (10%)þ THCOC (22%)þ TCOCC asy (10%)þ g OCNC asy (17%)
70 996.04 997.87 0.73 THCCC ring 2 (31%)þ THCCC ring 3 (36%)þ THCCC asy ring 1 (16%)
69 992.05 991.60 7.88 n CN4 (12%)þ n CC (14%)þ d OCC asy(11%) þ d CNN asy(11%)þ d NNC asy(10%)
68 981.01 982.10 0.73 THCCC ring 3 (21%)þ THCCC ring 2 (52%)
67 967.76 962.59 8.36 THCCC ring 3 (44%)þ THCCC ring 2 (17%)þ THCNN asy (22%)
66 956.45 962.28 17.66 THCCC ring 3 (18%)þ THCNN (63%)
65 939.49 944.14 14.29 THCCN (78%)
64 933.83 931.30 51.45 n NC (15%)þ n NC asy (15%)þ d ONO (12%)þ d ONO asy (12%)
63 894.81 892.70 2.35 THCCC ring 3 (21%)þ THCCC ring 2 (44%)þ TCCCCasy ring 2 (13%)
62 883.50 887.25 8.65 d CCC ring 2 (23%)þ d CCN ring 3 (14%)
61 872.19 875.06 5.95 THCCC ring 1 (40%)þ THCCN ring 1 (42%)
60 860.88 856.45 83.66 d HOH (14%)þ d OHN (11%)þ THNNC asy (24%)
59 849.57 852.86 40.92 d ON5O(22%) þ d ON4O (31%)
58 838.26 842.06 25.88 n CC ring 1(10%)þ n CC (12%)þ d ON5O asy(15%)þ d CCC ring1(11%)
Table 4 (continued )

FTeIR B3LYP/6e311þþG(d,p) Assignments with PED>10%

No
(cm )
—1
Scaled freq (cm )
—1
IIR

57 832.61 836.98 29.25 THCCC asy ring 2 (12%)þ TCCCN ring 3 (11%)þ TCCNCasy ring 3 (14%)þ TCCCC asy ring 1 (14%) þ gCCOC asy(13%)
56 815.64 817.01 3.01 d CCC ring3 (25%)þ d CCC ring2 (16%)þ d CCN asy ring3(10%)þ d CCC asy (16%)
55 804.33 807.00 54.76 THCCC ring 2 (19%)þ THCCC asy ring 3 (30%)þ TCCNC ring 3 (11%)þ
54 781.71 781.98 1.86 g CCCN1 asy (60%)þ g N2CCC asy (15%)
53 764.75 765.17 33.68 THCCC ring2 (35%)þ r HCCC asy ring2(22%)þT HCCC asy ring3(10%)
52 748.35 742.98 57.62 b ONO(11%)
51 742.69 740.82 36.47 g OHN(14%)
50 731.38 729.06 13.40 g OCON2 asy (58%)þ g OCON2(13%)
49 725.73 726.56 58.47 d OCC asy (10%)
48 714.42 717.53 8.76 n CC (10%) þ d CNC asy ring3(10%)
47 703.11 702.47 15.11 TCCCC asy ring2 (10%)þ g OCON1 asy (12%)
46 663.52 666.23 5.75 n CC ring1 (11%) þ bCCC ring1 (16%) þ bCCC (11%)
45 752.21 652.12 0.35 THCCC asy ring2 (10%)þ THCCC ring3 (13%)þ THCCC asy ring (14%)þ g CCOC asy (18%)
44 620,64 621,69 3.03 d CCC (20%)þ d COC (13%)
43 595.66 595.84 4.06 d CC ring1(20%)þ bOCC (11%)þ g OCNC asy (10%)
42 590.00 592.16 2.87 g CCCN ring3 (11%)þ g CCCC ring3 (19%)þ g CCNC asy ring3 (12%)þ g NCCO (19%)þ g CCOC asy (13%)
41 556.64 553.98 5.55 bCCC (31%)
40 534.02 536.02 2.33 bONC (37%)
39 522.71 521.61 4.46 bONC (15%)þ g CCCC ring1(17%)þ g NCCC (12%)þ g CCCC asy ring1(15%)þ ring1(17%)þ
38 511.40 515.88 59.60 d HCH asy (21%)þ THOHN asy (15%)
37 505.74 508.24 1.72 n CC (14%) þ d CNC ring3 (12%)
36 488.78 488.42 16.90 d CNC (12%)
35 466.16 474.99 0.56 g CCCN asy (29%)þ g CCCN ring3 (14%)þ g CCNC ring3(10%)þ g CCCC ring3(12%)
34 471.81 471.17 2.21 d NNC asy (15%)þ d CCC ring1(22%)
33 432.23 436.17 4,31 g CCCC ring3(10%)
32 420.92 419.06 1,69 d OCC asy (13%) þ d NCC (15%)
31 410.17 405.07 1,73 g ONC (17%)
n: stretching(elongation); ssy: symmetric; asy: asymmetric; b: in plane bending; g: outeof plane bending,u: wagging(agitation); T: twisting(torsion); d: bending; r: rocking
(balancement); vibrational modes are based on potential energy distribution (PED) and only contributions over 10% are given; scaled frequencies are in unit of cm—1;
IIR infrared inten. are in unit of km mol—1; ring 1: C13C14C15C16C17C18; ring 2: C4C5C6C7C8C9; ring 3: C1C2C3C4C9N1.

