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by density functional theory reported in our previous work
[4]. Synthesis and structural characterization of (E)-N'-
((Pyridin-2-yl) methylene) benzohydrazide by X-ray
diffraction, FT-IR, FT-Raman and DFT methods published by
N. Ramesh Babu et al. [5]. Due to the easy synthesis of such
compounds, a large number of hydrazone compounds have
been synthesized and structurally characterized by (Yehye et
al.,[6] ; Fun, Patil, Jebas et al.,[7] ; Fun, Patil, Rao et al., [8] ;
Yang et al.,[9] ). Recently Josephine Novina et.al reported
[10] the X-ray crystal structure of (E)-N'-(3,4-
Dimethoxybenzylidene)-nicotinohydrazide monohydrate.
With the guide of above seen literary works, it is clear that
there is no quantum mechanical study on this title molecule
which has spurred to do a nitty- gritty quantum mechanical
investigation for comprehension the vibrational modes,
NBO, HOMO–LUMO, MEP and thermodynamic properties of
title compound.
The present examination has been attempted to supply
adequate vibrational investigation of a compound
DMBNH∙H2O through FT-IR and FT-Raman spectra.
Subsequently, the present study intends to give a complete
depiction of the molecular geometry and molecular
vibrations of the title compound. The calculated vibrational
spectra were dissected on the premise of the potential
energy dispersion (PED) of each vibrational mode, which
permitted us to acquire a quantitative and also subjective
interpretation of the infrared and Raman spectra. ones
redistribution regarding electron density (ED) in a variety
of bonding in addition to antibonding orbitals in addition
to E2 energies have been calculated from natural bond
orbital (NBO) analysis applying DFT method to give clear
proof of stabilization originating by the hyper conjugation
associated with different inter and intra-molecular
interactions. The UV–Vis spectroscopic analysis along with
HOMO–LUMO examination has been utilized to clarify the
charge exchange inside of the molecule. The electric dipole
moment (ߤ) and first request hyperpolarizability (ߚ)
estimation of the particle have been figured utilizing DFT
system to study the NLO property. At last electronegativity
(χ), hardness (η), softness (S), properties, Molecular
Electrostatic Potential maps (MEP) and thermodynamic
properties were additionally computed.
2. MATERIALS AND METHODS
2.1. Synthesis
The title compound has been synthesized with the aid of
Reference [10].
2.2. FT-IR, FT-Raman and UV–Vis analysis
BRUKER Optik GmbH FT-IR spectrometer has been used to
record the FT-IR spectrum of DMBNH∙H2O compound
utilizing KBr pellet technique at room temperature. The
spectral range is 4000-400 cm-1, with 10 cm-1 scanning
speed, and 4 cm-1 spectral resolution. BRUKER RFS 27: FT-
Raman Spectrometer equipped with FT-Raman module
accessory was used to record FT-Raman spectrum of the
DMBNH∙H2O compound utilizing 1064 nm line of Nd: YAG
laser as excitation wavelength within the spectral range
3500-50 cm-1. The instrument was set to 2 cm-1 spectral
resolution in back scattering mode. The laser output was
held in 100 mW because of its solid sample. Cary 500 UV-
VIS-NIR spectrometer was used to record the UV absorption
spectra associated with DMBNH∙H2O were examined with
the range 200-800 nm. The UV pattern is usually
acknowledged from the 10-5 molar solution connected
with DMBNH∙H2O, dissolved with DMSO solvent.
2.3. Quantum chemical calculations
The whole quantum chemical computations have been done
at DFT (B3LYP) and M06-2X level of calculations with 6-
31G(d,p) basis set utilizing the Gaussian 09 program
package [11]. What's more, the figured vibrational
frequencies were elucidated by method for the potential
energy distribution (PED) investigation and assignments of
all the crucial vibrational modes by utilizing VEDA 4
program [12].
The high parameterized, empirical exchange functionals,
M05-2X and M06-2X, grew by Zhao and Truhlar [13] have
been indicated to depict noncovalent interactions superior
to density functionals which are as of now in like manner
utilization. On the other hand, these routines have yet to be
completely benchmarked for the sorts of connections critical
in biomolecules. M05-2X and M06-2X are asserted to catch
''medium-range'' electron relationship; in any case, the
''long-range'' electron correlation dismissed by these
functionals can likewise be vital in the coupling of non-
covalent complex
Additionally, these techniques have been utilized as a part of
various hypothetical studies, as of late [14,15]. To be able to
investigate the reactive sites of the title compound the
molecular electrostatic potential was evaluated. Moreover,
to show nonlinear optic (NLO) activity involving
DMBNH∙H2O molecule, ones dipole moment, linear
polarizability and also primary hyperpolarizability were
taken from molecular polarizabilities based on the finite-
field approach. Natural bond orbital (NBO) analyses [16]
were carryout employing NBO 3.1 process equally
implemented for the Gaussian 09W package for the above
said level. The thermodynamic functions changes (the heat
capacity, entropy, as well as enthalpy) have been
investigated for the distinct temperatures from the
vibrational frequency calculations of molecule.
3. PREDICTION OF RAMAN INTENSITIES
The Raman activities (Si) calculated by means of Gaussian 09
application [11] has been converted to comparitive Raman
intensities (IR). The hypothetical Raman intensity (IR), which
simulates the experimental Raman spectrum, is given by
way of the equation [17, 18]:
Ii R= C (ν0 − νi) 4νi-1 Bi-1 Si {1}
where Bi is a temperature element which accounts for the
depth contribution of excited vibrational states, and is
represented by means of the Boltzman distribution
Bi = 1 – (exp−hνic/kT) {2}
The theoretical Raman spectra have been calculated via the
Raint program [19].
4. RESULTS AND DISCUSSION
4.1. Conformational stability analysis
Fig. 1 shows a one-dimensional relaxed PES scan of the C21-
O20-C14-C13 dihedral angle using the B3LYP/6-31G(d,p)
level of calculation. The period of calculation, all the
geometrical parameters were simultaneously relaxed, while
the C21-O20-C14-C13 angle was varied in steps of 10°, 20°,
30°. ...360°. Ones program searched pertaining to a
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minimum point pertaining to each 10°. From the
conformational energy profile we observed that one maxima
at 170° (-1046.940 Hartree) and one local minima (stable
conformers) observed at 250° (-1046.963 Hartree) and for T
(C21-O20-C14-C13). Our own optimized geometry of an
molecule under study can be verified to become located
for the local actual minima on potential energy surface, In
the same way the calculated vibrational spectra contains
not any imaginary wavenumber. Excess results usually are
based towards the most stable conformer regarding
molecule DMBNH∙H2O to clarify molecular structure and
also assignments regarding vibrational spectra.
Energy=-1046.9633 Hartree at 250°
Structure of stable conformer of title molecule
Fig. 1. Dihedral angle-relative energy curves of the (E)-N'-(3,4-
Dimethoxybenzylidene)-nicotinohydrazide monohydrate by
B3LYP/6- 31G(d,p) level of theory.
4.2. Structural analysis
The optimized molecular structure of a compound
throughout atom numbering scheme adopted at the
computations is usually available within Fig.2. X-ray
diffraction analysis indicates the DMBNH∙H2O crystallizes
within monoclinic system in P21/n space group as well as
the calculated lattice constants tend to be a = 4.9128 Å, b =
25.137 Å, c = 12.2950 Å, ߙ= ߛ ൌ 90° and ߚ = 96.513°.
