Journal of Molecular Structure 1091 (2015) 183–195

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Journal of Molecular Structure

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

Theoretical analysis (NBO, NPA, Mulliken Population Method)

and molecular orbital studies (hardness, chemical potential,
electrophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-
2-methylphenylimino)methyl)-3-methoxyphenol
Zeynep Demircioğlu a,⇑, Çiğdem Albayrak Kasßtasß b, Orhan Büyükgüngör a
a
Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey
b
Department of Chemistry, Faculty of Arts and Science, Sinop University, TR-57000 Sinop, Turkey

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 FT-IR and various organic solvents

effect on UV–Vis has been studied.
 HOMO, LUMO, local reactivity,
chemical reactivity and Fukui
function analysis were performed.
 Mulliken Population Method, NPA
and NBO were investigated.

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

Article history: The molecular structure and spectroscopic properties of (E)-2-((4-hydroxy-2-methylphenylimino)-

Received 9 December 2014 methyl)-3-methoxyphenol, were characterized by X-ray diffraction, FT-IR and UV–Vis spectroscopy. All
Received in revised form 24 February 2015 of theoretical calculations and optimized geometric parameters have been calculated by using density
Accepted 24 February 2015
functional theory (DFT) with hybrid method B3LYP by 6-31G(d,p) basis set. The title compound of
Available online 5 March 2015
C15H15N1O3 have been analyzed according to electronic and energetics behaviors for enol-imine and
keto-amine tautomers. Both these tautomers engender six-membered ring due to intramolecular hydro-
Keywords:
gen bonded interactions. Two types of intramolecular hydrogen bonds (a) strong O–H  N interactions in
Natural population analysis (NPA)
Fukui function analysis
enol-imine form and (b) N–H  O interactions in keto-amine form are compared particularly. The theo-
Natural bond orbital analysis (NBO) retical vibrational frequencies have been found in good agreement with the corresponding experimental
Mulliken electronegativity data. A study on the electronic and optical properties, absorption wavelengths, excitation energy, dipole
moment, molecular electrostatic potential (MEP) and frontier molecular orbital energies are performed
using DFT method. Additionally, geometry optimizations in solvent media were performed with the same
level of theory by the polarizable continuum model (PCM). The effect of solvents on the tautomeric sta-
bility has been investigated. Mulliken Population Method and natural population analysis (NPA) have
been studied. NBO analysis is carried out to picture the charge transfer between the localized bonds
and lone pairs. The local reactivity of the molecule has been studied using the Fukui function. NLO prop-
erties related to polarizability and hyperpolarizability are also discussed.
Ó 2015 Elsevier B.V. All rights reserved.

⇑ Corresponding author. Tel.: +90 362 312 1919.

E-mail address: zeynep.kelesoglu@omu.edu.tr (Z. Demircioğlu).

http://dx.doi.org/10.1016/j.molstruc.2015.02.076
0022-2860/Ó 2015 Elsevier B.V. All rights reserved.
184 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195

