Synthesis and spectral characterization of hydrazone derivative of furfural using experimental and DFT methods

Article abstract of DOI:10.1016/j.saa.2013.09.089

The Spectral Characterization of (E)-1-(Furan-2-yl) methylene)-2-(1- phenylvinyl) hydrazine (FMPVH) were carried out by using FT-IR, FT-Raman and UV-Vis., Spectrometry. The B3LYP/6-311++G(d, p) level of optimization has been performed on the title compoun

Full text of DOI:10.1016/j.saa.2013.09.089

Accepted Manuscript
Synthesis and spectral characterization of hydrazone derivative of furfural using
experimental and DFT methods
N. Ramesh Babu, S. Subashchandrabose, M. Syed Ali Padusha, H. Saleem, Y.
Erdoğdu
PII:
S1386-1425(13)01096-2
http://dx.doi.org/10.1016/j.saa.2013.09.089
SAA 11068
DOI:
Reference:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
To appear in:
Received Date:
Revised Date:
Accepted Date:
26 June 2013
15 September 2013
26 September 2013
Please cite this article as: N. Ramesh Babu, S. Subashchandrabose, M. Syed Ali Padusha, H. Saleem, Y. Erdoğdu,
Synthesis and spectral characterization of hydrazone derivative of furfural using experimental and DFT methods,
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2013), doi: http://dx.doi.org/10.1016/j.saa.
2013.09.089
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Synthesis and spectral characterization of hydrazone derivative of furfural using
experimental and DFT methods
N. Ramesh Babua, S. Subashchandraboseb, M. Syed Ali Padushac, H. Saleemd*, Y. Erdoğdue
aDept. of Physics, M.I.E.T. Engineering College, Trichy, Tamil Nadu, India-620007.
bDept. of Physics, M.A.R College of Engineering &Technology. Trichy, Tamil Nadu, India-621316.
cPG and Research Dept. of Chemistry, Jamal Mohamad College (Autonomous) Tiruchirapalli-620020.
dDept. of Physics, Annamalai University, Annamalai Nagar, Tamil Nadu, India-608 002.
eDept. of Physics, Ahi Evran University, Kirsehir, Turkey-40040.
ABSTRACT
The Spectral Characterization of (E)-1-[(Furan-2-yl) methylene)-2-(1-phenylvinyl) hydrazine
(FMPVH) were carried out by using FT-IR, FT-Raman and UV-Vis., Spectrometry. The
B3LYP/6-311++G(d,p) level of optimization has been performed on the title compound. The
conformational analysis was performed for this molecule, in which the cis and trans conformers
were studied for spectral characterization. The recorded spectral results were compared with
calculated results. The optimized bond parameters of FMPVH molecule was compared with X-
ray diffraction data of related molecule. To study the intra-molecular charge transfers within the
molecule the Lewis (bonding) and Non-Lewis (anti-bonding) structural calculation was
performed. The Non-linear optical behavior of the title compound was measured using first order
hyperpolarizability calculation. The atomic charges were calculated and analyzed.
Keywords: FT-IR; FT-Raman; TED; NBO; furan; hydrazone;
*Corresponding author
E-mail: saleem_h2001@yahoo.com, nrbmiet@gmail.com (Dr. H. Saleem).
Mobile: +91 9443879295.

1. Introduction
The hydrazones in the organic molecule brings several physical and chemical properties.
Hydrazones are bearing the >C=N-N< leads the molecule towards nucleophilic and electrophilic
nature. In hydrazone moiety the nitrogen atom behaves as nucleophilic and carbon atom behaves
as nucleophilic as well as electrophilic nature [1-3]. The ability of hydrazones to react with both
electrophilic and nucleophilic reagents widens their application in organic chemistry and
designing the new drugs [1, 4, 5]. Several hydrazone derivatives have been reported as
insecticides, nematocides, herbicides, rodenticides and antituburculosis in addition to that some
of the hydrazone were found to be active against leukemia, sarcoma and illnesses [5, 6]. Two
types of photochemical reactions such as nitrogen-nitrogen bond cleavage and hydrogen
migration from nitrogen to carbon were described for hydrazone [7, 8]. The hydrazones were
also shown to be involved in bio-molecular reactions such as cycloadditions and condensations
[1, 4]. In hydrazone containing C=N-N moiety, reveals existence of structural isomerism (E-
entgegen 180° and Z-zusammen 0°), in which E conformer is most stable than Z conformer
[9].In the present investigations our main focus is to study the geometry of the molecule,
vibration behaviour, non-linear optical activity and intra-molecular charge transfer analysis. For
this we recorded FT-IR, FT-Raman and UV-Vis., spectra and also performed suitable theoretical
calculation using B3LYP/6-311++G (d, p) level of basis set.
2. Experimental details
2.1 Synthesis
The 2.1 ml (0.025 mol) ethanolic solution of furan-2-aldehyde was added to (0.025 mol),
3.4 g of aqeous solution benzohydrazide taken in a R.B flask. The reaction mixture was kept
2