The crystal data and parameters for structure refinement
details are given in Table 1. The streamlined geometrical
parameters are exhibited in Table 2.
The optimized C-C bond length of the phenyl ring varies in
the range from 1.384 Å to 1.409 Å and 1.389 Å to 1.414 Å
calculated by M06-2X and B3LYP level of calcuations
respectively, which is in great concurrence with XRD
information, 1.373 Å-1.412 Å. C-H bond lengths of the
phenyl ring will be fall on the quantity through 1.083 Å
to 1.086 Å by both M06-2X and B3LYP level of calcuations,
which is marginally more noteworthy than that of XRD
values at 0.930 Å. Then again the C-C bond length of the
pyrinine ring fluctuates from 1.389 Å to 1.399 Å/ 1.393 Å to
1.405 Å and 1.348 Å to 1.371 Å ascertained by M06-
2X/B3LYP and XRD individually. The C-N bond length of the
pyridine ring C5-N6=1.335 Å /1.340 Å /1.326 Å and N6-
C7=1.331 Å /1.335 Å /1.331 Å found by M06-2X /B3LYP/
XRD respectively. The C-H bond length of the pyridine ring
additionally marginally more noteworthy than that of
observed XRD esteem. Case in point the bond length C3-
H22=1.083 Å (M06-2X)/1.082 Å (B3LYP)/0.930 Å (XRD).
Then again little augmentations happen in the methoxy
group bond lengths. Case in point O−CH3 group C─H bond
lengths are C19-H31=1.089 Å/1.091 Å, C19-H32=1.096 Å
/1.097 Å and C19-H33=1.096 Å /1.097 Å calculated by M06-
2X/B3LYP level of calculations respectively.
Fig. 2. The optimized molecular structure of the title compound
with atom numbering scheme
Just like oxygen will be further electronegative compared
to carbon, the electrons with the C═O bond are drawn
on the oxygen. This implies that carbonyl compounds are
polar and get considerable dipole moments. The C1═O8
bond will be short 1.230 Å, 1.214 Å (M06-2X, B3LYP) / 1.232
Å (XRD). For the methoxy substitution of any benzene ring
the bond lengths of a benzene is actually not same;
pertaining to example bond length involving
C14─C15=1.409Å (M06-2X)/1.414Å (B3LYP)/ 1.412Å (XRD)
and C15─C16=1.397 Å (M06-2X)/1.402 Å (B3LYP) /1.373 Å
(XRD), which is more noteworthy than the C16-C17=1.391
Å(M06-2X) / 1.392 Å(B3LYP)/ 1.382 Å (XRD) at the rest of
the substituent, the reason for the elongation involving
these kind of bond lengths are usually due to the
substitution of an O−CH3 group of an benzene ring. The
ring carbon atom on the substituted benzene exert small
attraction for the valance electron cloud regarding
hydrogen atom resulting straight down with the C−H
force constant along with increase for the corresponding
bond length. Other bond lengths usually are exhibited
inside Table 2. From the theoretical values, we found the
idea most of our optimized bond lengths are slightly
larger than our experimental values due to be able to fact
that the theoretical calculations belong to be able to
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isolated molecules throughout gaseous phase as well as the
experimental results belong for molecules in the solid state.
Table 1. Crystal data and parameters for structure refinement of
the title compound
Compound (I)(a)
Molecular formula C15H15N3O3.H2O
Molecular weight 303.32
Crystal system Monoclinic
Space group P21/n
a(Å) 4.9128 (6)
b(Å) 25.137 (4)
c(Å) 12.2950 (16)
α(°) 90
β(°) 96.513 (4)
γ(°) 90
V(Å3) 1508.6 (4)
Z 4
Dcalc (g cm-3) 1.482
Crystal dimensions (mm) 0.50×0.35× 0.30
μ (mm-1) 0.1
Radiation λ (Å) 0.71073
Reflections measured 11633
(a)Taken from Ref. [10]
With the electron donating substituent on the benzene
ring, the symmetry of benzene rings are usually bended,
yielding in order to ring angles smaller in comparison with
(120◦
) in the simple steps associated with substitution.
For the electron donating effect connected with O−CH3
group, this can be observed which the bond angles for the
point of substitution in phenyl ring is usually
C13─C14─C15 =119.8° (M06-2X)/119.5° (B3LYP) / 119.6°
(XRD) and C14─C15─C16=119.3° (M06-2X)/119.2° (B3LYP)
/ 119.6° (XRD). This demonstrates that the inner bond angle
is less than 120°. The same pattern is seen on the pyridine
ring; because of the C1═O8 substitution on the pyridine ring
the ring is mutilated, the bond angle C3-C2-N7=
118.2°(M06-2X)/117.7°(B3LYP) /116.4°(XRD), which is to
be smaller when compared with 120°. The bond angle of
the water molecule is H38-O37-H39=108.6° (M06-
2X)/108.9° (B3LYP) which is great concurrence with XRD
esteem at 108°. The molecule of the title hydrazide
derivative, DMBNH∙H2O, exists in a trans adaptation
concerning the C11═N10 double bond with the torsion angle
C1 −N9−N10−C11 =174.6°(M06-2X)/175.1° (B3LYP) which
is great concurrence with XRD values at 178.8°. One of an
methoxy group can be almost coplanar with the C15−C16
benzene ring whereas the various other sole deviates
somewhat with the benzene ring plane [torsion angles:
C19−O18−C15−C16 = -1.5°/-1.4°/−3.9°, C21−O20−C14−C13
= -16.7°/-16.2°/16.5°] calculated by M06-2X/B3LYP as
well as XRD respectively. Crystal packing of the title
compound viewed along the b axis. Hydrogen bonds are
demonstrated as dashed lines in Fig.3. The crystal packing of
the title compound viewed along the ‘a’ axis. Hydrogen
bonds are drawn as dashed lines and a representative C–
H...π contact is shown as a dotted line shown if Fig.4.
Fig.3.Crystal packing of the title compound viewed along the b
axis. Hydrogen bonds are shown as dashed lines.
Fig .4 .The crystal packing of the title compound viewed along the
‘a’ axis. Hydrogen bonds are drawn as dashed lines and a
representative C–H···π contact is shown as a dotted line.
4.3. Vibrational spectral analysis
Density aesthetic theory will be known pertaining to
good performance with the estimation involving
vibrational spectra involving organic compounds, and also
it can be observed in the molecule DMBNH∙H2O.The
combined FTIR as well as FT–Raman spectra of a title
compound under investigation are usually shown within
Figs. 5 and 6.
The observed in addition to calculated frequencies
employing DFT-M06-2X/6-31G(d,p) in addition to
B3LYP/6-31G(d,p) levels associated with calculations and
as well as it's relative intensities, probable assignments
plus the potential energy distribution (PED) of our title
molecule are usually summarized inside Table 3.
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Fig.5. Comparison of theoretical M06 2X/6-31G (d,p) and
B3LYP/6-31G (d,p) and experimental FT-Raman spectra for (E)-
N'-(3,4-Dimethoxybenzylidene)-nicotinohydrazide monohydrate
The calculated wavenumbers are generally higher when
compared with the equivalent experimental values, for the
combination involving electron correlation effects, basis set
deficiencies plus the potential energy surfaces tend to be
too deep. Immediately after applying, the scaling factor,
ones theoretical wave numbers are generally throughout
good agreement within experimental wavenumbers.