Introduction way of molecular orbital framework. In the paper, all calculations

are valuable for providing insight into molecular properties of
During the last few decades, there has been a considerable Schiff base compounds.
interest in the chemistry of Schiff base compounds [1]. Schiff bases
exhibit unique properties which make them favorable for an array
of applications such as catalysis and medicinal chemistry [2]. Most Experimental and computational methods
Schiff bases have antibacterial, anticancer, antinflammatory and
antitoxic properties [3]. Organic molecules with carbon nitrogen Synthesis
double bond are known as Schiff bases and prepared by a reaction
of a primary amine and an aldehyde. Schiff bases containing hydro- For the preparation of (E)-2-((4-hydroxy-2-methylphenylim-
xyl group have received the interest of chemists and physicists due ino)methyl)-3-methoxyphenol compound the mixture of 2-hy-
to their special photochromic and thermochromic characteristics. droxy-6-methoxybenzaldehyde (0.5 g, 3.3 mmol) in ethanol
An intramolecular proton transfer associated with a change in p- (20 ml) and 4-hydroxy-2-methylaniline (0.41 g, 3.3 mmol) in etha-
electronic system from the hydroxyl oxygen atom to the imine nol (20 ml) was stirred for 2 h under reflux. The crystals suitable
nitrogen atom and the potential energy profile of this transfer for X-ray analysis were obtained from ethanol by slow evaporation
forms the special thermochromic and photochromic properties (yield; %86, m.p.; 452–454 K).
[4,5]. From observations on some thermochromic and pho-
tochromic Schiff base compounds, it was proposed that molecules
exhibiting thermochromism are planar, while those exhibiting Instrumentation
photochromism are non-planar [6,7]. o-hydroxy schiff base ligands
are of interest mainly because of the existence of typical hydrogen The FT-IR spectrum of the title compound was recorded in the
bonds and tautomerism between the O–H  N in enol-imine and 4000–400 cm1 region with a Bruker Vertex 80V FT-IR spectrome-
N–H  O in keto-amine forms and N+–H  O in zwitterionic forms ter using KBr pellets. Absorbtion spectra were determined on
[8–10]. This compound shows the keto-amine tautomer. These Unicam UV–vis spectrometer.
Schiff base compounds with proton transfer potential have differ-
ent applications in photochromic materials [11–13], optical data
storage [14–16], as nonlinear optical materials [12,13], anticorro- Crystal structure determination
sive materials or anticancer medicines [17–19]. Such proton
exchanging materials can be applied for the design of different The single-crystal X-ray data were collected on a STOE IPDS II
molecular electronic devices [20]. image plate diffractometer at 296 K. Graphite-monochromated
Research for determination of structural stability of Schiff bases Mo Ka radiation (k = 0.71073 A) and the w-scan technique were
in theoretical modeling of drug design by experimental and theo- used. The structure was solved by direct methods using SHELXS-
retical methods is necessary. Different molecular properties such 97 [30] and refined through the full-matrix least-squares method
as vibrational frequencies, electrostatic potentials, and non-linear using SHELXL-97 [31], implemented in the WinGX [32] program
optical properties can be predicted by computational methods suite. Non-hydrogen atoms were refined with anisotropic dis-
[21–23]. Density functional theory (DFT) method has been placement parameters. All H atoms were located in a difference
accepted as a popular post-HF approach for the computation of Fourier map and were refined isotropically. Data collection: Stoe
structural characteristics, energies of molecules and vibrational X-AREA [32], cell refinement: Stoe X-AREA [32], data reduction:
frequencies by the ab initio community and for the accuracy with Stoe XRED [33]. The general-purpose crystallographic tool
respect to the evaluation of a number of molecular properties PLATON [34] and ORTEP-3 [32] was used for the structure analysis
[24–26]. and presentation of the results. Details of the data collection con-
A new (E)-2-((4-hydroxy-2-methylphenylimino)methyl)-3- ditions and the parameters of the refinement process are given in
methoxyphenol compound was synthesized and it was determined Table 1.
by single crystal X-ray diffraction technique. In the present study,
it is planned to have a joint experimental and theoretical investiga-
tion of FT-IR and UV–vis spectra. According to X-ray, FT-IR and UV– Table 1
Crystal data and structure refinement parameters.
vis results, the compound shows the keto-amine form. Electronic
absorption spectra of the title compound were predicted for Chemical formula C15H15N1O3
enol-imine and keto-amine states by using TD-DFT (time- Color/shape Yellow/plate
Formula weight 257.28
dependent density functional theory) [27–29] in the calculation Temperature 296 K
of electronic excitation energies for gas and solution phases Crystal system Monoclinic
(different solvent media). The excitation energies, dipole moments, Space group C2/c
oscillator strengths, total energies and etc. were also obtained at Unit cell parameters a = 8.9695(12) Å
b = 16.011(2) Å
TD-DFT level at the optimized geometry. Additionally, it was also
c = 18.163(2) Å
planned to illuminate theoretical determination of the optimized b = 98.058(10)°
molecular geometries, HOMO–LUMO energy gap, MEP, NLO, Volume 2582.7(6) Å3
Mulliken charges, NPA and NBO analysis of the titled compound Z 8
by using Density Functional Theory (DFT) with B3LYP/6-31G(d,p) Density 1.323 Mg m3
Absorption coefficient 0.093 mm1
basis set. Diffractometer/meas. meth. STOE IPDS 2/--scan
The electronic property of the title molecule was calculated h range for data collection 2.26–26.50°
from the total energies and the Koopmans’ theorem. These are Measured reflections 18,761
related to especially Frontier molecular orbitals. The other impor- Independent/observed reflections 2687/2024
Goodness of fit on F2 1.070
tant quantities such as ionization potential (I), electron affinity
Final R indices [I > 2r(I)] R1 = 0.05, wR1 = 0.120
(A), electrophilicity index (w), chemical potential (l), electronega- R indices (all data) R2 = 0.075, wR2 = 0.133
tivity (v), hardness (g), and softness (S) are also evaluated in the
 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195
Computational details
In order to obtain stable structures, the geometrical parame-
ters of title compound in the ground state was optimized at
DFT/B3LYP level theory by using 6-31G(d,p) basis set. The
calculations were performed with the Gaussian 03W [35] pro-
gram package, invoking gradient geometry optimization [36]
using personal computer. The calculated vibrational frequencies
are scaled by 0.9627 for B3LYP/6-311G(d,p) basis set [37], the
optimized structural parameters were used in the vibrational fre-
quency calculation at DFT levels to characterize all stationary
minima. In the present work using GAUSSVIEW program with
symmetry considerations along with available related molecules,
optimized structure, vibrational frequency assignments were
made with a high degree of accuracy. The HOMO–LUMO analysis
has been carried out to explain the charge transfer within the
molecule. The global hardness (g), global softness (t), elec-
tronegativity (v) and chemical potential (l) have been calculated
using the highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO). The natural bonding orbi-
tal (NBO) calculations [38] were performed using NBO 3.1 pro-
gram as implemented in the Gaussian 03W package at the
above said level in order to understand various second order
interactions between the filled orbital of one subsystem and
vacant orbital of another subsystem, which is a measure of the
intermolecular and intramolecular delocalization or hyper
conjugation.
For calculating the excitation energies, dipole moments, oscil-
lation strengths (f), wavelengths (k) and energy gaps of the mole-
cule, TD-DFT calculations started from gas phase and solution
phases optimized geometries were carried out using the same
level of theory. Theoretical UV–Vis spectra of the titled com-
pound in enol and keto forms were also obtained by TD-DFT
excited state calculation. This calculations are also very impor-
tant in determining solvent polarity effect on tautomerism.
Because of literature indicates that the enol form is less polar
than the keto tautomer because of the intramolecular hydrogen
bonding. Thus, an increase in solvent polarity favors the more
polar keto form. Since solvent effects play an important role in
absorption spectrum of the compound, in this paper, the integral
equation formalism polarizable continuum model (PCM) [39,40]
dealing with solvent effect was chosen in total energies, excita-
tion energies, oscillator strengths, dipole moments and frontier
orbital energies. In addition, the energy gap (DE) between the
highest occupied molecular orbital (HOMO) and the lowest-lying
unoccupied molecular orbital (LUMO), dipole moment and total
energies increase with the polarity of the solvent and this
increasing was observed both the enol-imine and keto-amine
forms. The calculated values for solvents which are different
dielectric constants, as well as two tautomers of enol-keto
forms have also compared with experimental UV–Vis spectrum
results.
Molecular electrostatic potential (MEP) analysis has been used
to find the reactive sites of the compound. The electrostatic poten-
tial contour map with the negative regions (assigned to red) of MEP
are related to electrophilic attacks and positive regions (assigned to
blue) are related to nucleophilic reactivity. In addition, in this
paper the net charges is calculated with Mulliken Population
Method and natural population analysis (NPA). The calculated
natural atomic charge values from the natural population analysis
procedures are obtained from NBO analysis. For minimal and small
split valence basis sets, this methods quickly gives chemically
intuitive charge sign on atoms and usually reasonable charge mag-
nitudes. These analysis have been used to study for illuminating
the electronic effects.
185
Results and discussion
Crystal structure and optimized geometry
The optimized molecular structure of the Schiff base with atom
numbering scheme adopted in this study. The X-ray (experimen-
tal) and optimized (theoretical) geometry parameters for enol-keto
tautomers, namely bond lengths, bond angles and torsions were
calculated by B3LYP/6-31G(d,p) method are listed in Table 2.
The tautomerism appears in o-hydroxy Schiff bases as a result
of intramolecular proton transfer from oxygen atom to nitrogen
atom. This proton transfer resulted in two tautomeric structures