Table 5
Theoretical and experimental electronic transitions, oscillator strength and major contributions for the title

compound. Experimental Theoretical Major contributions with

l (nm)
B3LYP/6-311þþG(d,p) l (nm) Osc. strength

312 460 0.0034 HOMO/LUMO (99%) HOMO-1 / LUMO þ1(13%) HOMO/LUMOþ1 (4%)
397 0.2166 HOMO-1 / LUMO
(81%)
237 389 0.0223 HOMO/LUMOþ1 (95%) HOMO-1 / LUMO (4%)

Fig. 5. A comparison of experimental and theoretical UVeVis spectra for DBQA.

Fig. 6. The frontier molecular orbitals for DBQA obtained by using B3LYP method.

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].
 Table 6
The experimental and calculated 1H and13C NMR data (ppm) for DBQA. hyperpolarizability (b) of the Gaussian 09 output are reported in
atomic units (a.u.), the calculated values have been converted into
Atoms Experimental B3LYP/6e311þþG(d,p)
electrostatic units (esu) (for a ; 1 au ¼
0.1482 × 10 24 esu, for b ; 1
Gas Water Chloroform au ¼
8.6393 10× esu).
—33 —
1
H The total molecular dipole moment, polarizability and first
H1 8.92 8.98 9.16 9.13 hyperpolarizability are 8.8128 Debye, 36.5 10—24 esu× and
H2 7.58 7.57 7.78 7.73
47.3 ×10—30 esu, respectively and are depicted in Table 7. The first
H3 8.30 8.32 8.56 8.47
H5 7.58 7.57 7.84 7.77 hyperpolarizability parameter of pNA and urea were reported to be
H6 7.62 7.71 7.90 7.88 15.5 ×
10—24 and 0.13 10× —24
esu, respectively [67e69]. B3LYP re- sults
H7 7.33 7.31 7.43 7.41 demonstrated that DBQA molecule exists approximately 3 and 363
H10A 5.02 5.15 5.26 5.25
H10B
times higher first hyperpolarizability parameter than pNA and urea,
4.21 4.76 5.19 5.05
HN2 13.42 13.26 13.46 13.41
respectively. This high value of the parameter may be explained by
H12 8.92 8.91 8.64 8.68 the donor and acceptor functional substituents such as NO2, C O
H15 9.02 9.00 8.64 9.13 ¼
and aromatic rings. Another reason for the high value of the first
H17 9.01 9.00 9.14 8.60 hyperpolarizability may be considered as the length of the bridge
H18 9.11 9.01 8.71 8.76
HW1 2.48 1.37 1.72 1.66
between the end groups of molecule. The longer length of the
HW2 7.35 7.55 8.17 8.03 bridge between electron donor and acceptor groups may improve
13
C the nonlinear optical properties of DBQA molecule. The small
C1 148.13 153.55 154.65 154.16 HOMO-LUMO energy gap also indicates that the DBQA is a good
C2 122.68 127.19 128.07 127.83
candidate to NLO materials.
C3 137..54 143.30 145.03 144.34
C4 130.85 136.66 136.67 136.62
C5 120.92 125.61 126.67 126.14
4.7. Molecular electrostatic potential (MEP)
C6 130.05 134.30 135.13 135.10
C7 112.18 113.80 114.16 114.25
C8 155.33 161.56 161.14 161.38 Molecular electrostatic potential (MEP) is related to the elec-
C9 147.88 146.98 146.22 146.56 tronic density and is a very useful descriptor in understanding sites
C10 87.58 71.98 71.49 71.64
for electrophilic attack and nucleophilic reactions as well as
C11 166.72 170.98 175.77 174.67
C12 134.74 141.85 145.62 144.20
hydrogen bonding interactions [70e72]. The electrostatic potential
C13 141.71 144.43 145.21 144.88 V(r) is also well suited for analyzing processes based on the
C14 127.74 133.98 134.21 157.38 ‘‘recognition” of one molecule by another, as in drug receptor, and
C15 127.57 133.61 135.46 129.24 enzyme substrate interactions, because it is through their poten-
C16 149.61 154.22 155.11 155.18