Throughout my own produce investigation, the scale
factor associated with 0.9701 [22] are considered
intended for M06-2X/6-31G(d,p) and 0.9608 [23]
pertaining to B3LYP/6-31G(d,p)
Fig .6. Comparison of theoretical M06 2X/6-31G (d,p) and
B3LYP/6-31G (d,p) and experimental FT-Raman spectra for (E)-
N'-(3,4-Dimethoxybenzylidene)-nicotinohydrazide monohydrate
level regarding calculations. After scaling having a scaling
factor, the deviation with the experiments is actually less
as compared to 10 cm-1 with few exceptions. In line with
theoretical calculations, studied DMBNH∙H2O molecule has
assumed to have a good planar structure associated with C1
point group symmetry. The 111 normal modes connected
with vibrations are usually distributed in the same way 38
stretching modes, 37 bending modes and also 36 torsional
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modes considering C1 symmetry. The many fundamental
vibrations are generally active with both IR and Raman.
Each of the calculated normal modes is generally numbered
with the major to the smallest frequency within each
fundamental wavenumber.
Root mean square (RMS) values were obtained in the study
using the following expression:
ට
ଵ
ିଵ
∑ ൫ݒ
െ ݒ
௫
൯
ଶ
Where n will be the number of a experimental or even
calculated data. The RMS error was calculated between
scaled M06-2X/6-31G(d,p), B3LYP/6-31G(d,p) and
experimental frequencies.
This really is quite obvious because the frequencies
calculated to the basis involving quantum mechanical
force fields usually differ appreciably via observed
frequencies. That is partly for the neglect associated with
anharmonicity and also partly for the approximate nature
of any quantum mechanical methods. To help reproduce
our own observed frequencies,
refinement involving scaling details were applied and
optimized coming from least square refinement algorithm
that will resulted inside a good weighted RMS deviation
of the observed IR along with Raman bands usually are
found in order to possibly be 6.79 and 4.65 by M06-2X and
3.65 and 2.71 by B3LYP methods respectively. Small
differences between experimental in addition to calculated
vibrational modes tend to be observed. The idea must end
up being because of its fact that hydrogen bond vibrations
offer at the crystal lead to be able to strong perturbation
of any IR wavenumbers as well as intensities connected
with numerous additional modes.
4.3.1. Vibrations of the pyridine ring
The ring stretching vibration ߴ(C-H) bands are focused for
the most part on 3090–3020 cm−1 [24,25]. In our present
study the C-H stretching vibrations of the pyridine ring saw
at 3091, 3127, 3127 and 3170 cm-1 in M06-2X and 3042,
3075, 3079 and 3120 cm-1 by B3LYP level of calculations.
The FTIR band at 3077 cm-1 has been recognized as C-H
stretching vibration of the pyridine ring. The in-plane
bending ߜ(C-H) vibrations are usually combined with the
pyridine ߴ(C−C) stretching mode and show up in the
accompanying locales: 1300–1000 cm-1. In our title
molecule, in-plane bending ߜ(C-H) vibrations are
distinguished at 1623, 1480, 1205 and 1131 cm-1 by M06-2X
and 1578, 1457, 1188 and 1112 cm-1 by B3LYP level of
calculations. The out-off-plane bending vibrations happen
dependably beneath 1000 cm-1. For our title molecule ߛC-H
vibrations saw at 968 cm-1 in FTIR and 966 cm-1 in FT-
Raman spectra. The hypothetically anticipated
wavenumbers at 1000, 974, 946 and 822 cm-1 and 964, 947,
923 and 803 cm-1 by M06-2X and B3LYP level of calculations
respectively, which is great concurrence with experimental
discoveries.
The band observed at 1269 cm−1 both within IR as well as
Raman are usually issued to the pyridine ring C-C
stretching vibrations. Our own computed wavenumbers in
1623, 1480, 1278, 1246 cm-1 via M06-2X and also 1578,
1457, 1259, 1257 cm-1 through B3LYP level regarding
calculations tend to be identified just like C−C vibrations
of any pyridine ring, the calculated value by the B3LYP
method is great concurrence with experimental discoveries.
The C–C–C inplane twisting groups are distinguished at
mode.nos: 69, 70 and 78 separately. The CCC out-off-plane
vibrations saw at the FTIR band 968cm-1 and FT-Raman
groups at 966 and 705 cm-1 separately. The C-N vibrations of
the pyridine ring are recognized at mod.nos:22 and 23.
4.3.2. Vibrations of the benzene ring
The aromatic C-H stretching vibrations connected with
heteroaromatic structures usually are essential to be able
to appear for the 3100–3000 cm-1 frequency ranges, in
multiple weak bands. The nature regarding substituents
are unable to affect the bands much inside the region
[26].
The C-H in-plane bowing vibrations show up by sharp yet
frail to medium intensity bands in the 1500–1100 cm-1
region. These kinds of bands usually are not sensitive
towards nature of substituents [27]. The out-of-plane
bending vibrations happen in the wavenumber range 1000-
800 cm-1 [27]. Throughout my work C-H stretching
vibrations of the benzene ring saw at 3060 cm-1 in FT-Raman
spectrum. The hypothetically anticipated wavenumbers at
3144/3101, 3140/3080, 3117/3070 cm-1 are allotted as
ߴC-H vibrations by M06-2X /B3LYP level of calculations
individually, the commitment of PED for this mode is over
98%. The CH in-plane bending vibrations saw at 1269 cm-1
in both FTIR and FT-Raman spectra. The computed
wavenumbers at 1287/1274, 1278/ 1259 and 1131/1112
cm-1 by M06-2X /B3LYP level of estimations separately. Ones
observed band in 871 cm-1 and also 937/914, 884/863,
728/708 cm-1 coming from M06-2X /B3LYP level
associated with calculations respectively were identified
Just as ߛC-H vibrations of any benzene ring.
The ring C–C stretching vibration happens in the region
1625–1430 cm-1 [28]. With this work, our middle in order
to strong bands tend to be observed with 1601, 1269 cm-1
inside FT-IR and also strong bands observed on 1594,
1269 cm-1 in FT-Raman usually are given to help
aromatic C-C stretching vibrations, which might be good
concurrence within theoretically calculated value in
1640/1593, 1457/1437, 1418/1391, 1287/1274,
1278/1259, 1238/1215 cm-1 from M06-2X /B3LYP level
involving calculations respectively. The aromatic ring
distortion vibrations show up in region of 625–605 cm-1 for
the mono substituted ring and 475–425 cm-1 for the
trisubstituted ring. The C-C-C in-plane bending vibration
ascertained at 558/550 cm-1 by M06-2X / B3LYP strategy
(mode no:80). The C-C out-of-plane bending vibration is
allocated to 728/708, 639/630, 632/621, 285/259 cm-1
[mode no: 72, 76, 77, 93] in M06-2X/ B3LYP technique.
Tentatively this mode is seen at 714, 618 cm-1 in FTIR band
and at 620 cm-1 FT-Raman band.