in the solid state. These tautomeric forms are related to two types
of intramolecular hydrogen bonds as O–H  N in enol-imine form
and N–H  O in keto-amine form (Fig. 1).
X-ray investigation shows that the title compound indicates
keto-amine form. The results are show that the C8–N1 bond length
is 1.296(2) Å, C8@C1 bond length is 1.410(2) Å, C2@O1 bond length
is 1.300(2) Å and N1–H1 bond length is 0.86(2) Å. They are consis-
tent with the distances of the single bonds (C–N, N–H) and the
double bonds (C@O, C@C) which are reported in previous studies
[41,42].
A significant intramolecular interaction (N1–H1  O1) is noted
involving phenol atom O1 and nitrogen atom N1 and hydrogen
bond constitutes a six-membered ring S(6) (Fig. 2) [43]. The inter-
molecular O3–H3A  O1 hydrogen bond is important in the crystal
packing of title compound, giving rise to the chain motif (Fig. 3,
Table 2).
As an another way of confirming if titled molecule exists in enol
form, the harmonic oscillator model of aromaticity (HOMA) index
is calculated by using Eq. (1) for benzene rings [44,45].
" #
aX
n
2
HOMA ¼ 1  ðRi  Ropt Þ ð1Þ
n i¼1
n is the number of bonds in ring, a is the constant equal to 257.7
and Ropt is equal to 1.388 Å for C–C bonds. For the purely aromatic
compounds HOMA index is equal to 1 but, for non-aromatic com-
pounds it is equal to 0. We calculated HOMA index of C1–C6 and
C9–C14 rings. The calculated HOMA indices for C1–C6 and C9–
C14 rings are 0.785 and 0.97, respectively. These results also indi-
cate that the titled compound exists in keto form and rings are
the aromatic. X-ray results show the dihedral angle between the
planes of two aromatic rings is 4.03(11)° and in optimized geometry
it is 15.47°. The planar aromatic rings show the thermochromic
properties. In addition, the dihedral angle between the nearly pla-
nar S(6) (O1/H1/N1/C8/C1/C2) ring with C1–C6 and C9–C14 aro-
matic rings are 0.67(11)° and 3.95(11)°, respectively. Molecular
packing manner in the lattice, molecular geometry and spectro-
scopic details supported the thermochromic tendency for titled
compound.
The selected bond lengths, bond angles and torsion angles were
listed in Table 3. As expected, the results indicated that a little dif-
ferences in experimental and computational processes. The differ-
ences observed between the experimental and calculated
Table 2
Hydrogen bonding geometry for the titled compound.
D–H  A D–H H  A D  A D–H  A
N1–H1  O1 0.86 1.82 2.5424 164
O3–H3A  O1i 0.93 2.57 3.2239 128
D: donor; A: Acceptor.
(symmetry code: (i): 3/2  x, 1/2 + y, 1/2  z).
186 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195
Fig. 1. Keto-amine and enol-imine tautomeric forms of title compound.
Fig. 2. Ortep 3 diagram for (E)-2-((4-hydroxy-2-methylphenylimino)methyl)-3-
methoxyphenol, with the atom numbering scheme. Dashed lines are show the N1–
H1  O1 intra molecular hydrogen bonds.
parameters were due to the ignored effects for gas phase.
Theoretical methods were not take into account the molecular
interactions.
Namely, the optimized geometry with B3LYP is preferred more
planar conformation than X-ray geometry. The structural dis-
crepancies between the optimized molecule and crystallographi-
cally observed geometry can be analyzed quantitatively by root
mean square (r.m.s.) overlay. The r.m.s. fit of the atomic positions
of experimental and calculated geometries are 0.148 Å and 0.382 Å,
indicating the two geometries for keto-amine form and enol-imine,
respectively (Fig.4). The compound shows keto-amine form in solid
state therefore high r.m.s value for enol-imine form is not
surprising.
Vibrational spectra
In order to obtain the spectroscopic signature of title com-
pound, we performed a frequency calculation analysis. The aim
of the vibrational assignments is to conclude which of the vibra-
tional modes give rise to each of these observed bands.
Theoretical calculations were made for a molecule in vacuum,
where experiments were performed in solid phase. Therefore the
theoretical vibrational analysis values are generally somewhat
greater than the experimental values due to neglect of anhar-
monicity in real system. These discrepancies can be corrected
either by computing anharmonic corrections explicitly or by intro-
ducing a scaled field or directly scaling the calculated wavenum-
bers with proper factor. A tentative assignment is often made on
the basis of unscaled frequencies by assuming the observed fre-
quencies so that they are in the same order as the calculated ones.
Then, for an easier comparison to the observed values, the calcu-
lated frequencies are scaled by the scale to less than 1, to minimize
the overall deviation. Thus, empirical scaling factors are usually
used to match the experimental vibrational frequencies [45]. In
order to improve the agreement between the calculated and the
experimentally observed values, the vibrational frequencies have
been scaled by 0.9627 [46]. The frequencies obtained by theoretical
method is in accordance with the observed FT-IR spectrum. Also, it
should be noted that the experimental results belong to solid phase
and theoretical calculations belong to gaseous phase. A better
agreement between the computed and experimental frequencies
can be obtained by using different scale factors for different
regions of vibrations. For that purpose, we have utilized different
scaling factors for all fundamental modes to obtain the scaled fre-
quencies of the compound.
C–H vibrations
The title compound is fused with an aromatic rings are benzene.
Hence, the molecular structure of the title compound shows the C–
H stretching vibrations. The C–H stretching vibration of benzene
derivatives generally appear in the region 3000–3100 cm1, which
is the characteristic region for ready identification of C–H stretch-
ing vibration [47,48]. Accordingly, in the present investigation, the
C–H symmetric stretching vibrations of are observed at
3077.5 cm1, 3079.69 cm1 in the theoretical FT-IR spectrum and
3014.45 cm1 is found in the experimental FT-IR spectrum. The
asymmetric stretching vibrations are observed at 3108.5 cm1
(theoretical) and 3037.5 cm1 (experimental). These modes are
supported by the literature [49].
The C–H in-plane bending frequencies appear in the range of
1000–1300 cm1 and are very useful for characterization purpose
[50]. The C–H in-plane bending vibrations appear as medium strong
to strong bands in theoretical FT IR spectrum at 1386 cm1,
1623 cm1. Besides experimental results show that C–H in-plane
bending vibrations are occur as range of 1010.43–1251.95 cm1
for benzene groups. The C–H out-of-plane bending vibrations are
strongly coupled vibrations and occur in the region 1000–
750 cm1 [51]. The aromatic C–H out-of-plane bending vibrations
are assigned to the bands observed at 856.51 cm1, 945.85 cm1 in
theoretical FT-IR spectrum. Accordingly, the experimental
investigation these bands observed at 827.96–956.92 cm1.
C–C vibrations
The bands between 1200 and 1650 cm1 in the aromatic com-
pounds are assigned to skeletal C–C stretching modes. The bands
 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195
Fig. 3. A partial packing diagram with O3–H3A  O1i intermolecular hydrogen bonds shown as dashed lines [symmetry code: (i): 3/2  x, 1/2 + y, 1/2  z].
are observed in the range of 1257.76–1548.73 cm1 in experimen-
tal FT-IR spectrum. In addition, theoretical results are 1169.5 cm1,
1332.78 cm1, 1537.3 cm1.
N–H and C–N vibrations
The N–H stretching vibration is very sensitive to inter- and
intramolecular hydrogen bonds and lies in the region 3300–
3500 cm1 in FT-IR spectrum. It gives rise to the vibrations as
stretching vibration. In experimental and theoretical results show
that 3200–3500 cm1 and 2794.2 cm1 absorption bands are
attributed to the t(N–H) stretching vibration which broaden owing
to the formation of strong intramolecular hydrogen bonding N1–
H1  O1 in the structure.
The c(N1–H1) rocking vibrations lie in the region 1537.3–
1637.1 cm1 for theoretical calculations. The band observed at
1610.03 cm1 was assigned to experimental N–H rocking vibration
for the titled compound.
In aromatic compounds, the C–N stretching vibration usually
lies in the region 1400–1200 cm1. The absorption band located
at 1640.9 cm1 and 1624.16 cm1 for the theoretical and experi-
mental results are attributed to t(C8–N1) stretching vibration. C–
N–C stretching vibration observed at 1307.5 cm1 for theoretical
FT-IR spectrum. According to experimental results C–N–C stretch-
ing vibration occured in the range of 1291.95–1365.17 cm1.
CH3 and O–H vibrations
The assignments of C–H stretching vibrations showed that the
place of methyl group within a molecule. The asymmetric and
the symmetric C–H3 vibrations in methyl group is observed
between 2952.6 cm1 (symmetric) and 3055.7 cm1, 3044 cm1
(asymmetric) for theoretical FT-IR, whereas the experimental
187
values are observed at 2964.3 (symmetric) and 3014.45 cm1
(asymmetric). The observed symmetric and asymmetric C–H3
vibrations for methoxy group are 2933.5 cm1 and 3055.7 cm1.
The experimentals are 2912.4 cm1 and 2964.3 cm1 (asymmet-
ric); 2933.2 cm1 (symmetric).
In addition, calculations out of plane bending of C–H vibrations
were observed at 1455–1475 cm1 (theoretical) and 1365.17–
1339.75 cm1 (experimental). Besides, in plane bending of C–H vibra-
tions were observed at 1456.62 cm1, 1501.6 cm1, 1476.28 cm1,
1470 cm1 (theoretical) and 1436.09 cm 1 , 1827.75 cm 1
(experimental).
The O–H stretching vibrations showed at 3709.55 cm1 (theo-
retical) and 3701.26 cm1 (experimental).
The substituent sensitive modes of the phenyl ring and other
modes are also identified and assigned (Table 4, Fig. 5). Most of
the modes are not pure but contains significant contributions from
other modes also. Most of the characteristic modes for title com-
pound are good agree with the literature data which are involve
same vibration range [52].
Analysis of Frontier molecular orbitals (FMOs)
The highest occupied molecular orbitals (HOMOs) and the low-
est-lying unoccupied molecular orbitals (LUMOs) are named as
Frontier molecular orbitals (FMOs). Highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)
are very important parameters for quantum chemistry and UV–
Vis spectra. We can determine the way the molecule interacts with
other species; hence they are called the frontier orbitals. HOMO,
which can be thought the outermost orbital containing electrons,
tends to give these electrons such as an electron donor. On the
other hand; LUMO can be thought the innermost orbital containing
free places to accept electrons [53].
188 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195