over a magnetic stirrer and stirred well in an ice cold condition for an hour. The colorless solid
separated out was filtered and dried over vacuum.
2.2 FT-IR, FT-Raman and UV-Vis., spectra
The FT-IR spectrum of FMPVH was recorded in the region 400-4000 cm-1 on an IFS
66V spectrophotometer using the KBr pellet technique. The spectrum was recorded at room
temperature with a scanning speed of 10 cm-1 per minute and at the spectral resolution of 2.0 cm-
1 in SAIF Laboratory, IIT madras, Tamilnadu, India. The FT-Raman spectrum of title compound
was recorded using the 1064 nm line of a Nd:YAG laser as excitation wavelength in the
region 50-3500 cm-1 on Bruker model IFS 66V spectrophotometer equipped with an FRA 106
FT-Raman module accessory and at spectral resolution of 4 cm-1. The FT-Raman spectral
measurements were carried out from SAIF Laboratory, IIT Madras, and Tamilnadu, India. The
ultraviolet absorption spectrum of FMPVH was recorded in the range of 200-500 nm using a
Perkin Elmer Lambda-35 spectrometer, UV pattern is taken from a 10-5 molar solution of
FMPVH dissolved in methanol.
3. Computational details
In order to establish the stable possible conformations, the conformational space of
FMPVH compound was scanned with molecular mechanic simulations. For meeting the
requirements of both accuracy and computing economy, theoretical methods and basis sets were
considered. Density Functional Theory (DFT) has been proved to be extremely useful in treating
electronic structure of molecules. The entire calculations were performed at B3LYP/6-
311++G(d, p) level of basis set using Gaussian 03W [10] program package, invoking gradient
geometry optimization [10, 11]. The optimized structural parameters were used in the vibrational
frequency calculations at the DFT level to characterize all stationary points as minima. Then,
3

vibrationaly averaged nuclear positions of FMPVH were used for harmonic vibrational
frequency calculations resulting in IR and Raman frequencies together with intensities and
Raman depolarization ratios. The vibrational modes were assigned on the basis of TED analysis
using SQM program [12].
It should be noted that Gaussian 03W package was able to calculate the Raman activities.
The Raman activities were transformed into Raman intensities using Raint program [13] by the
expression:
1
i
Ii 1012 (0 i )4   RA
(1)
i
Where Ii is the Raman intensity, RAi is the Raman scattering activities, νi is the
wavenumber of the normal modes and ν0 denotes the wavenumber of the excitation laser [14].
4. Results and discussion
4.1 Molecular Geometry
The Optimization of FMPVH molecule was performed with B3LYP/6-311++G(d, p)
level of basis set. The molecular geometry of FMPVH was well reproduced with x-ray
diffraction data [15]. The optimized structure has shown in Figure 1. In the present molecule due
to the rotation of C14-N12-N11-C9 dihedral angle there seems a distortion in hydrazone linkage
between phenyl and furan rings, rest of the bonds could not been disturbed. In FMPVH molecule
the bond length of C1-C2, C1-C9 and C2-C3 are calculated 1.370, 1.445 and 1.425 Å. The
experimental bond lengths of above are observed about 1.348, 1.432 and 1.415 Å [15]. The bond
C1-O5 is appeared as ζ bond character, its bond length is calculated about 1.364 Å. Similarly, the
ζ and π character of C14=O15 bond is calculated about 1.212 Å. The experimental value of
C14=O15 bond is at 1.231 Å [15], which coincides well with calculated value. The ζ and π bond
4

characters of N12-C14 and C9-N11 are calculated as 1.390 and 1.282 Å are positively deviated with
experimental (1.348 Å and 1.273Å) data [15]. The deviation of bond length C9-N11 is about 0.009
Å, it seems a good linearity with X-ray value [15]. The bond length of N11-N12 is observed about
1.384 Å [15] which positively deviated (about 29 Å) from our theoretical value. The other
calculated bond lengths in FMPVH were not much distorted in both conformers.
The bond angle of N12-N11-C9 is calculated about 116.68°. Similarly, the bond angle of
N11-N12–C14 is calculated as 121.31°, which nearly matches with experimental value of 119.16°
[15]. From this investigation it fairly explores that, during the course of rotation of the bond, the
entire molecule gets disturbed and the properties of the molecule also changes. From the
literature [16] and our theoretical investigation, the optimized structure is more stable. The
optimized bond parameters of FMPVH are listed in the Table 1.
4.2 Vibrational Assignment
The vibrational analysis of FMPVH was studied on the basis of B3LYP/6-311++G (d,p)
level of basis set. The vibrational assignments were carried out on the basis of furan, methylene,
phenylvinyl and hydrazine group of this molecule. Furthermore, the molecule was predicted at
local lowest minima on the potential energy surface and therefore none of the imaginary
vibrational frequencies appeared. The title molecule is planar and belongs to C1 point group. It
consists of 26 atoms and hence it can have 72 normal modes of vibrations in which 25 stretching
and 47 bending modes. To investigate the exact vibrational behavior of this molecule the total
energy distribution (TED) analysis was performed on the gas phase. The calculated
wavenumbers were compared with recorded vibrational frequencies of FT-IR and FT-Raman
spectra. Some discrepancies could be identified in between real and gas phase molecule and
which were scaled down by proper scale factor [17]. The complete vibrational assignments
5