4.3.3. Vibrations of methoxy groups
In our own spectra connected with methoxy groups the
overlap of a region which both asymmetric stretching [29]
asCH3 absorb having a weak to help medium intensity
(2985 ± 25 in addition to 2970 ± 30 cm-1) is actually not
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large along with regularly seen above 3000 cm-1. With
regard to title molecule our own methyl ester group
symmetric stretching vibrations calculated with
3082/3032, 2963/2909, 2960/2903 cm-1 in addition to
antisymmetric vibrations calculated with 3079/3026,
3047/2987, 3029/2966 cm-1 via M06-2X/B3LYP level
connected with calculations respectively. IR band observed
at 2965 cm-1 continues to be allocated to symmetric
stretching vibrations of the methyl group. With methyl
esters the cover of the districts in which methyl awry
distortions are dynamic (1460 ± 25 and 1450 ± 15 cm-1) is
very solid, which prompts numerous concurring
wavenumbers [29]. This is self-evident for the deviated
distortions, as well as for the symmetric deformations [29]
generally showed in the reach 1380 ± 45 cm-1.
In this work δasCH3 in addition to δsCH3 bending
vibrations are usually designated at 1481/1465,
1481/1458, 1467/1446, 1464/1441 cm-1 as well as
1444/1426, 1418/1391 cm-1 from M06-2X/B3LYP level of
calculations respectively. Experimentally the mode
continues to be identified with 1470, 1423 cm-1 in IR band
as well as at 1425 cm-1 with FT-Raman band. The methyl
rocking wavenumbers are generally necessary for the
regions [29] 1100 ± 95 in addition to 1080 ± 80 cm-1. The
observed IR band at 1167 cm-1 and the hypothetically
anticipated band at 1182/1166, 1147/1132, 1146/1131 cm-
1 have been assigned as by methyl rocking vibrations by
M06-2X/B3LYP level of calculations separately, which is
great concurrence with test discoveries. A methoxy group
attached to an aromatic ring give ߴasC-O-C in the range
1310–1110 cm-1 and ߴsC-O-C in the range [29,30] 1050–
1010 cm-1. The M06-2X/B3LYP level of computations gives
the wavenumbers at 1317/1303; 1246/1257 cm-1 and
1047/1025, 1038/1012 cm-1 are allocated ߴas C-O-C and ߴs
C-O-C vibrations separately. The tentatively watched
wavenumbers at 1309, 1022 cm-1 in IR and 1309 cm-1 in
Raman are distinguished this mode.
4.3.4. Vibrations of carbonyl group
The carbonyl extending mode [29] is normal in the region
1750–1600 cm-1 and for the title aggravate this very strong
mode shows up at 1653 cm-1 in the IR spectrum and at
1694/1662cm-1 hypothetically M06-2X/B3LYP level of
calculations individually, this concur well with experimental
wavenumber. The in-plane and out-of-plane C═O
deformations are generally necessary at the regions, 725 ±
95 and also 595 ± 85 cm-1, respectively [29]. With regard to
identify molecule the IR band with 819 cm-1 as well as
computed values with 828/810 cm-1 from M06-2X/B3LYP
level associated with calculations are generally designated
as inplane C═O vibrations. The out-off plane C═O
distortions modes are recognized at 618 cm-1 in IR and 620
cm-1 in Raman spectrum and processed wavenumbers at
632/621 cm-1 by M06-2X/B3LYP level of computations
individually.
4.3.4. Vibrations of amide group
The writing work [29] demonstrates the NH stretching
vibration shows up emphatically and comprehensively in the
district 3390 ± 60 cm-1. In the present work the watched
wavenumber at 3224 cm-1 in FTIR range and the
hypothetically anticipated wavenumbers at 3207/3157 cm-1
by M06-2X/B3LYP level of counts are credited to NH
stretching vibration. This is an unadulterated mode; the
commitment of PED is 98%. The experimentally observed
peak on 3224 cm-1 inside IR spectrum is shifted through
71 cm-1 from the computed wavenumber at 3153 cm-1 by
B3LYP level associated with calculation. The reason about
this prolonged deviation can be due to the N9-H26.....O37
intermolecular interactions between our own NH group
along with water molecule. This demonstrates the
debilitating of the NH bonding about proton exchange to the
neighboring oxygen. The CNH vibration which N along
with H atoms move with opposite direction involving
carbon atom with the amide moiety appears from 1531
cm-1 [30]. For title compound ߜ CNH vibrations observed
the FTIR band at 1470 cm-1 and the computed wavenumbers
at 1481/1465 cm-1 with the aid of M06-2X/B3LYP level of
calculations. The computed wavenumbers at 834 cm-1 via
M06-2X method and 838 cm-1 via B3LYP method has been
recognized as NH out-off plane bending vibration.
4.3.5. Vibrations of the C=N, C−N and N−N group
The C═N stretching skeletal bands are anticipated inside the
range 1672–1566 cm-1 [31]. In our molecule computed
wavenumber with 1642 cm-1 in addition to 1617 cm-1
coming from M06-2X and also B3LYP level involving
calculations tend to be identified just as C═N stretching
vibration. The observed FTIR peak at 1355 cm-1 as well as
theoretically predicted band at 1382 cm-1 by M06-2X and
1363 cm-1 by B3LYP level of calculations are designated in
the same way ߜCH═N vibration. Mode no: 60 may be
identified just as C═N out-off plane bending vibration.
The C–N stretching vibration [29] combined with the δNH, is
moderately to strongly active in the region 1275 ± 55 cm-1.
In my provide work C–N stretching vibration observed at
1355 cm-1 in FTIR and 1382 cm-1 and 1363 cm-1 M06-2X and
B3LYP level of calculations respectively. The δC−NH bending
vibrations observed at 1470 cm-1 in FTIR spectrum and
predicted wavenumber at 1481 cm-1 by M06-2X and 1465
cm-1 in B3LYP level of calculations. The out-off plane C–N
vibrations attributed at 834/838 cm-1 by as well as B3LYP
level involving calculations. The N−N stretching has been
reported at 1115 cm-1 by Crane et al. [32]. For our title
compound ߴN−N vibrations observed at medium intensity
band 1118 cm-1 by M06-2X and 1095 cm-1 by B3LYP level of
calculations. The ߜN−NH inplane bending vibrations
observed at 1512 cm-1 with IR as well as Raman and also
1535/1504 cm-1 in M06-2X /B3LYP level of calculations.