Table 3 EHOMO(keto) = 5.072 eV, ELUMO(keto) = 1.680 eV, DE(keto) =

Bond lengths (Å), bond angles (°) and dihedral angles (°) obtained by X-ray and DFT/ 3.392 eV and EHOMO(enol) = 5.452 eV, ELUMO(enol) = 1.563 eV,
B3LYP/6-31G(d,p).
DE(enol) = 3.889 eV. As can be seen from calculated results that
Bond lengths (Å), Experimental DFT/6-31G(d,p) DFT/6-31G(d,p) keto form is a lower chemical reactivity and higher kinetic stability
bond angles (°) and keto-amine enol-imine than enol form. The calculations indicate that titled compound
torsions (°)
have 69 occupied molecular orbitals. HOMO and LUMO energies
C8–N1 1.296(2) 1.3298 1.2967 and surfaces can be seen in Fig. 6.
C1–C8 1.410(2) 1.3993 1.4473
C2–O1 1.3001(19) 1.2691 1.3375
The narrow energy gap between HOMO and LUMO facilitates
N1–C9 1.4068(19) 1.4076 1.4079 makes the material to be NLO active. In addition, FMOs are directly
C12–O3 1.3422(19) 1.3666 1.3674 related to chemical hardness and softness abilities of molecules.
O2–C6 1.3596(18) 1.366 1.3652 We will discuss each of these capabilities in detail later in this
C7–O2 1.417(2) 1.4202 1.4202
paper.
C12–O3 1.3422(19) 1.3666 1.3674
C14–C15 1.502(2) 1.5093 1.5084
C4–C5 1.395(2) 1.3695 1.4029 Analysis of molecular electrostatic potential (MEP) surface
C1–C6 1.421(2) 1.4383 1.4222
C10–C9 1.387(2) 1.3995 1.4024 The MEP is a very useful feature to study reactivity given that an
C9–C14 1.396(2) 1.415 1.4164
approaching electrophile will be attracted to negative regions (the
C12–C13 1.385(2) 1.3982 1.3993
N1–H1 0.86 1.0546 1.6722 electron distribution in where effect is dominant). In the majority
O1–H1 2.5424 1.6093 1.0041 of the MEPs, while the maximum negative region which preferred
C8–N1–C9 128.74(14) 128.0006 121.3281 site for electrophilic attack indications as red color, the maximum
C1–C8–N1 122.07(14) 121.6163 121.7436
positive region which preferred site for nucleophilic attack symp-
C3–C2–O1 121.61(15) 122.0754 118.5864
C1–C2–O1 120.54(14) 121.267 121.1446 toms as blue color. The importance of MEP lies in the fact that it
C7–O2–C6 118.24(13) 118.202 118.5451 simultaneously displays molecular size, shape as well as positive,
C1–C6–O2 114.83(13) 114.6763 115.252 negative and neutral electrostatic potential (MEP) of compound
C11–C12–O3 124.09(15) 123.001 122.9362 is shown in Fig. 7. The MEP is a plot of electrostatic potential
C13–C12–O3 117.65(14) 117.373 117.297
mapped onto the constant electron density surface.
N1–C9–C14 117.47(14) 117.9669 118.0793
C1–C6–C8 119.77(14) 120.1682 120.5352 The different values of the electrostatic potential at the surface
C5–C6–O2 124.67(14) 124.5685 123.8085 are represented by different colors. Potential increases in the order
C5–C6–O2–C7 1.5(3) 0.5903 0.3969 red < orange < yellow < green < blue. The color code of these maps
C8–C1–C6–O2 179.86(16) 0.3175 0.17
is in the range between 6.797 a.u. (deepest red) and 6.797 a.u.
C1–C6–O2–C7 178.13(18) 179.553 179.742
O1–C2–C1–C8 0.6(3) 0.171 0.1613
(deepest blue) in compound, where blue shows the strongest
C1–C8–N1–C9 178.82(17) 179.9231 176.7496 attraction and red shows the strongest repulsion. Regions of nega-
C10–C9–N1–C8 3.5(3) 15.4921 33.9333 tive V(r) are usually associated with the lone pair of electronega-
C14–C9–N1–C8 175.84(18) 165.0153 148.4705 tive atoms. As can be seen from the MEP map of the title
C15–C14–C9–N1 2.2(3) 0.3731 1.2026
molecule, while regions having the negative potential are over
C2–C1–C8–N1 1.0(3) 0.6664 0.0626
O3–C12–C11–C10 178.6(2) 179.7955 179.9091 the electronegative atoms (oxygen atoms in the S(6) ring), the
O3–C12–C13–C14 179.14(18) 179.9002 179.5098 regions having the positive potential are over the hydrogen atoms.
C15–C14–C13–C12 179.39(18) 179.9758 179.7332 Gions having the positive potential are over the hydrogen atoms. In
accordance with this the oxygen atoms in the S(6) ring behaves as
electrophiles region and it is denoted as red color.
The calculated electrostatic energy for N1, O1, O2, O3 are about
17.22 eV, 17.19 eV, 14.55 eV, 15.21 eV. Similarly, the nucle-
ophiles region was graphically shown as blue color and expressed
as electron deficiency in those regions, which also denotes nucle-
onic energy of the LUMO orbitals. The calculated electrostatic
potential energy are about H1 and H3A are 9.57 eV and 8.65 eV
for the hydrogen atoms. According to these obtained results, we
can say that the H atoms indicate the strongest attraction and O
atoms indicate the strongest repulsion.
Fig. 4. Superimposition of the X-ray structure (red) and calculated structure (black)
of the enol-imine and keto amine forms of the title molecule. (For interpretation of Natural bond orbital (NBO) analysis
the references to color in this figure legend, the reader is referred to the web version
of this article.) Weak occupancies of the valence antibonds signal irreducible
departures from an idealized localized Lewis structure which
means true ‘delocalization effects’. NBO analysis provides the most
accurate possible natural Lewis structure picture, because all the
Owing to the interaction between HOMO and LUMO orbital of a orbital details are mathematically chosen to include the highest
structure, transition state transition of p ? p⁄ type is observed possible percentage of the electron density. A useful aspect of the
with regard to the molecular orbital theory [54]. The frontier orbi- NBO method is that it gives information about interactions in both
tal gap helps characterize the chemical reactivity and the kinetic filled and virtual orbital spaces that could enhance the analysis of
stability of the molecule. A molecule with a small frontier orbital intra and inter molecular interactions [56].
gap is generally associated with a high chemical reactivity, low The natural bond orbital (NBO) calculations [57] were per-
kinetic stability and is also termed as soft molecule [55]. In these formed using NBO 3.1 program implemented in the Gaussian 03
processes, the potentially interesting electronic transitions are package at the DFT/B3LYP/6-31G(d,p) method. It offers a handy
those involving narrow energy gaps. The calculated energy values basis for exploring charge transfer or conjugative interaction in
for enol-imine and keto-amine forms in gas phase are; molecular systems and is an efficient method for interactions
 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195 189

Fig. 5. Experimental (red) and theoretical DFT/B3LYP/6-31G(d,p) (black) FT-IR spectrum. (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)