along with the frequencies are presented in Table 2. The both recorded and theoretical spectra
are shown in Figure 2 and Figure 3.
4.2.1 C-H Vibrations
The heteroaromatic molecule shows the presence of C-H stretching mode in the region
3100-3000 cm-1 which is the characteristic region for the ready identification of C-H stretching
[18, 19]. In this molecule nine C-H stretching vibrations are expected to occur, in which five
from phenyl ring, three from furan ring and one from hydrazone linkage. The phenyl ring C-H
stretching vibrations observed at 3060 (medium: m), 2923 (weak: w) and 3064 cm-1 (w) in FT-IR
and FT-Raman spectra respectively. The calculated wavenumbers for the same mode lies at
3075, 3065, 3055, 3038 and 2908 cm-1 (mode numbers (mode nos.) 5-7, 9 and 10). The
harmonic C-H stretching modes corresponding to furan ring are assigned to 3151 (FT-IR:
3141w), 3126 and 3114 cm-1 (mode nos. 2-4). The mode number 8 (3045 cm-1) belongs to C-H
stretching in hydrazone linkage. These assignments are in agreement with literature [18-20]. In
aromatic compounds the C-H in-plane bending frequencies appear in the range 1000-1300 cm-1
and C-H out-of-plane bending appear in the range 750-1000 cm-1 [21, 22]. In the present work,
the in-plane pending vibration of δCCH is recorded at 1392 cm-1(w), 1150 and 1014 cm-1 (m) in
FT-IR spectrum and their Raman counterpart observed at 1393 and 1291 cm-1 as a medium
strong band. On comparing these recorded values with theoretical values, the mode numbers 19,
22 and 27 are agreeable. The bands observed at 937, 896 (FT-IR) and 951, 790 cm-1 (FT-
Raman) are assigned to C-H out-of-plane bending in FMPVH. The computed wavenumbers for
the same mode observed at 953, 924, 904 and 786 cm-1(mode nos.38, 39, 41 and 46). The
observed and computed values for both C-H in-plane and out-of-plane modes show good
linearity with one and other and also find support from literature [23].
6

4.2.2 N-H Vibrations
The stronger hydrogen band (HB) causes an increase of intensity, bandwidth and their
wave number shift to lower value for the stretching vibration and higher wave numbers for
bending vibration [24]. In the present study the frequency of the vibrational mode of amine
group (N-H) appears as pure and strong at 3246 cm-1 in FT-IR spectrum, while the computed
wave number for this mode is 3362 cm-1 (mode no. 1). As per the investigation of Lorenc et al.
[25] the N-H stretching mode appeared at 3262 (IR) and 3247 (Raman) cm-1. When comparing
our investigation with Lorenc et al. [26], the lowering of experimental frequency may be due to
inter-molecular HB in the solid phase. The calculated TED values for this mode showed 100%
pure as mentioned above. In-plane bending vibration of N-H mode is assigned at 1476 and 1477
cm-1 (medium strong) in FT-IR and FT-Raman spectra respectively. Furthermore the theoretical
value showed about 1488 cm-1 with 53% of TED value. The out-of-plane bending vibration of
N-H modes lies at 937 (m) and 535(w) cm-1 by FT-IR as mixed modes and are supported by
harmonic mode numbers 39, 40 and 56.
4.2.3 C = O, C-O Vibrations
The presence of carbonyl group in FMPVH reveals several molecular properties.
Studying the carbonyl group, the electron density of this group increases with decreasing bond
length and hence the vibrational frequency shifted to the lower range. In evidence with this, the
carbonyl peak appeared at 1646 cm-1 as a strong band. On contrary the DFT result assigned at
1692 cm-1 (mode no.11) as pure as 74% of TED contribution.
In-plane-bending of δC=O contributes as a mixed vibration of δO15-C14-N12, (mode nos. 42
and 63) and δO15-C14-C16(mode no. 57) at 879, 264 and 500 cm-1 respectively. While comparing
this with the experimental values 883 and 269 cm-1 as a weak band in FT-Raman spectrum, the
7

contribution of δC=O calculated about 49% of TED. Out-of-plane mode of this group is recorded
at 690 and 535 cm-1 in FT-IR, whereas the calculated frequency (mode nos. 50 and 56)
contributes about 11 and 20% of TED respectively.
The frequency calculated for νC1-O5 and νC4-O5 lies at 1193, 905 (28%, 12%) and 1138,
1065 cm-1 (and 22%, 37%) respectively, their corresponding experimental value observed at
1078 cm-1 (FT-1R). This negative deviation may be due to the inter-molecule charge
delocalization within the furan ring and the maximum energy delocalization takes part in the σ-
σ* transition. This mode is supported by considerable TED values. On the basis of in-plane
(δOCC
,
OCH) and out-of-plane ГOCCC
,
,
bending the vibrational wavenumber assigned to
OCCH COCH
mode numbers 18, 28, 43 and 39, 46, 49, 53, 55 respectively. While comparing these modes
with experimental one, the mode number 53 shows a good agreement.
4.2.4 Diazo linkage group (-C=N-N-C-) Vibrations
The hydrazone linkage fuses the phenyl and furan rings, which leads the vibrations as
C=N, N-N and C-N as stretching as well as bending modes. The azo group stretching frequency
undergoes a large down shift due to greater conjugation and π electron delocalization [27]. It is
evident from our work, the bond length of π C9=N11is lowered by decreasing electron density
(ED)/1.923e and ζ C14-N12 is higher with increasing ED (1.989e) in the respective bond. Silver
stein et al. [28], assigned the C-N stretching band at 1382-1266 cm-1for aromatic amines. In an
azo compound this mode expected in the region of 1200-1130 cm-1 [29, 30]. Subramanian et al.
[23] recorded a very intense Raman band at 1555 cm-1 originated from the stretching mode of
C=N in the azo group. Our study predicted that the stretching of νC9 = N11 and νC14-N12 groups
were recorded as strong bands at 1616/1618 cm-1 (FT-IR/FT-Raman) and at1223 cm-1(FT-
Raman) respectively. Its theoretical values were predicted near to 1614 and 1251cm-1 (mode
nos.12, 24). The expected bending vibration of δCNH, CCN modes occurred at 1476 (FT-IR: m) and
8