4.3.6. Vibrations of the Water molecule
The water molecule frames H–bonds with
nicotinohydrazone molecules. N−H...O, O−H...O, O−H...N and
C−H...O hydrogen bonds are produce with the crystal
system. One of the H atoms of the water molecule forms
bifurcated hydrogen bonds to the azomethine nitrogen and
the carbonyl oxygen atoms of one neighboring molecule
(Fig.3). The water molecule acts as a hydrogen bond
acceptor towards another nicotinohydrazone molecule
through N–H...O and C−H...O hydrogen bonds [10]. The OH
stretching vibrations of the water molecule observed at
3787 and 3414 cm-1 in FTIR spectrum. The computed
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ij
jiF
iij qEE εε −=∆=
2
),(
2
wavenumbers at 3780/3708 cm-1 by M06-2X and B3LYP
level of calculations are assigned as OH stretch vibrations of
the water molecule. This is an unadulterated mode; the
contribution involving PED is actually above 98%. The
experimentally observed peak from 3787 cm-1 throughout
IR spectrum is usually shifted through 79 cm-1 with the
computed wavenumber at 3708 cm-1 from B3LYP level
involving calculation. Our reason about this very long
deviation is actually to its O37-H39...O8 intermolecular
interactions between C═O group as well as OH of the
water molecule. This shows the debilitating of the OH bond
bringing about proton exchange to the neighboring oxygen
atom. Throughout my previous work [4] we have reported
medium band at 1571 cm-1 in FT-Raman spectra and also
computed wavenumbers at 1637, 1585 and 1581 cm-1
issued to help H2O deformation modes. For title compound
the computed wavenumber at 1660 via M06-2X and 1627
cm-1 coming from B3LYP level of calculation may be
given just like H2O deformation mode (mode no:19). The
stretching vibration of O−H...O hydrogen bonding appears at
142 cm-1 [4]. In our present work the O37−H39...O8
stretching vibration observed at 176/170 cm-1 by M06-2X
and B3LYP level of calculations respectively. Mode no’s: 70
and 91 have been distinguished as O37−H39...O8 inplane
bending and H38−O37−H39...O8 torsional modes
respectively.
4.3.7. Analysis of vibrational calculations
The correlation aesthetic in which describes harmony
between our own calculated and experimental
wavenumbers will be exhibited inside Fig.7. Equally
watch by the figure, ones experimental fundamental offers
a correlation within B3LYP level. The relations between
calculated and also experimental wave numbers tend to be
linear and, mentioned by the right after equations:
ߴcal =0.987 ߴexp-5.554; (R2=0.998) at DFT/M06-2X level
ߴcal =1.004 ߴexp4.774; (R2=0.999 ) at DFT/ B3LYP level
We calculated R2 values (R2 = 0.999 for B3LYP and R2 =
0.998 for M06-2X) between the calculated and experimental
wavenumbers. Therefore, the exhibitions of the B3LYP
strategy with of the forecast of the wavenumbers within the
molecule were close.
4.4. Natural bond orbital (NBO) analysis
NBO analysis associated with molecules illustrate the
deciphering of our molecular wave function throughout
terms Lewis structures, charge, bond order, bond type,
hybridisation, resonance, donor–acceptor interactions, etc.
Strong electron delocalisation on the Lewis structure shows
up as donor acceptor interaction.NBO theory makes it
possible for the assignment of a hybridization associated
with atomic lone pairs as well as of a atoms involved
within bond orbitals. Interaction between atomic orbitals
can be interpreted utilizing NBO theory. Natural bond orbital
analysis required a efficient process for studying intra
in addition to inter molecular bonding and interaction
among bonds, and provide the handy basis regarding
investigating charge transfer or conjugative interaction
with molecular systems [33].
Fig.7. Correlation graphs of experimental and theoretical
(scaled) wavenumbers of the N-(E)-N'-(3,4-
Dimethoxybenzylidene)-nicotinohydrazide monohydrate
The bonding–anti holding communication can be
quantitatively portrayed regarding the NBO approach that is
communicated by method for second- order perturbation
interaction energy E(2) [34]. This energy represents the
estimate of the off-diagonal NBO Fock matrix element. The
stabilization energy E(2) associated with i (donor) j
(acceptor) delocalisation is estimated from the second-order
perturbation approach as given below
where qi is the donor orbital occupancy, are ߝi and ߝj
diagonal elements and F(i,j) is the off diagonal NBO Fock
matrix element.
The second order perturbation analysis of Fock matrix
involving DMBNH∙H2O is summarized in Table 4.
The NBO investigation gives a portrayal of the structure of a
compound by an arrangement of localized bond, antibond
and Rydberg additional valence orbitals to recognize and
affirm the conceivable C–H...O inter-molecular, N–H...O,
O−H...O, O−H... inter- and intra-molecular and C–H...
ߨ stacking connections between the units that would shape
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the best possible and inappropriate hydrogen bonding. The
NBO investigation plainly demonstrates the presence of
solid N–H...O and O–H...O inter-molecular hydrogen bonds
throughout DMBNH∙H2O monomer structure. The inter-
molecular O–H...O hydrogen bonding is formed owing to the
orbital overlap between LP (2) O8 and σ*(O37 –H39) with
E(2) value 10.47 kJ mol-1 which results in ICT, causing
stabilization of H-bonded systems. Another inter-molecular
N–H...O hydrogen bonding is formed due to orbital overlap
between LP(2) O37 σ*( N9- H26) resulting stabilization
energy of about 13.81 kJ mol-1 , that will result within
charge transfer occurs between water molecule in order to
amide group of a title molecule.
The intra-molecular hyper conjugative interactions are tend
to be formed by orbital overlap between π(C–C), π(N-C),
LP(1)N, LP(2)O and π*(C–C), π*(C–O), π*(C–N), π*(O–N)
bond orbitals, which results in an ICT causing stabilization of
the system. The π-bonds conjugation from π(C2-C3) π*C1-
O8 , π*(C4-C5) stabilizes the molecule resulting stabilization
energy of about 19.94, 16.38 kJmol-1. The lone pair donor
orbital, LP(1)N9 interaction between the nitrogen (N9) lone
pair and the π*(C1-O8) antibonding orbital has a
stabilization energy 57.23 kJ mol-1, which indicate that intra
molecular charge transfer between amide group to carbonyl
group of the title molecule. The hyper conjugative
interaction between lone pair of LP (2) O8 σ*(C1-C2)
resulting stabilization energy is 18.61 kJmol-1, this really is
responsible because of its ICT between carbonyl group and
also pyridine ring. The hyperconjugative interaction
between methoxy oxygen and the π*(C15–C16) antibonding
orbital is 30.40 kJ mol-1; this indicates the intra molecular
charge transfer between the electron donating methoxy
group to electron accepting benzene ring. The maximum
energies occurs from antibonding π*(C15-C16) to
antibonding π*(C12-C17) and π*(C13-C14) with
delocalization energy 240.19 and 284.12kJ mol-1
respectively. The hyper conjugative interaction between
lone pair of oxygen to hydrogen atom LP (1) O37 RY*(2)
H38 with E(2) value 10.47 kJ mol-1 which results in ICT,
causing stabilization of the water molecule.
4.5. First order hyperpolarizibility analysis
The first order hyperpolarizability (β0) of this novel
molecular system is calculated using M06-2X/B3LYP-6-
31G(d,p) level of estimation, based on the finite field
approach. At the presence of applied electric field, the
energy of a system is really a function of an electric
field. The primary hyperpolarizability can be a third rank
tensor that is actually pointed out via 3 3 3 matrix.
The 27 segments of the 3D lattice can be lessened to 10 parts
because of the Kleinman symmetry [35]. The segments of β
are characterized as the coefficients in the Taylor
arrangement extension of the vitality in the external electric
field. At the point when the external electric field is feeble
and homogeneous, this extension is given underneath:
E=Eo -µαFα − 1/2 ααβFα Fβ− 1/6 βαβγFαFβFγ+……
where Eo is the energy of the unperturbed
molecules, Fα is the field at the origin, μα ,ααβ and βαβγ are the
components of dipole moment, polarizability and first
hyperpolarizability, respectively.