Table 4 the whole system. The NBO analysis is already proved to be an

Comparison of the experimental and calculated vibrational frequencies (cm1). effective tool for chemical interpretation of hyperconjugative
Experimental IR DFT/B3LYP/631-G(d,p) Assignmentsa
interaction and electron density transfer from the filled lone pair
with KBr electron. The hyper-conjugative interaction energy was deduced
3701.26 3709.55 t (O–H) from the second-order perturbation approach.
3014.45 3077.5 t symmetric (C–H) R1, R2
F 2 ði; jÞ
3079.69 Eð2Þ ¼ qi ð2Þ
3037.5 3108.5 t asymmetric (C–H) R1, R2 ej  ei
1010.43 1386 b in plane (C–H) R1, R2
1251.95 1623 where qi is the donor orbital occupancy, ej and ei are diagonal ele-
827.86 856.51 b out of plane (C–H) R1, R2 ments and F(i, j) is the off diagonal NBO Fock matrix element. The
956.92 945.85 importance of hyper-conjugation and electron density transfer from
1365.17 1455 b out of plane (C–H3)
lone electron pairs of the Y atom to the X–H anti-bonding orbital in
1339.75 1475
1436.09–1827.75 1456.62 b in plane (C–H3) the X–H  Y system has been reported [58–60]. A summary of elec-
1501.6 tron donor orbitals, acceptor orbitals and the interaction stabiliza-
1476.28 tion energy that resulted from the second order perturbation
1470.7
theory calculation results are the aim of the NBO. In the light of
1257.76 1169.5 t (C–C) R1, R2
1548.73 1332.78
these, NBO results showing the formation of Lewis and non-Lewis
1537.3 orbital by the valence hybrids corresponding to the intramolecular
1610.03 1537.3 c (N1–H1) bonds are given in Table 5. In addition the most important interac-
1637.1 tions between ‘filled’ (donors) Lewis-type NBOs and ‘empty’ (accep-
3200–3500 2794.2 t (N1–H1)
tors) non-Lewis NBOs are also reported. In NBO analysis large E(2)
2933.2 2933.5 t symmetric (C–H3)methoxy
1624.16 1640.9 t (N–C) value shows the intensive interaction between electron-donors
2912.4 3055.7 t asymmetric (C–H3) methoxy and electron-acceptors and greater the extent of conjugation of
2964.3 the whole system. The most important possible intensive interac-
1291.95 1307.5 t (C–N–C) tions are given in Table 5. The second order perturbation theory
1365.17
3100–3150 3123 t (C8–H8) analysis of Fock matrix in NBO basis shows strong intramolecular
3110.4 hyperconjugative interactions of p electrons.
3014.45 3055.2 t asymmetric (C–H3)methyl A summary of electron donor orbitals, acceptor orbitals and the
3044.03 interaction stabilization energy that resulted from the second-
2964.3 2952.6 t symmetric (C–H3)methyl
order perturbation theory is reported in Table 5. As can be seen
a
m, stretching; c, rocking; b, bending. Abbreviations: R1, C1–C6; R2, C9–C14 from this table, NBO analysis revealed that the p(C5–C6) ?
phenyl ring. p⁄(C13–C14), p(C11–C12) ? p⁄(C13–C14), p(C5–C6) ? p⁄(C3–
C4), interactions give a strong stabilization to the system of the
among bonds. The larger the stabilization energy value, the more title compound by 253.12 kJ/mol, 218.51 kJ/mol and
intensive is the interaction between electron donors and electron 126.21 kJ/mol, respectively. The interaction between lone pair
acceptors, i.e. the more donating tendency from electron donors n(O1) and the antibonding orbital r⁄(N1–H1) shows the existence
to electron acceptors and the greater the extent of conjugation of of N–H  O intermolecular hydrogen bonding that have
190 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195
Fig. 6. Molecular orbital surfaces and energies of HOMO and LUMO.
Fig. 7. Total electron density mapped with molecular electrostatic potential
surface.
stabilization energies 36.25 kJ/mol. In the case of p(C1–C8) orbital
the p⁄(C2–O1) and p⁄(C5–C6) shows stabilization energy of 29.35
and 26.58 kJ/mol. The interactions p(C–C) and their antibonding
p⁄ interactions are responsible for conjugation of respective
p-bonds in benzene rings. The electron density at the conjugated
p bonds (0.33–1.65) of benzene rings and p⁄ bonds (0.23–0.40)
of benzene rings indicate strong p-electron delocalization
within ring leading to a wide range of stabilization with
26.58–253.12 kcal/mol. The charge transfer interactions are
formed by the orbital overlap between bonding (p) and antibond-
ing (p⁄) orbitals, which results in steric interactions charge transfer
(ICT) causing stabilization of the system. The movement of
p-electron cloud from donor to acceptor i.e. ICT can make the
molecule more polarized and it must be responsible for the NLO
properties of molecule. Therefore, the titled molecule can be ideal
material for non-linear optical applications in future.
The other primary hyperconjugative interactions lone pair NBO
orbitals of n(O1) ? r⁄(N1–H1) and r(C2–O1) ? r⁄(N1–H1) are
stabilized to the molecule up to 36.25 kcal/mol and 1.52 kcal/mol,
respectively. These E(2) values are chemically significant and they
could be used as a measure of the intramolecular delocalization
because of N1–H1  O1 intramolecular bonding.
The energies for the interaction r(C1–C8) ? RY⁄(N1), rC9–
C10) ? r⁄(C9–N1), r(C2–O1) ? RY⁄(C2), r(C2–O1) ? r⁄(C1–C8),
r(C8–N1) ? r⁄(C1–C8), r(C2–O1) ? r⁄(C8–H8), r(C9–N1) ?
r⁄(C8–N1), r(N1–H1) ? RY⁄(C8), n(N1) ? p⁄(C1–C8) and
n(O1) ? RY⁄(C2) are 0.85, 4.24, 1.17, 1.38, 2.02, 0.55, 2.36, 0.7,
62.95 and 10.01 kcal/mol, respectively. These interactions are
clearly demonstrate the single-double bond arrangement which
are leads to enol-keto tautomerism. Besides, the higher stabiliza-
tion of E(2) energy is related to the resonance in benzene rings
and effect of stabilization of the H-bond systems. The efficient
p ? p⁄ and n ? p⁄ interactions significantly influence crystal pack-
ing, electron absorption and charge transfer interactions. As can be
seen from results, the conjugation of transition apparent that intra
and inter hydrogen bonds interactions significantly influence crys-
tal packing with this molecule. Besides, p ? p⁄ and n ? p⁄ interac-
tions are also closely related the UV–Vis absorption bands.
Mulliken population analysis and natural population analysis
The calculation of atomic charges plays an important role in the
application of quantum mechanical calculations to molecular sys-
tems [61]. Our interest here is in the comparison of different meth-
ods to describe the electron distribution in title compound as
broadly as possible, and assess the sensitivity of the calculated
charges to changes in first, the choice of the basis set and second
is the choice of the quantum mechanical method. Mulliken
charges, calculated by determining the electron population of each
atom as defined in the basis functions.
The total atomic charge values are obtained by Mulliken
population analysis with optimized geometry and natural charges
are obtained by natural bond orbital analysis (NBO) [62] are listed
in Table 6. The two methods predict the same tendencies. As can be
seen in results that all the hydrogen atoms have a net positive
charge.
According to Mulliken and NBO methods, the obtained atomic
charge shows that the H1, H3A and C2 atoms has bigger positive
atomic charges (0.352e(M); 0.472e(NBO)), (0.318e(M);
0.492e(NBO)) and (0.394e(M); 0.454e(NBO)), than the other
hydrogen atoms. This is due to the presence of N1–H1  O1 strong
intramolecular and O3–H3A  O1 intermolecular bonding. N1, O1,
O2 and O3 atoms are most negative atomic charges (0.633e(M);
0.547e(NBO)), (0.632e(M); 0.671e(NBO)), (0.535e(M);
0.532e(NBO)) and (0.559e(M); 0.688e(NBO)).
According to these results, a major part of NBO’s net charges are
slightly longer than Mulliken charges. The intention is to accurately
model partial charge magnitude and location within a molecule.
Mulliken population analysis is a good way to account for differ-
ences in electronegativities of atoms within the molecule and fre-
quently uses for supporting the MEP and Fukui analysis. The
results are good harmony with each other and MEP results. MEP
and Mulliken Population Method can be use for interpreting and
predicting the reactive behavior of a wide variety of chemical sys-
tems in both electrophilic and nucleophilic reactions.
 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195 191

Table 5
Second order perturbation theory analysis of Fock matrix in NBO basis.