1477 cm-1 (FT-Raman: m), their corresponding computed value at 1488 cm-1 (mode no.16) with
24% of TED contribution. Similarly, the out-of-plane deformation was recorded and computed at
535 (w) and 525 cm-1 respectively, which abide good with reported literature value [23].
4.2.5 C=C, C-C Vibrations
The phenyl ring carbon-carbon stretching vibrations occur in the regions of 1625-1590
1590-1575, 1540-1470, 1465-1430 and 1380-1280 cm-1were given by Varsanyi [31]. Carbon-
carbon stretching bands of furan ring were recorded at 1553, 1531, 1555 and 1520 cm-1 for 2-
furaldehyde dimethyl hydrazone [16]. In our present study, the carbon-carbon band observed at
1569 (m), 1392 (w), 1288 (strong: s) and 1150 (m) in FT-IR spectrum, on the other hand FT-
Raman bands observed at 1563 (m), 1393 (m), 1276 (m) and 1151 (w) cm-1 for six membered
ring. For six membered Skelekal νC=C and νC-C bands were predicted at 1576, 1555, 1417, 1280
and 1155 cm-1 by B3LYP/6-311++G (d,p) basis set. These computed wave numbers were
calculated as mixed of π(C=C) and ζ(C-C) bond character. Similarly, the furan ring C-C bands
were assigned to 1540 (s), 1337 (m), 1078 (w) and 1014 (m) cm-1 in FT-IR and 1338 (w) in FT-
Raman spectra. On comparing these values with computed frequencies, the mode numbers (15,
20, 21, 31 and 33) are in line with experimental values. These modes are mixed with C-H in-
plane bending vibration in this region. The reported value of C-C bands [31] coincides well with
observed, as well as computed values. The phenyl ring in-plane bending deformation was
reported as a weak band at 1000 cm-1 [32]. Similar trend has been observed in the present case as
observed at 1001 cm-1 in FT-Raman spectrum of FMPVH. The mode number 35 belongs to δccc
mode with 35% of TED.
The out-of-plane deformation of ГCCCC group is expected to occur in the range lower than
δCCC group. The out-of-plane bending ГCCCC in furan ring appear as mixed vibrations of ГCCCH
,
9

HCCC, OCCC and ГCOCC with considerable TED values. The observed frequencies 790 (FT-Raman),
638 (FT-IR) and 119 cm-1 (FT-Raman) are assigned to the same mode. Their corresponding
theoretical wave numbers are 786, 655 and 114 cm-1. Both the recorded and computed values are
agreeable and also find support from literature [23].
4.3 Prediction of Hyperpolarizability
The first order hyperpolarizabilities of FMPVH molecule is calculated using B3LYP/6-
311++G(d,p) level of basis set, based on the finite-field approach. In the presence of an applied
electric field, the energy of a system is a function of the electric field. First hyperpolarizability is
a third rank tensor that can be described by a 3x3x3 matrix. The 27 components of the 3D matrix
can be reduced to 10 components due to Kleinman symmetry [33]. It can be given in the lower
tetrahedral format. It is obvious that the lower part of the 3x3x 3 matrixes is a tetrahedral. The
components of β are defined as the coefficients in the Taylor series expansion of the energy in
the external electric field. When the external electric field is weak and homogeneous, this
expansion becomes:
E  E0   F 1/ 2 F F 1/6 F F F
(2)




Where E0is the energy of the unperturbed molecules, Fα is the field at the origin, and
 , ,
 is the components of the dipole moment, polarizability and the first order
hyperpolarizabilities respectively. The total static dipole moment μ, the mean polarizability α0,
the anisotropy of polarizabilityΔα and the mean first hyperpolarizability β0, using the x, y, z
components are defined as
  (x2  y2  z2 )1/2
(3)
10

xx yy zz
0 
(4)
3
  21/2   2    2    2  6 2 2 2

1/2 (5)

xx 

yy 

zz 

xz 

xx
yy
zz
xy
yz



1/ 2
x2  y2  z2

(6)
0 

Many organic molecules, containing conjugated π electrons were characterized by large values
of molecular first order hyper polarizabilities and analyzed by means of vibrational spectroscopy
[34-37]. The intra-molecular charge transfer from the donor to acceptor group through a
single-double bond conjugated path can induce large variations on both the molecular
dipole moment and the molecular polarizability making IR and Raman activity strong at
the same time [38].
The total molecular dipole moment (µ) and mean first order hyperpolarizability (β0) are
given as 1.0516 Debye and 17.866 x 10-30esu, respectively. The total dipole moment of the title
compound is approximately higher and the first order hyperpolarizability (β0) of the title
molecule is forty eight times greater than that of the urea, hence this molecule has considerable
NLO activity. The hyperpolarizabilities of FMPVH are given in Table 3.
4.4 Natural bond orbital (NBO) analysis
The hyperconjugation may be given as stabilizing effect that arises from an overlap
between an occupied orbital with another neighboring electron deficient orbital, when these
orbitals are properly oriented. This non-covalent bonding (antibonding) interaction can be
quantitatively described in terms of the NBO analysis, which is expressed by means of the
second-order perturbation interaction energy (E(2)) [39-42]. This energy represents the estimate
11