Since the estimations of the polarizabilities (α) and
hyperpolarizability (β) of the Gaussian 09 output are reported
in atomic units (a.u.), the calculated values have been
converted into electrostatic units (esu) (For α: 1a.u. = 0.1482
× 10-24 esu; pertaining to β: 1a.u. = 8.639 ×10-33 esu). The
mean polarizability αо and total polarizability ∆α of our title
molecule are 31.254×10-24 esu (M06-2X) and 32.684×10-24
esu(B3LYP) and 12.677×10-24 esu (M06-2X) and 24.959×10-24
esu (B3LYP) respectively. The total molecular dipole moment
and first order hyperpolarizability are 2.225 Debye (M06-2X)
and 2.277 Debye (B3LYP) and 7.244×10-30esu (M06-2X) and
13.254×10-30esu (B3LYP) respectively and are depicted in
Table 5.
The initial order hyperpolarizability associated with my
title molecule calculated via B3LYP level regarding
calculation is approximately 36 times greater than it
connected with urea as well as M06-2X level regarding
calculation is actually approximately 19 times in excess of
it regarding urea (β involving urea can be 0.373×10-30 esu
[4]. The actual result indicates ones good nonlinearity of a
title molecule.
4.6. Electronic properties:
4.6.1. UV–Vis spectral analysis
Time dependent DFT method will be able to receive
accurate absorption wavelengths on an relatively small
computing time that corresponds for to vertical
electronic transitions computed towards ground state
geometry, especially in the study connected with solvent
effect [36]; the excitation energies, absorbance and oscillator
strengths for the title molecule at the optimized geometry in
the ground state were obtained in the framework of TD-DFT
calculations with the M06-2X/B3LYP/6-31G(d,p) level of
calculations. Moreover, the exploratory and hypothetical UV
spectra of the DMBNH∙H2O are demonstrated in Fig. 8. The
experimental and computed electronic values, such as
absorption wavelength, excitation energies, frontier orbital
energies, and oscillator strengths are organized Table 6.
These kind of calculations continues to be completed
considering the effect connected with DMSO as solvent.
Usually, in line with Frank–Condon precept, the maximum
absorption peak (max) corresponds in the UV–visible
spectrum to vertical excitation. The theoretically predicted
absorption maxima values have been discovered to be
343.03/291.39, 289.96/257.28, and 282.44/249.54 nm for
DMSO, 329.19/283.26, 291.45/263.84, 283.62/249.70 nm
for gas phase at B3LYP/M06-2X level of calculations
respectively. In our case the calculated absorption bands
have slight red-shift (Bathochromic shift) with the values of
343.03/291.39 nm in DMSO comparing with the gas phase
calculations of 329.19/283.26 by TD-DFT- B3LYP/M06-2X
level of calculations. Electronic absorption spectra of title
molecule in DMSO solvent demonstrated three bands at
340.10, 305.6 and 228.13 nm through experimental
observation, these excitations correspond to π - π*
transition. In case of π - π* transitions, the excited states are
more polar than the ground state and the dipole-dipole
interactions with solvent molecules lower the energy of the
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excited state more than that of the ground state. Therefore a
polar solvent decreases the energy of π - π* transition and
absorption maximum appears 13.84 and 8.13 nm by B3LYP
and M06-2X level of associated with calculations are red
shifted inside going coming from gas phase to be able to
DMSO solvent respectively.
Fig.8. UV-visible spectrum (DMSO) of (E)-N'-(3,4-
Dimethoxybenzylidene)-nicotinohydrazide monohydrate
4.6.2. Frontier molecular orbitals
The many keys to press orbitals within a great molecule
are generally the frontier molecular orbitals (FMOs), called
highest occupied molecular orbital (HOMO) as well as
lowest unoccupied molecular orbital (LUMO) and also very
helpful with regard to physicists as well as chemists
usually are the main orbital taking part in chemical
reaction. The HOMO (H) energy characterizes the ability
connected with electron giving; LUMO (L) characterizes the
ability connected with electron accepting. the energy of an
HOMO will be directly regarding to ionization potential,
while LUMO energy can be instantly concerning to
electron affinity [37]. Here four ticks molecular orbitals
(MOs) were analyzed: the second highest and highest
occupied MOs and the lowest and the second lowest
unoccupied molecular orbits which can be denoted in the
same way HOMO-1, HOMO, LUMO and LUMO+1,
respectively. The plots of (HOMOs) and (LUMOs) are
demonstrated in Fig. 9. The energy values of the HOMO and
LUMO are calculated at -5.7148 eV/-7.0485 eV and -1.6012
eV/-0.7168 eV by B3LYP/M06-2X level of calculations
respectively. Similarly, the HOMO-1 and LUMO+1 energy
values are -6.7061 eV/ -8.2031 eV and -0.9821 eV / -0.0389
eV by B3LYP/M06-2X level of calculations respectively. In
this molecule, the estimation of energy separation between
the HOMO − LUMO / HOMO-1 − LUMO+1 is -4.1136eV/ -
6.63317 eV and -5.7148 eV/ -8.1642 eV by B3LYP and M06-
2X level of calculations respectively. From the Fig.9, HOMO
and HOMO-1; LOMO and LUMO+1 localized on the benzene
and pyridine ring exception of methyl and water molecule
which is identified by B3LYP /M06-2X method.
Based on density functional theory, global chemical
reactivity descriptors of title compound such as hardness
(η), chemical potentialሺߤሻ, softness(S), electro negativity
(χ) and electrophilicity index (ω) has been calculated by
M06-2X and B3LYP level of calculations and listed in
supplementary material 1. employing Koopman’s theorem
[38] pertaining to closed-shell molecules, ߟ, ߤ and ߯ can
be defined as η = ሺܫ െ ܣሻ / 2; μ = െሺܫ ܣሻ / 2; χ =
ሺܫ ܣሻ / 2; where I and A are the ionization potential and
electron affinity of the compounds respectively. I and A can
be communicated through HOMO and LUMO orbital energies
as I = - EHOMO and A = - ELUMO. Electron affinity refers towards
the capability connected with ligand to accept precisely
single electron coming from the donor. Softness is a
property of the molecule that measures the extent of
chemical reactivity. It is the reciprocal of hardness: S = 1/2η.
Considering the chemical hardness, large HOMO-LUMO
energy gap represent a hard molecule and small HOMO–
LUMO energy gap represents a soft molecule. The HOMO–
LUMO energy gap of the title molecule is high 6.3317 eV
/4.1136eV calculated by M06-2X/B3LYP level of
calculations, so we infer that our title molecule is hard
molecule, which is apparent from the count concoction
hardness is 3.1659/2.0568 which are more noteworthy than
that of compound chemical softness 0.1579/3.2528
computed by M06-2X/B3LYP level of estimate.
Fig.9.The atomic orbital compositions of the frontier molecular
orbital for (E)-N'-(3,4-Dimethoxybenzylidene)-nicotinohydrazide
monohydrate.
4.6.3. Molecular Electrostatic Potential analysis
MEP is actually relating to our electron density and also
is often a very helpful descriptor in understanding sites
intended for electrophonic along with nucleophilic
reactions along with hydrogen bonding interactions [39].