Donor (i) Type EDA, % Acceptor (j) Type EDA, % E(2)a (kcal/mol) Ej  Eib (a.u.) F(ij)c (a.u.)
(occupancy) EDB, % (occupancy) EDB, %
BD C1–C8 r 50.45 RY⁄C2 – – 1.09 1.60 0.037
(1.97601) 49.55 (0.01245)
BD C1–C8 r 50.45 RY⁄N1 – – 0.85 1.98 0.037
(1.97601) 49.55 (0.00334)
BD C1–C8 r 50.45 BD⁄C1–C2 r⁄ 47.24 2.56 1.2 0.05
(1.97601) 49.55 (0.05439) 52.76
BD C1–C8 r 50.45 BD⁄C9–N1 r⁄ 61.67 4.24 1.14 0.062
(1.97601) 49.55 (0.03091) 38.33
BD C1–C8 p 61.86 RY⁄C9 – – 0.87 2.12 0.042
(1.65131) 38.14 (0.00099)
BD C1–C8 p 61.86 BD⁄C2–O1 p ⁄
73.09 29.35 0.28 0.082
(1.65131) 38.14 (0.43061) 26.91
BD C1–C8 p 61.86 BD⁄C5–C6 p⁄ 43.2 26.58 0.29 0.079
(1.65131) 38.14 (0.33267) 56.8
BD C2–O1 r 35.06 RY⁄C2 – – 1.17 1.87 0.042
(1.99514) 64.94 (0.01245)
BD C2–O1 r 35.06 BD⁄C1–C8 r ⁄
49.24 1.38 1.50 0.041
(1.99514) 64.94 (0.02813) 50.76
BD C2–O1 r 35.06 BD⁄N1–H1 r⁄ 22.50 1.52 1.40 0.042
(1.99514) 64.94 (0.09926) 77.50
BD C6–O2 r 32.20 RY⁄C7 – – 1.44 1.63 0.043
(1.99123) 67.80 (0.00158)
BD C6–O2 r 32.20 BD⁄C1–C2 r ⁄
47.24 1.70 1.39 0.044
(1.99123) 67.80 (0.05439) 52.76
BD C8–N1 r 38.07 RY⁄C9 – – 2.30 2.00 0.061
(1.98632) 61.93 (0.00702)
BD C8–N1 r 38.07 BD⁄C1–C8 r⁄ 49.55 2.02 1.38 0.047
(1.98632) 61.93 (0.01695) 50.45
BD C8–N1 r 38.07 BD⁄C8–H8 r⁄ 37.72 0.55 1.31 0.024
(1.98632) 61.93 (0.01864) 62.28
BD C9–N1 r 38.33 BD⁄C8–N1 r ⁄
61.93 2.36 1.33 0.050
(1.98505) 61.67 (0.01704) 38.07
BD C11–C12 p 53.99 RY⁄O3 – – 1.02 1.29 0.036
(1.65322) 46.01 (0.00132)
BD C11–C12 p 53.99 BD⁄C9–C10 p⁄ 48.53 22.09 0.29 0.072
(1.65322) 46.01 (0.40876) 51.47
BD C11–C12 p 53.99 BD⁄C13–C14 p ⁄
47.60 16.51 0.30 0.063
(1.65322) 46.01 (0.33464) 52.40
BD C12–O3 r 33.03 BD⁄C11–C12 r ⁄
49.95 0.71 1.47 0.029
(1.99484) 66.97 (0.02663) 50.05
BD N1–H1 r 77.50 RY⁄C8 – – 0.70 1.83 0.032
(1.97520) 22.50 (0.02228)
BD O3–H3 r 74.91 RY⁄C12 – – 1.58 1.65 0.046
(1.98894) 25.09 (0.00755)
LP N1 – – BD⁄C1–C8 p ⁄
38.14 62.95 0.27 0.12
(1.51370) (0.36884) 61.86
LP N1 – – BD⁄C9–C10 p⁄ 48.53 34.5 0.28 0.089
(1.51370) (0.40876) 51.47
LP O1 – – RY⁄C2 – – 10.01 1.5 0.11
(1.96345) (0.03035)
LP O1 – – BD⁄C2–C3 r⁄ 50.13 14.21 0.83 0.099
(1.85030) (0.04105) 49.87
LP O1 – – BD⁄ N1–H1 r ⁄
22.50 36.25 0.72 0.147
(1.97426) (0.09926) 77.50
LP O2 – – BD⁄C5–C6 p⁄ 43.20 31.94 0.36 0.1
(1.83928) (0.33267) 56.80
LP O3 – – BD⁄C11–C12 p⁄ 46.01 29.04 0.34 0.096
(1.98706) (0.40324) 53.99
BD C1–C8 p 38.14 BD⁄C5–C6 p ⁄
43.20 91.26 0.02 0.067
(0.36884) 61.86 (0.33267) 56.80
BD C2–O1 p 73.09 BD⁄C3–C4 p ⁄
45.79 88.85 0.03 0.081
(0.43061) 26.91 (0.23666) 54.21
BD C5–C6 p 43.20 BD⁄C3–C4 p⁄ 45.79 126.21 0.02 0.075
(0.33267) 56.80 (0.23666) 54.21
BD C5–C6 p 48.53 BD⁄C13–C14 p⁄ 47.60 253.12 0.01 0.082
(0.40876) 51.47 (0.33464) 52.40
BD C11–C12 p 60.57 BD⁄C13–C14 p ⁄
47.60 218.51 0.01 0.082
(1.59930) 39.43 (0.33464) 52.40

Percentage electron density over bonded atoms (EDA,B, %).

a
E(2) means energy of hyperconjucative interactions (stabilization energy).
b
Energy difference between donor (i) and acceptor (j) NBO orbitals.
c
F(i, j) is the Fock matrix element between i and j NBO orbital.
192 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195

Table 6 regions where a chemical species (molecule) will amend its density
Calculated net charges by Mulliken Population Method and Natural Population when the numbers of electrons are modified or it indicates the ten-
analysis (NPA).
dency of the electronic density to deform at a given position upon
Atom B3LYP/6-31G(d,p) B3LYP/6-31G(d,p) (NPA) accepting or donating electrons [65]. The condensed or atomic
Mulliken charges natural charges 
Fukui functions on the jth atom site, for electrophilic f j (r), nucle-
C1 0.086160 0.25891 þ  0 þ
ophilic f j (r), and free radical f j attacks are defined as f j f j ¼
C2 0.395167 0.45432
 0
C3 0.125255 0.33055 qj ðN þ 1Þ  qj , fj
¼ qj ðNÞ  qj ðN  1Þ and ¼ 12 ½qj ðN þ 1Þ
fj
C4 0.083807 0.18350
qj ðN  1Þ respectively, where qj is the atomic charge (Mulliken or
C5 0.172009 0.38698
C6 0.343158 0.37012 NBO, etc.) at the jth atomic site in the anionic (N + 1), cationic
C7 0.078015 0.32477 (N  1) or neutral molecule. Parr and Yang [64,65] showed that
C8 0.170805 0.13257 sites in chemical species with the largest values of Fukui function
C9 0.274035 0.12556
(fj) shows high reactivity for corresponding attacks. The Fukui
C10 0.099919 0.23811
C11 0.154040 0.31250 functions calculated from the NBO charges have been reported to
C12 0.340503 0.32819 be in good acceptation [66].
C13 0.155927 0.27583 The values of calculated Fukui functions based on NBO charges,
C14 0.102349 0.01544
given in Table 7 indicates that in title compound the reactivity order
C15 0.391953 0.71636
N1 0.633034 0.54735
for the nucleophilic case is H3A > H1 > C2 > C12 > C6 > H3 >
O1 0.632767 0.67159 H13 > H4 > H15A > H8 > H5 > H15B > H15C > H10 > H7C > H7A >
O2 0.535076 0.53223 H7B > C9 > C14 and the electrophilic reactivity order is O3 >
O3 0.559203 0.68892 C15 > O1 > N1 > O2 > C5 > C3 > C11 > C1 > C7 > C13 > C4 > C10 > C14
H1 0.352713 0.47224
while the order of sites for free radicals attack is H3A > H1 >
H3 0.083275 0.24658
H3A 0.318164 0.49225 C2 > C6 > C12 > H15B > H15C > H13 > H15A > H3 > H10 > H5 > H4 >
H4 0.085381 0.23937 H8 > H7C > H7A > H7B > C8 > C9. The local softness condensed to
H5 0.077676 0.23990 
an atom location defined by s
j ¼ f j S [67] and local electrophilicity
H7A 0.117910 0.21018