of the off-diagonal NBO Fock matrix elements. It can be deduced from the second-order
perturbation approach [43]
F(i, j)2
 j i
E(2)  Eij  qi
(7)
Where qi is the donor orbital occupancy, εi and εj are diagonal elements (orbital energies) and
F(i,j) is the off diagonal NBO Fock matrix elements. NBO analysis of FMPVH has been
performed, in order to explain the intra-molecular charge transfer and delocalization of π-
electrons. The intra-molecular hyperconjugative interaction is due to the overlap between π(C-C)
and π*(C-C) the orbitals, which results in intra-molecular charge transfer, appeared in the
molecular system [38].
In this present study, the NBO analysis has been carried out with B3LYP/6-311++G(d,p)
level of basis set and which deals the intra-molecular charge transfer within the molecule. In any
molecule, the π character of the bond plays an important role when compare with σ bond
character. In such a way that this molecule delivers maximum delocalization energy during the
transition between π and π* bond whereas the ED of the donor (Lewis) bond decreases with
increasing of ED of acceptor (Non-Lewis) bonds. In accordance with the above, the title
molecule shows 67.53 and 81.59 KJ/mol of energy during the interaction between πC1-C2 and
π*C3-C4, π*C9-N11 bonds, on the other hand the ζC1-C2 and σ*C1-C9 shows about 15.56 KJ/mol
energy. The electron densities of the above bonds are about 1.982e (ζC1-C2) and 0.029e (ζ* C1-
C9) for the donor and accepter bond respectively. The electron densities of πC1-C2 and π* C3-C4
are calculated about 1.793e and 0.262e respectively. From these observations the ζ-ζ* and π- π*
interaction reveals that, the ED of particular π bond decreases with increasing of π* ED and vice
versa for ζ and ζ* bond which may be due to the delocalization. Similarly, the π and π*
12

interaction in the molecule appear as the maximum delocalization energy which leads the
molecule become highly active. The lone pair of oxygen and nitrogen atoms play great role in
the molecule. The O5 atom transfers 119.75 kj/mol and 118.95 kj/mol to π* C1-C2 and π* C3-C4
bonds respectively. In the same way the N12 transfers 122.17 kj/mol to π* C9-N11 and O15
transfers 120 kj/mol to π* N12-C14. The maximum hyperconjugative E(2)energy of heteroatoms
during the intra- molecular interaction leads the molecule towards medicinal and biological
applications. The lewis and non-lewis NBO’s of the FMPVH are given in Table S1 (Supporting
information).
4.5 HOMO-LUMO Analysis:
The highest occupied molecular orbital (HOMO) and Lowest unoccupied molecular
orbital (LUMO) are the main orbitals that take part in chemical stability. The HOMO represents
the ability to donate an electron, LUMO as an electron acceptor represents the ability to obtain
an electron. This also predicted that the nature of electrophiles and nucleophiles to the atom
where the HOMO and LUMO are stronger. The energy gap FMPVH was calculated using
B3LYP/6-311++G(d,p) level. In this title compound, highest electronic energy lies at furan ring
and hydrazone linkage and the HOMO is calculated about -6.093 eV. The kinetic energy of the
56th occupied level (HOMO) is calculated as 1.59 a.u. The lowest electronic energy appeared in
the phenyl ring, which exhibited at 57th virtual orbital and measured as LUMO value -1.927 eV,
along with kinetic energy of 1.618 a.u. The energy gap of HOMO and LUMO could be
determined about - 4.166 eV, which leads the molecule becomes less stability and more
reactivity. Moreover, the separation of Homo and Lumo determines that the molecule becomes
active in any field. In such a way, the energy of occupied levels 55, 54, 53 and 52 were
calculated about -7.143, -7.468, -7.556 and – 7.875 eV whereas the unoccupied levels lies in the
13

ranges at -1.927 (V57) – 1.139 (V58), -0.842 (V59),-0.541 (V60) and -0.198 (V61). The calculated
energies of frontier molecular orbitals are listed in Table 4. Corresponding frontier molecular
orbitals are shown in Figure 4.
4.6 Electrostatic Potential
The information provided by inspection of the Homo and Lumo is thus visualizing the
electrostatic potential (ESP). The electrophiles tend to negative ESP and nucleophiles tend to
region of positive ESP. In accord with this the carbonyl and furan ring behaves as electrophiles
region and it is denoted as exo face (top) as red colour. The molecular electrostatic potential was
calculated with B3LYP/6-311++G(d,p) level of basis set. The calculated electrostatic energy is
about -606.67 eV and -609.52 eV for O5 and O15 respectively. Similarly, the nucleophiles region
was graphically shown as in the endo face (bottom) region. It is possibly denoted by the blue
colour and expressed electron deficiency in those regions, which also denotes nucleonic energy
of Lumo orbitals. The calculated nucleophiles energies are about -499.51 (N11) and -498.67 eV
for the hydrazone region. The ESP diagram is shown in Figure 5 and calculated electrostatic
energies are given in Table S2. The atomic charge plot of FMPVH is shown in Figure S1
(Supporting information).
4.7. UV-analysis
The ultraviolet spectrum which results from the promotion of an electron in an occupied
molecular orbital (MO) of ground electronic state molecule into a virtual MO, thus forming an
electronically excited state [44]. The UV analysis was carried out using B3LYP/6-311++G(d,p)
level of basis set for FMPVH. The recorded electronic spectrum of FMPVH shows the
transitions at 352 nm and 302 nm, which clearly understands that the recorded region 352 nm
relatively coincides with calculated value of 317 nm. The calculated results of FMPVH possess
14