Molecular electrostatic potential (MEP) connected with
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(DMBNH∙H2O) are delineated in Fig. 10 in color quantity
from-5.220e-2 (deepest red) to be able to +5.220e-2
(deepest blue). Our own MEP which is a great plot
associated with electrostatic potential mapped on to the
constant electron density surface. The color scheme for the
MEP surface will be partially negative charge or maybe
red-electron rich; partially positive charge or maybe blue-
electron deficient; yellow slightly electron packed region;
light blue-slightly electron deficient region, respectively.
Potential increases in the order red < orange < yellow <
green < blue through the MEP this really is evident how
the negative charge covers the H2O, carbonyl in addition
to pyridine and also the positive region is actually over
the NH group along with slightly electron loaded region
can be over the methoxy group in addition to slightly
electron deficient region through the methyl along with
almost all proton regions. Most of these sites allow
specifics regarding the region through during which the
compound can have intermolecular interactions.
Fig.10.Molecular electrostatic potential map of the title
compound
5. THERMODYNAMIC PROPERTIES
On the premise of vibrational analysis, the statically
thermodynamic functions: heat capacity (Cop;m), entropy
(Som), and enthalpy changes ( Hom) for DMBNH∙H2O
molecule were processed utilizing B3LYP/M06-2X level of
calculations from the theoretical harmonic frequencies and
arranged in supplementary material 2. The Table S2
shows that this entropies, heat capacities, along with
enthalpy changes were increasing in temperature ranging
by 100 for you to 1000 K due to the fact that this
molecular vibrational intensities increase with temperature
[40]. these types of observed relations of the
thermodynamic is effective vs. temperatures were fitted
from quadratic formulas, plus the corresponding fitting
regression details (R2) is actually 0.991/0.992,
0.962/0.963 along with 0.978/0.977 calculated from
B3LYP/M06-2X level of calculations pertaining to heat
capacity, entropy and also enthalpy changes respectively.
our current correlation graphics involving temperature
dependence from thermodynamic functions connected
with DMBNH∙H2O molecule tend to be shown in Fig.11.
Vibrational zero-point energy of our molecule DMBNH∙H2O
is actually 778.65/795.61 kJmol-1 calculated through
B3LYP/M06-2X level involving calculations.
Fig.11. Correlation graphs of thermodynamic properties at
different temperature for (E)-N'-(3,4-Dimethoxybenzylidene)-
nicotinohydrazide monohydrate.
6. CONCLUSION
(E)-N′-(3,4Dimethoxybenzylidene) nicotinohydrazide
monohydrate compound was synthesized and characterized
with the aid of FT-IR, FT-Raman, and X-ray single-crystal
diffraction techniques. The crystallization of the compound
indicates it is in monoclinic space group P21/n. Molecular
structure in addition to vibrational frequencies of
DMBNH∙H2O have been investigated by DFT/M06-2X and
B3LYP level of calculations. Computed along with
experimental geometric parameters, vibrational frequencies
of the DMBNH∙H2O have become compared. The scaled
frequencies recognize nicely with the experimental
wavenumbers. It is viewable that the DFT/B3LYP level
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regarding calculations tend to be effective methodology
pertaining to comprehension the FT-IR, FT-Raman in
addition to UV-Visible spectra associated with organic
compounds as compared to DFT/M06-2X level involving
computations. Because, our performances of the B3LYP
level with the prediction of our wavenumbers for the
molecule were quite near. The water molecule acts to be an
acceptor (hydrogen bond) for the nicotinohydrazone
molecule in the course of N–H•••O as well as O—H•••O
hydrogen bonds. Vibrational and NBO investigation affirms
the development of hydrogen bond by the orbital overlap
between LP (2) O8 σ*(O37 –H39) and LP(2) O37 σ*(
N9- H26) which comes about intramolecular charge transfer
(ICT), results in stabilization of the hydrogen bonded O−H
....O and N−H ....O system. The first order hyperpolarizability
of our title molecule calculated by B3LYP level of calculation
is approximately 36 times greater than that of urea and
M06-2X level of calculation is approximately 19 times
greater than that of urea. This outcome demonstrates the
great nonlinearity of the title molecule. The figured HOMO
and LUMO alongside their plot has been introduced for
comprehension of charge exchange happening inside the
particle. The energies of essential molecular orbitals,
absorption wavelength ( max), oscillator strength and
excitation energies of the compound were also determined
by the TD-DFT method and compared with the experimental
values. The calculated absorption bands have slight red-shift
(Bathochromic shift) with the values of 343.03/291.39 nm in
DMSO comparing with the gas phase calculations of
329.19/283.26 by TD-DFT- B3LYP/M06-2X level of
calculations. Based on the frequencies scaled and the
principle of statistic thermodynamics, the properties of
thermodynamics ranging from 100 to 1000 K were obtained
and it is clear that, the gradients of C0p and S0m to the
temperature decrease, but that of ∆H0m increases, as the
temperature increases. We trust our outcomes will be of aid
in the mission of the exploratory and hypothetical proof for
the title particle in response intermediates, nonlinear optical
and will likewise be useful for the configuration and
combination of new materials.
supplementary material 1: Calculated energy values of (E)-N'-(3,4-Dimethoxybenzylidene)-nicotinohydrazide monohydrate by M06-
2X/B3LYP/6-31G (d,p) level of calculations.
Energies Values
M06-2X B3LYP
EHOMO (eV) -7.0485 -5.7148
ELUMO (eV) -0.7168 -1.6012
EHOMO-1 (eV) -8.2031 -6.7061
ELUMO+1 (eV) -0.0389 -0.9821
EHOMO -ELUMO gap (eV) 6.3317 4.1136
EHOMO-1 - ELUMO+1 gap (eV) 8.1642 5.7148
Chemical hardness (η) 3.1659 2.0568
Softness (S) 0.1579 0.2431
Chemical potential (μ) -3.8827 -3.658
Electronegativity ( χ) 3.8827 3.658
Electrophilicity index (ω) 2.3809 3.2528
supplementary material 2: Thermodynamic properties at different temperatures at the B3LYP/6-31G(d,p) and M06-2X level of
calculations for of (E)-N'-(3,4-Dimethoxybenzylidene)-nicotinohydrazide monohydrate
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Table 5 The electric dipole moment, polarizability and first order hyperpolarizability of (E)-N'-(3,4-Dimethoxybenzylidene)-
nicotinohydrazide monohydrate by M06-2X/B3LYP/6-31G(d,p) level of calculations.