H7B 0.117487 0.20983 indices [68] defined by ¼ w
j fj
w are also calculated to illustrate
H7C 0.121532 0.23007 the reactivity of atoms. These equations envisage the most elec-
H8 0.139445 0.23868
H10 0.095112 0.24099
trophilic site in a system has the maximum value of s+ and w+
H11 0.079022 0.23562 while maximum value of s- and w-corresponds to the nucleophilic
H13 0.096256 0.25121 site in the molecule. The local reactivity descriptors like s;0
j and
H15A 0.112398 0.24862
H15B 0.145466 0.25926 w;0
j provide the reactivity tendencies of local site during
H15C 0.139313 0.25747

Table 7
Mulliken electronegativity, chemical activity and Fukui function Values of the Fukui function considering Natural Population analysis (NPA).

analysis Atom fj  fj + f0 j
C1 0.16297 0.18595 0.25891
The global reactivity descriptors like chemical potential, elec- C2 0.24625 0.45507 0.45432
tronegativity, hardness, softness and electrophilicity index and C3 0.17956 0.23901 0.33055
local reactivity descriptor like Fukui functions can be calculated C4 0.05338 0.19148 0.18350
C5 0.23004 0.24334 0.38698
using DFT. Following Parr and Pearson [63], the electronic chemical
C6 0.22599 0.36916 0.37012
potential, describing the escaping tendency of electron from a C7 0.15757 0.33765 0.32477
stable system can be calculated as l = (IP + EA)/2. C8 0.18659 0.12935 0.13257
Electronegativity (v) is described as negative of the electronic C9 0.08048 0.13750 0.12556
chemical potential. Chemical hardness which demonstrates the C10 0.09653 0.21035 0.23811
C11 0.17475 0.28804 0.31250
resistance to alteration in electron distribution is given by C12 0.17329 0.38199 0.32819
g = (IP  EA)/2, and is well correlated with the stability and C13 0.15416 0.25956 0.27583
reactivity of the chemical system. The inverse of the hardness is C14 0.00561 0.01274 0.01544
expressed as the global softness S = (1/g). The global electrophilic- C15 0.35268 0.72782 0.71636
N1 0.26898 0.47593 0.54735
ity index (x), introduced by Parr et al. [64] is calculated in terms of
O1 0.33204 0.53493 0.67159
chemical potential and the hardness as x = l2/2g and assess the O2 0.26362 0.51199 0.53223
lowering of energy due to maximal electron flow between donor O3 0.35271 0.63960 0.68892
and acceptor. Here the ionization potential (IP) and electron affin- H1 0.22930 0.47715 0.47224
ity (EA) are defined as the difference in ground state energy H3 0.10679 0.27660 0.24658
H3A 0.23758 0.51068 0.49225
between the cationic and neutral system and difference in ground H4 0.09858 0.27362 0.23937
state energy between neutral and anionic system. The values of H5 0.10495 0.27039 0.23990
electronegativity, chemical hardness, softness, and electrophilicity H7A 0.09760 0.22261 0.21018
index for keto and enol forms are 3.376 eV, 1.696 eV, 0.589 eV and H7B 0.09735 0.22247 0.20983
H7C 0.10448 0.25256 0.23007
3.36 eV and 3.5 eV, 1.944 eV, 0.514 eV, 3.15 eV in gas phase,
H8 0.09649 0.26093 0.23868
respectively. Considering the chemical hardness, if one molecule H10 0.11491 0.25492 0.24099
has large HOMO–LUMO gap, it is a hard molecule or small H11 0.10545 0.26060 0.23562
HOMO–LUMO gap it is a soft molecule. One can also relate the sta- H13 0.11344 0.27522 0.25121
bility of molecule to hardness, which means that the molecule with H15A 0.11201 0.27219 0.24862
H15B 0.12634 0.26676 0.25926
least HOMO–LUMO gap means it is more reactive. The local
H15C 0.12672 0.26315 0.25747
reactivity descriptor like Fukui function indicates the preferred
 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195 193

nucleophilic or electrophilic attacks. MEPs contour and Fukui func-
tion analysis demonstrate that the most electrophilic sites in title
compound are O3, C15, O1, N1 and O2 whereas the most nucle-
ophilic site is H3A, H1 and C12.
Lower values of hardness and Mulliken electronegativity is sup-
ported that the compound is more stable and more lower chemical
activity. Position of reactive electrophilic sites and nucleophilic
sites are accordance with the total electron density surface and
chemical behavior. If one compares the three kinds of attacks it
is possible to observe that, electrophilic attack is bigger reactivity
comparison with the nucleophilic and radical attack.
Solvent effect on tautomerism and UV–vis absorption spectra
TD-DFT at B3LYP/631G(d,p) level by adding polarizable contin-
uum model (PCM) calculations were started from gas phase and
solution phase. The experimental UV–Vis spectra of titled com-
pound in various organic solvents (benzene, chloroform, ethanol
and DMSO) were recorded within 200–800 nm range (Fig. 8). The
theoretical UV–Vis absorption bands of the molecule for keto-
amine and enol-imine forms in gas phase, ethanol, DMSO, chloro-
form and benzene are comparatively given in Table 8. These four
solvents have different dielectric constants and dipole moments;
benzene e = 2.3, l = 0 D; chloroform e = 4.9, l = 1.04 D; ethanol
e = 24.3, l = 1.69 D and DMSO e = 46.7, l = 3.96 D, respectively.
The greater the dielectric constant, the greater the polarity (in this
paper; DMSO = high, gas phase = low). A second comes from
directly measuring the dipole moment. Results obtained from used
solvents having different polarities are shown in Table 8. In present
work, total energies, dipole moments, EHOMO and ELUMO values
increase with increase of the polarity of the solvent for both enol
and keto forms.
As mentioned above, solvents are important because protic sol-
vents can participate in hydrogen bonding, which is a powerful
intermolecular or intramolecular force. Protic solvents have N–H
or O–H bonds and these bonds can serve as a source of protons
(H+). Aprotic solvents may have hydrogens on them somewhere,
but they lack O–H or N–H bonds, and therefore cannot hydrogen
bond with themselves. The chosen solvents are chloroform and
benzene is a nonpolar solvent and DMSO is a polar aprotic solvent.
Besides, ethanol is a polar protic solvent acting as both hydrogen
donor and acceptor. Charge delocalization of the molecule
increases with the increasing polarity of solvents, therefore,
induces the dipole moments raised. However, oscillator strength
(f) and DE values were not changed linearly with increasing polar-
ity. Forwhy, deviations from linearity is likely related to chemical
properties of solvents.
In experimental electronic spectra involves all contributions to
the transitions. In the UV–Vis spectra of o-hydroxy schiff base
compounds, the presence of an absorption band at less than
400 nm indicates the enol imine tautomeric form. On the other
hand, compounds adopt keto-amine tautomeric form show a new
absorption band at greater than 340 nm [69,70]. As for that men-
tioned above, the experimental UV–Vis absorbance bands in differ-
ent solvents could be clarifies both enol-keto tautomerism.
Because electrons are so movable and these transitions can be
shown smoothly. All of the maximum peaks are inholds also keto
and enol forms for different solutions. But it is known that the
structure tends to keto-amine form and all other calculations sup-
ported that the compound display keto-amine form in solid state.
The theoretical and experimental absorbtion bands for different
solvents are given in Table 8.