three excited states (ES), in which ES-1 appeared at 317.98 nm (3.899 eV), ES-2 at 292.72 nm
and ES-3 lies at 271.10 nm. The ES-1 reveals the transition between HOMO56 to LUMO57 and
also next level LUMO58. And for ES-2 there are three transitions from HOMO53-LUMO57,
HOMO55-LUMO57 and LUMO58. In which the transition of electron from HOMO53 to LUMO57
is larger on comparing with other transitions. The calculated band gap (292.72 nm) of ES-2
coincides well with the recorded value of 303.49 nm. In the same way, ES-3 has two transition
namely HOMO56-LUMO58 and LUMO59 and their band gap energy is about 4.573 eV (271.10
nm). The excitation energies of FMPVH are listed in Table 5. The UV-Vis. spectrum of
FMPVH has shown in Figure 6.
5. Conclusion
The complete vibrational analysis has been performed for the first time to the FMPVH.
The optimized geometrical parameters are agrees well with literature value. The observed FT-IR
and FT-Raman spectral values are well supported by calculated values. The vibrational
frequencies for C=O and C=N (functional groups) are shifted to lower frequency, which is due to
the presence of π-bonds. The calculated first order hyperpolarizability of FMPVH molecule is
found to be 17.866 x10-30 esu, which is forty eight times greater than that of urea. NBO result
reflects the charge transfer within the molecule and the maximum charge delocalization takes
place during π-π* transition. The band gap of FMPVH molecule was determined about -4.166
eV, which leads the molecule becomes less stability and more reactivity. The MEP represents
that the carbonyl group and furan ring behaves as electrophiles region and hydrozone region
behaves as nucleophiles. The recorded UV-Vis., spectral values agree well with calculated
values.
15

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239.
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41.
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Wiley New York, 1997.
18

Fig. 1 The optimized molecular structure of FMPVH.

0.00
0.02
0.04
0.06
0.08
0.10
FT-IR
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
IR/B3LYP
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
Fig. 2 The combined experimental and Theoretical IR spectrum of FMPVH.

0.50
0.40
0.30
0.20
0.10
FT-Raman
0.00
1.00
0.80
0.60
0.40
0.20
0.00
Raman/B3LYP
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
Fig. 3 The combined experimental and Theoretical Raman spectrum of FMPVH.

HOMO
LUMO
Fig. 4 The frontier molecular orbital of FMPVH

Fig. 5 Molecular electrostatic potential of FMPVH

1.0
0.8
0.6
0.4
0.2
0.0
302.06905
UV/B3LYP/6-311++G(d,p)
3.5
353
303
3.0
2.5
2.0
1.5
1.0
0.5
0.0
UV-Vis.,
100
200
300
400
500
600
Wavelength (nm)
Fig. 6 The UV-spectrum of FMPVH

Table 1. The optimized bond parameters of FMPVH using B3LYP/6-311++G(d,p) level.
X-ray dataa
1.348
X-ray dataa
Parameters
C1-C2
C1-O5
C1-C9
C2-C3
C2-H6
C3-C4
C3-H7
C4-O5
Parameters
O5-C4-H8
C1-O5-C4
C1-C9-H10
C1-C9-N11
Bond length (Å)
1.373
1.364
1.440
1.427
1.079
1.362
1.078
1.358
1.077
1.097
1.282
1.355
1.016
1.390
1.212
1.504
1.401
1.400
1.394
1.085
1.391
1.083
1.393
1.084
1.395
1.084
1.084
Bond angle (º)
115.76
107.19
114.86
122.85
122.29
116.68
119.40
121.31
118.85
123.36
113.95
122.68
123.47
117.29
119.21
120.34
120.59
119.02
120.37
118.55
121.08
120.07
119.79
120.14
120.16
119.80
120.04
119.85
120.03
120.12
124.5
105.68
119.10
121.81
119.10
115.43
120.40
119.16
120.4
122.65
116.08
121.24
123.59
117.59
118.82
120.22
119.9
119.9
120.39
119.6
119.6
120.23
119.9
119.9
119.89
119.6
120.1
120.03
120.0
1.366
1.432
1.415
0.9300
1.327
0.9300
1.368
0.9300
0.93
1.273
1.384
0.860
1.348
1.2306
1.490
1.390
1.387
1.379
0.930
1.377
H10-C9-N11
C9-N11-N12
N11-N12-H13
N11-N12-C14
H13-N12-C14
N12-C14-O15
N12-C14-C16
O15-C14-C16
C14-C16-C17
C14-C16-C18
C17-C16-C18
C16-C17-C19
C16-C17-H20
C19-C17-H20
C16-C18-C21
C16-C18-H22
C21-C18-H22
C17-C19-C23
C17-C19-H24
C23-C19-H24
C18-C21-C23
C18-C21-H25
C23-C21-H25
C19-C23-C21
C19-C23-H26
C21-C23-H26
C4-H8
C9-H10
C9-N11
N11-N12
N12-H13
N12-C14
C14-O15
C14-C16
C16-C17
C16-C18
C17-C19
C17-H20
C18-C21
C18-H22
C19-C23
C19-H24
C21-C23
C21-H25
C23-H26
0.9300
1.380
0.930
1.376
0.93
0.93
X-ray dataa
110.11
130.51
119.36
106.54
126.70
126.7
Parameter
C2-C1-O5
C2-C1-C9
O5-C1-C9
C1-C2-C3
C1-C2-H6
C3-C2-H6
C2-C3-C4
C2-C3-H7
C4-C3-H7
C3-C4-O5
C3-C4-H8
Bond angle (º)
109.66
130.48
119.86
106.47
126.10
127.42
105.94
127.58
126.48
110.74
133.50
120.0
106.65
126.70
126.7
111.01
124.5
a
Ref. [15]