Dipole moment, μ
(Debye)
Polarizability α First order hyperpolarizability β
Para
meter
Value (DB)
Para
meter
a.u. esu (×10-24)
Param
eter
a.u. esu (×10-30)
M06-
2X
B3LYP
M06-
2X
B3LYP
M06-
2X
B3LYP
M06-
2X
B3LY
P
M06-
2X
B3LYP
µx 1.958 2.012 αxx 250.54 264.407 37.13 39.185 βxxx -535.57
-
807.44
4
-
6975.5
1
-
6975.51
µy
-
0.879
-0.91 αxy
-
98.843
-109.63 -14.65 -16.25 βxxy 388.398
599.21
4
3355.3
72
5176.61
3
µz 0.588 0.552 αyy 158.22 166.559 23.448 24.684 βxyy -271.26 -426.7
-
2343.4
2
-
3686.27
µ 2.225 2.277 αxz
-
13.481
-14.957 -1.998 -2.217 βyyy 146.399
252.37
5
1264.7
44
2180.26
5
αyz 6.339 7.46 0.939 1.106 βxxz 91.615
155.79
9
791.46
3
1345.94
7
αzz 223.92 230.659 33.185 34.184 βxyz -32.67
-
74.758
-
282.23
9
-
645.833
αo 210.89 220.542 31.254 32.684 βyyz 4.651 29.972 40.176 258.93
∆α 85.539 168.414 12.677 24.959 βxzz 13.704
-
14.988
118.38
5
-
129.485
βyzz 12.049 37.101 104.09 320.515
βzzz -165.32
-
150.12
5
-
1428.1
6
-
1296.93
βtot 838.61
1533.1
13
7.244 13.245
Table 6 Comparison of experimental and calculated absorption wavelength (λ, nm), excitation energies (E, eV) and oscillator strength
( ) of (E)-N'-(3,4-Dimethoxybenzylidene)-nicotinohydrazide monohydrate
TD-DFT/ B3LYP/6-31G(d,p) TD-DFT/ M06-2X/6-31G(d,p) Experimental
λ (nm) E (eV) f(a.u) Major contributes
λ
(nm)
E (eV) f(a.u) Major contributes
λ
(nm)
Abs
DMSO
343.03 3.6144 0.5 H→L 291.39 4.9685 0.9149 H→L H → L+2 340.1 2.8094
289.96 4.2759 0.315 H →L+1 H →L+2 257.28 4.8191 0.0131 H →L+1 H →L+2 305.06 3.3855
282.44 4.3897 0.0159
H-4→L+1
249.54 4.255 0.0006
H-1 → L+1 7
228.13 3.2504H-2→L+1 H-1 → L+2
H →L+3
Gas Phase
329.19 3.7663 0.4419 H→L H→L+1 283.26 4.3771 0.8038 H→L H → L+2
291.45 4.254 0.0054
H-2→L+1
263.84 4.6992 0.0117
H →L+1 H →L+2
H-2 →L+2
H-3 → L+1H-3 →
L+2
H-1→L
283.62 4.3715 0.2415
H → L H → L+1
249.7 4.9653 0.0005
H-1 → L H-1 →
L+1 H → L+3H → L+2
23. Int. J. Adv. Sci. Eng. Vol. 2 No.1 36-57 (2015) 57 ISSN 2349 5359
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International Journal of Advanced Science and Engineering www.mahendrapublications.com
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![Int. J. Adv. Sci. Eng. Vol. 2 No.1 36-57 (2015) 36 ISSN 2349 5359
Govindarasu et al
International Journal of Advanced Science and Engineering www.mahendrapublications.com
ABSTRACT: The solitary crystal of proficient novel Hydrazone derivative (E)-N'-(3,4-Dimethoxybenzylidene)-
nicotinohydrazide monohydrate DMBNH∙H2O crystal has been grown, the growned crystal has been
characterized through FTIR (4000-400 cm-1), FT-Raman (3500-50 cm-1), UV-Visible (200-800 nm) and single-
crystal X-ray diffraction techniques. X-ray diffraction analysis indicates that DMBNH∙H2O crystallizes in
monoclinic system with P21/n space group and the calculated lattice constants are a = 4.9128 Å, b = 25.137 Å, c =
12.2950 Å, ߙ= ߛ ൌ 90° and ߚ = 96.513°. Density functional (DFT) calculations continues to be performed for
title compound through DFT- B3LYP/ M06-2X level regarding theories making use of 6-31G(d,p) basis set
utilizing Gaussian09 software. The geometry of the structure was optimized without any symmetry constraints
using the DFT-B3LYP/ M06-2X with 6–31G(d,p) levels of calculations. The targeted interpretation of the
vibrational spectra intended to the basis of calculated potential energy distribution matrix (PED) utilizing VEDA
program. The assignments are based on the experimental IR and Raman spectra and apparently predicted IR and
Raman spectra by DFT-B3LYP and M02-2X level of calculations acquire been proposed. The empiric vibrational
wavenumbers were compared with the calculated results. Steadiness of the molecule emerging from
hyperconjugative associations and charge delocalization was concentrated on utilizing natural bond orbital
analysis. The outcomes demonstrate that adjustment in electron density in the σ∗ and π∗ antibonding orbitals
and E2 energies affirm the event of intramolecular charge exchange inside of the molecule. The lowering of HOMO
and LUMO energy gap appears to be the cause for its enhanced charge transfer interactions. The first order
hyperpolarizability (β0) and related properties (β, α0 and ∆α) of DMBNH∙H2O were calculated. The
thermodynamic functions of the title compound were also performed by B3LYP and M06-2X with basis set 6-
31G(d,p) using Thermo.pl software. Accordingly, the exhibitions of the B3LYP system with of the forecast of the
wavenumbers inside of the molecule were close.
KEY WORDS: DMBNH∙H2O; XRD; NBO; FTIR; FT-Raman; UV-Vis.
© 2015 mahendrapublications.com, All rights reserved
*Corresponding author: sundaraganesan_n@yahoo.com
Received: 01.08.2015 Accepted: 20.08.2015 Published on: 25.08.2015
Synthesis, Molecular Structure and Quantum Chemical
Computational Interpretations on (E)-N'- (3, 4-Dimethoxy
benzylidene)-Nicotinohydrazide Monohydrate by DFT-B3LYP
and M02-2X level of Calculations; A Comparative Study
K. Govindarasu1, E. Kavitha1, N. Sundaraganesan1*, M.Suresh2 and M. Syed Ali Padusha2
1Department of Physics (Engg.), Annamalai University, Annamalainagar-608 002, India.
2PG & Research Department of Chemistry, Jamal Mohamed College, Tiruchirappalli-20, India
1. INTRODUCTION
Joining crystallography with molecular modelling has picked
up prevalence in the late years for portrayal of molecules
and to investigate their physical and chemical properties.
DFT, HF and M06-2X alongside other modelling systems are
broadly utilized as a part of the hypothetical modelling of
molecules to comprehend the physical and chemical
properties. Hydrazones constitute a vital class of organically
dynamic medication particles that have pulled in the
consideration of restorative scientific experts because of
their extensive variety of pharmacological properties [1].
Hydrazone subsidiaries containing an azomethine
(–CONHN═CH–) gathering have been indicated to show
antiproliferative exercises and go about as cytotoxic
specialists with the capacity to anticipate cell movement in
cancerous cells through diverse components [2].
Benzylidene constitute an imperative chic of Schiff bases
that have been broadly utilized as a coordinate, restorative
and natural science. They forces noteworthy anticancer
calming exercises and may additionally serve as reagents for
stereo specific organic synthesis [3]. Schiff base mixes have
been additionally under scrutiny amid years ago on account
of their potential appropriateness in optical
correspondences and large portions of them have NLO
behavior(E)-N'-(3,4-Dimethoxybenzylidene)-nicotino-
hydrazide monohydrate is another Hydrazones subordinate
which demonstrates an expansive non-linear absorption.
Synthesis, structural and spectral analysis of (E)-N'-(4-
Methoxybenzylidene) pyridine-3 carbohydrazide dihydrate](data:image/gif;base64,R0lGODlhAQABAIAAAAAAAP///yH5BAEAAAAALAAAAAABAAEAAAIBRAA7)