Nonlinear Optical Effects (NLO)

Nonlinear optical (NLO) effects arise from the interactions of

Fig. 8. The solvent effect on UV–Vis spectra of the title compound in DMSO, ethanol
and chloroform and benzene.
electromagnetic fields in various media to produce new fields
altered in phase, frequency, amplitude or other propagation char-
acteristics relative to the incident optical fields. When a beam of
light propagates through a material, the interaction of the optical
field with organic molecules in the material induces charge varia-
tion and displacement of associated atoms [71].

Table 8
Electronic properties of calculated energies, excitation energies, oscillator strengths, dipole moments and frontier orbital energies for the keto-amine and enol-imine
tautomerism.

Gas phase Benzene Chloroform Ethanol DMSO

ETOTAL (a.u.) keto-amine form 861.0658 861.0775 861.0835 861.0881 861.0884
ETOTAL (a.u.) enol-imine form 861.0915 861.0813 861.0863 861.9649 861.9804
EHOMO (eV) keto-amine form 5.072 5.171 5.243 5.288 5.294
EHOMO (eV) enol-imine form 5.452 5.414 5.438 5.454 5.459
ELUMO (eV) keto-amine form 1.680 1.763 1.812 1.849 1.857
ELUMO (eV) enol-imine form 1.563 1.501 1.507 1.564 1.568
DE (eV) keto-amine form 3.392 3.408 3.431 3.439 3.447
DE (eV) enol-imine form 3.889 3.913 3.901 3.89 3.891
Excitation energy (nm) keto-amine form 365.12 365.44 366.62 367.3 369.04
Excitation energy (nm) enol-imine form 363.46 363.76 364.1 363.72 365.65
Experimental wavelength (nm) – 381 381 382 391
Oscillator strength (f) keto-amine form 0.4012 0.4422 0.4738 0.4635 0.4673
Oscillator strength (f) enol-imine form 0.6227 0.6619 0.6508 0.6308 0.657
l (D) Keto-amine form 6.1034 6.7348 7.26 7.3002
l (D) enol-imine form 5.8531 4.9879 5.4042 5.5875 5.7724
194 Z. Demircioğlu et al. / Journal of Molecular Structure 1091 (2015) 183–195

Linear and non-linear optical properties of molecular crystals Conclusion

have attracted considerable attention for both practical and theo-
retical reasons, organic materials can present large non-linear opti- This study demonstrates that scaled DFT (B3LYP) calculations
cal (NLO) responses while being resistant optical damage. The are powerful approach for understanding the vibrational spectra
method predicts and interprets the molecular properties, the of the title molecule. A complete vibrational and molecular struc-
polarizabilities and hyperpolarizability, which are more advanced ture analysis have been performed based on the quantum
and can often achieve good agreement with experiment. mechanical approach by DFT calculation. The difference between
The first hyperpolarizability (b) is a third-rank tensor that can the observed and scaled wavenumber values of most of the
be described by a 3  3  3 matrix. The 27 components of the 3D fundamentals are very small. Therefore, the assignments made at
matrix can be reduced to 10 components due to the Klein man DFT level of theory with only reasonable deviations from the
symmetry [72,73]. The components of b are defined as the coeffi- experimental values seem to be correct.
cients in the Taylor series expansion of the energy in the external The net charge distribution of title compound was calculated by
electric field. When the external electric field is weak and homoge- the Mulliken Population Method and natural population analysis.
nous, this expansion becomes: The MEP shows that the negative potential sites are on elec-
tronegative atoms as well as the positive potential sites are around
E ¼ E0  la F a  1=2aab F a F b  1=6babc F a F b F c þ . . . ð3Þ
the hydrogen atoms The calculated HOMO and LUMO energies can
where E0 is the energy of the unperturbed molecules, Fa, the field at be used to semiquantitatively estimate the ionization potential,
the origin and la, aab and babc are the components of dipole electron affinity, electronegativity, electrophilicity index, hardness
moment, polarizability and the first hyperpolarizabilities, respec- and chemical potential.
tively. The total static dipole moment l, polarizability a, mean In order to understand electronic transitions of the molecule,
polarizability a0 and the mean first hyperpolarizability b0, using TD-DFT calculations on electronic absorption spectra in several
the x, y, z components are defined as follows [74]: solvents and gas phase were performed comparatively.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Computational and experimental UV–Vis studies for various
l¼ ðl2x þ l2y þ l2z Þ ð4Þ organic solvents of different polarities indicate that the stability
of the molecule increases upon an increase in the polarity of sol-
axx þ ayy þ azz vent. The experimental results show that molecule exists enol
a¼ ð5Þ and keto forms even in solvent media. However in solid state
3
calculations and experimental results shows the compound tends
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi to keto-amine form.
btop ¼ ðbxxx þ bxyy þ bxzz Þ2 þ ðbyyy þ byzz þ byxx Þ2 þ ðbzzz þ bzxx þ bzyy Þ2 Fukui function helps to identifying the electrophilic and nucle-
ð6Þ ophilic nature of a specific site within a molecule. According to sta-
bility of the molecule to softness, which means that the molecule
The dipole moment, polarizability and the first with least energy gap and means that it is more reactive molecule.
hyperpolarizability were calculated with the level of B3LYP/6- Natural bond orbital (NBO) calculations reveals the delocalization
31G(d,p). and hyperconjugation interaction, intramolecular charge transfer
Since the values of the polarizability (a0) and hyperpolarizabil- and stabilization energy of molecule. According to NBO results,
ity (btot) of the Gaussian 03 output are reported in atomic units we can determine the ideal Lewis type structure. NBO analysis
(a.u.), the calculated values have been converted into electrostatic indicating the strong intramolecular hyperconjugative interaction
units (esu) (a: 1 a.u. = 0.148  1024 esu and b: 1 a.u. = 8.639  within the molecule and stability of the molecule. This ideality
1033 esu). As can be seen in Table 9, the calculated values of elec- has also been arised percentage of valence hybrids of the atoms
tronic dipole moment (l), polarizability (a) and the first and the weight of each atom in each localized electron pair bond,
hyperpolarizability (b) for the titled molecule are 5.03 D, clearly. We hope all conclusions of this study will help researchers
30.716 Å3 and 2.35  1029 cm5/esu. to analyze and synthesize new materials.
The large value of hyperpolarizability, bo which is a measure of
the non-linear optical activity of the molecular system, is asso-
ciated with the intramolecular charge transfer, resulting from the Supplementary data
electron cloud movement through p conjugated frame work from
electron donor to electron acceptor groups. The physical properties CCDC 1037960 contains the supplementary crystallographic
of these conjugated molecules are governed by the high degree of data for this paper. These data can be obtained free of charge via
electronic charge delocalization along the charge transfer axis and www.ccdc.cam.ac.uk/data_request/cif, by emailing data_request@
by the low band gaps. So we can conclude that the title molecules ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic
are an attractive object for future studies of nonlinear optical Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44
properties. 1223 336033.

Table 9
Calculated dipole moments (l), polarizability (a) and first hyperpolarizability (b)
Acknowledgement
components for the title compound.
The authors wish to acknowledge the Faculty of Arts and
lx = 0. 183 a.u. bxxx = 2788.401 a.u.
ly = 1.970 a.u. bxxy = 85.661 a.u.
Sciences, Ondokuz Mayis University, Turkey, for the use of the
lz = 0.051 a.u. bxyy = 110.422 a.u. STOE IPDS 2 diffractometer (purchased under grant F.279 of the
ltot = 5.03 D byyy = 39.433 a.u. University Research Fund).
axx = 346.987 a.u. bxxz = 49.53 a.u.
axy = 17.837 a.u. bxyz = 31.946 a.u.
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