Table 2.The experimental and calculated frequencies of FMPVH (trans) using B3LYP/6-311++G(d,p) level of basis set [harmonic
frequency (cm−1), IR , Raman intensities (Km/mol), reduced masses (amu) and force constants (mdynA°−1)].
Frequencies
No Unscaled
Observed
Intensity
Sl.
Red.
Force
Const.
7.76
Vibrational Assignments TED ≥10%d
νN12H13 (100),
νC3H7 (13), νC4H8 (84),
ν C2H6 (87),
Scaleda FT-IR
FT-Raman IRb Ramanc Mass
3362
3151
3126
3114
3075
3065
3055
3045
3038
2908
1692
1614
1576
1555
1535
1488
1462
1442
1417
1368
1307
1299
1280
1251
1203
1193
1155
1138
3246s
1.18
0.04
0.15
1.18
1.69
3.45
4.45
0.72
1.46
10
3499
3279
3253
3241
3200
3190
3180
3170
3162
3026
1761
1680
1640
1619
1598
1549
1521
1501
1475
1424
1360
1352
1332
1302
1252
1242
1203
1184
1.44
0.85
0.57
0.54
0.88
1.22
0.46
0.54
0.16
0.38
4.86
100
1.08
1.11
1.1
1.09
1.09
1.1
1
2
3
4
5
6
7
8
3141w
7
6.84
6.76
6.61
6.57
6.5
6.44
6.4
5.86
νC3H7 (81),
νC18H22 (81), νC21H25 (14),
νC19H24(38), νC23H26(39),
νC17H20(13), νC19H24(33), νC21H25(38), νC23H26(11),
νC9H10 (100),
νC17H20(27), νC21H25(36), νC23H26(34),
νC17H20(54), νC19H24(28), νC23H26(13),
3060m
3064w
1.09
1.09
1.09
1.09
11.11
6.98
5.52
5.52
5.08
1.97
2.24
3.52
2.17
2.88
1.5
1.69
3.45
3.8
3.19
1.61
1.15
1.12
9
2923w
1646vs
1616s
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
80.6
5.53
0.84
1.13
12.3
81.7
3.31
12.6
0.66
0.57
3.85
0.42
0.26
4.14
100
20.31 ν C14=O15 (74),
1618vs
1563ms
11.6
8.75
8.51
7.64
2.78
3.06
4.67
2.78
3.44
1.64
1.81
3.6
ν C9=N11 (59),
νC19C17(19), νC21C18(21),
1569ms
10.85
0.37
2.29
5.9
νC17C16(15), νC18C16(14), νC23C19(19), νC23C21(19),
νC2C1(38), νC4C3(14), νC9C1(17),
δH13N12N11(29), δH13N12C14(24),
νCC(18), δCCH(17), δHCC(27)
νC2C1(12), νC4C3(40), νO5C4H8(12),
νC19C17(10), νC21C18(10), δH26C23C19(14), δH26C23C21(14),
νC3C2(16), νC4C3H7(12), δH8C4C3(12),
νC3C2(14), δH10C9C1(16), δH10C9N11(23),
δH20C17C16(16), δC19C17H20(14), δH22C18C16(14), δC21C18H22(11),
νC17C16(20), νC18C16(20),
1540s
1476m
1477ms
2.17
22.95
0.14
10.76
6.61
0.31
0.19
2.06
26.72
1.4
1392w
1393m
1338w
1337ms
1291ms
1276m
1223
1288s
3.8
νC14N12(15), νC16C14(16),
2.95
1.46
0.98
0.92
νC16C14(11), δH6C2C1(12), δC3C2H6(11),
νO5C1(28), δH10C9N11(12),
νC19C17(11), δH24C19C17(12), δC23C19H24(13),
νO5C4(22), O5C4H8(12),
0.15
8.4
1150m
1151w
1.86
0.21
0.11