tials that the two species first ‘‘see” each other [73,74]. Being a real
C17 123.25 128.76 129.44 13.83
C18 154.58 156.26 157.53 153.75 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).
The non-linear optical response of an isolated molecule in an
electric field can be represented as a Taylor series expansion of the X ð 0
ZA rðrÞdr
total dipole moment, mtot, induced by the field: V ðrÞ¼
jRA — rj
0
r —
A—
r
mtot ¼ m0 þ aijEj þ bijkEjk þ …
where ZA is the charge on nucleus A located at RA and r(r) is the
where a is the linear polarizability,m0 is the permanent dipole electron density. The first term in the expression represents the
moment and bijk are the first hyperpolarizability tensor compo- effect of the nuclei and the second represents that of electrons. The
nents. The isotropic (or average) linear polarizability is defined as two terms have opposite signs and therefore opposite effects. V(r) is
[66]: their resultant at each point r; it is an indication of the net elec-
trostatic effect produced at the point r by the total charge distri-
1. bution (electrons þ nuclei) of the molecule. Electrostatic potential
atot ¼ axx þ ayy þ azz correlates with dipole moment, electronegativity, partial charges
3Σ
The mean first-order hyperpolarizability is
Table 7
. Σ1
b ¼ b þ 2b þ b2 2 2 Total static dipole moment (m, in Debye), the mean polarizability
(hai, in 10—24 esu), the mean first-order hyperpolarizability (hbi, in

tot x y z
10—30 esu) for DBQA.
where Parameter B3LYP/6-311þþG(d,p)
mx —8.6219
bx ¼ bxxx þ bxyy þ bxzz my 1.4500
mz —1.1070
m 8.8128
axx 391
by ¼ byyy þ byzz þ byxx
ayy 335
azz 226
hai 36.5
bz ¼ bzzz þ bzxx þ bzyy
bx 5121.119
by 1299.1059
m, a, and b parameters have been examined in gas phase, water, bz —1433.5444
and ethanol solvents. hbi 47.3
Since the values of the polarizabilities (a) and

Fig. 7. Molecular electrostatic potential (MEP) surface for DBQA.
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 electro- static 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 Fig. 7. To predict
reactive sites for electrophilic and nucleophilic attack for the
investigated molecule, MEP was calculated at the B3LYP/6-
31G þþ
(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 Fig. 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 [77e81]. According to Fig. 7,
the regions around¼NO2 and C O groups are represented by red
color, indi- cating that these regions are the electron-rich parts of
DBQA molecule. As for the most positive potential region of DBQA
molecule, Fig. 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.
5. Conclusion
The organic compound (Z)-N'-(2,4-dinitrobenzylidene)-2-(qui-
nolin-8-yloxy) acetohydrazide, was synthesized, and characterized
by spectroscopic (FT-IR, NMR and UVeVis) and structural (XRD)
techniques. The X-ray structure is a little different from its opti-
mized 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-(quino-
lin-8-yloxy) acetohydrazide has been obtained at B3LYP level in
conjunction with the 6-311 G(d,
þþ 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 6e311þþ G(d, p) basis set., The theo-
retical 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, theo-
retical 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 com-
pound 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.
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