1136
1116
1065
1061
1032
1006
996
976
970
953
924
905
904
879
868
848
826
786
775
762
725
690
676
666
655
608
581
525
500
469
404
398
7.29
55
1182
1162
1108
1104
1074
1047
1037
1016
1010
992
961
942
941
915
903
882
860
818
807
793
754
718
704
693
682
632
604
547
521
489
421
414
2.95
12.14
0.95
1.39
2.39
2.42
3.63
4.58
0.04
0.08
1.16
0.19
0.47
0.18
1.19
0.18
0.23
0.08
2.41
0.74
0.23
0.3
2.14
3.65
2.12
2.02
3.34
2.36
1.38
5.81
1.32
1.37
3.51
1.44
1.49
6.46
6.13
1.33
1.25
1.34
3.01
4.6
1.27
1.72
3.11
6.38
4.88
6.3
2.95
3.8
1.29
5.34
4.62
2.94
1.76
2.9
δC23C21H25(10), δH26C23C19(17), δH26C23C21(15),
νN12N11(11), δC14N12(14),
νC3C2(11), νC4C3(12), νC4O5 (37),
νC19C17(15), νC21C18(14),
νC23C19(22), νC23C21(20),
νC3C2(22), δC3C2H6(16), δC3C2H7 (13), δC4C3H7(11),
δCCC(35)
νN12N11(15), νC18C16(10),
ГH25C21C18H22(22), ГH26C23C19H24(13), ГH26C23C21H25(26),
ГH24C19C17H20(21), ГH25C21C18H22(13), ГH26C23C19H24(18),
ГH10C9C1C2(11), ГH10C9C1O5(16), ГN12N11C9H10(34),
νO5C1(12), ГN12N11C9H10(16),
ГH24C19C17H20(15),
δC14N12N11(11), δO15C14N12(13),
δC4C3C2(22), δO5C4C3(23), δH7C3C2(10),
ГH7C3C2H6(38), ГH8C4C3H7(24),
ГC19C23C21H25(10),
ГC4C3C2H6(17), ГH6C2C1O5(13), ГH8C4C3H7(23), ГH6C2C1C9(19),
ГC17C16C14N12(10), ГC18C16C14O15(12),
δN12N11C9(11),
ГH7C3C2C1(13), ГO5C4C3H7(19), ГH8C4C3C2(30), ГC1O5C4H8(15),
ГO15C14N12H13(11),
ГCCCC(51), ГHCCC(22)
δC19C23C21(16),
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1078w
1014m
4.03
2.69
1.37
3.91
6.58
0.82
0.17
0.36
10.8
1.52
1.89
5.27
2.37
0
1.53
1.45
2.27
1.53
0.87
3.53
0.8
0.79
1.91
0.75
0.78
3.19
2.95
0.61
0.54
0.53
1.15
1.71
0.43
0.52
0.91
1.8
1057w
1001w
951w
883w
790w
937m
896w
0.32
2.14
1.48
4.23
17.5
16.5
1.84
5.77
0.18
0.26
2.25
4.67
11.2
0.17
2.36
0.04
763ms
690m
0.05
0.3
638m
600w
0.12
0.73
0.04
1.32
1.18
0.5
1.34
1.48
0.63
0.67
0.21
0.75
0.48
0.3
ГC3C2C1O5(16), ГC4O5C1C2(16),
δC19C17C16(13), δC21C18C16(13), δC23C19C17(15), δC23C21C18(15),
ГC4C3C2C1(16), ГC1O5C4C3(18), ГO5C4C3C2(26),
ГH13N12N11C9(33), ГO15C14N12H13(20), ГC16C14N12H13(34),
δC16C14N12(12), δO15C14C16(20),
535w
νC9C1(11),
0.54
0.1
δC2C1C9(15), δO5C1C9(15), δ N12N11C9(20),
δCCC(11), ГCCCC(20)

372
354
264
248
228
174
127
114
67
0.53
0.17
2.75
0.13
3.44
1.09
0.41
0.85
0.27
0.28
0.2
387
369
275
258
237
181
133
119
70
0.15
0.25
0.32
0.91
0.87
1.1
0.89
1.18
3.97
3.2
7.67
6.18
3.91
6.27
4.39
5.37
5.92
6.12
6.18
5.71
4.01
5.54
0.68
0.49
0.17
0.25
0.15
0.1
ГC23C19C17C16(12), ГC23C21C18C16(12),
61
62
63
64
65
66
67
68
69
70
71
72
N12N11C9C1(28),
269w
δO15C14N12(16), δC18C16C14(21),
ГC3C2C1C9(12), ГH10C9C1C2(15), ГC14N12N11C9(11),
δN12N11C9(11),
δC14N12N11(14),
δC16C14N12(10),
192w
162w
0.06
0.05
0.02
0.01
0.00
0.00
119w
79ms
ГC3C2C1C9(11), ГN11C9C1O5(31),
ГN12N11C9(13), ГC17C16C14N12(14), ГC17C16C14O15(11),
ГC16C14N12(10), ГC18C16C14N12(13), ГC18C16C14O15(10),
ГN11C9C1O5(12), ГH13N12N11C9(15), ГC16C14N12N11(15),
ГC14N12N11C9(22), ГC16C14N12N11(23),
49
51
37
33
36
8.88
3.48
32
0.21
a
b
: Stretching, δ: in-plane-bending, Γ: out-of-plane bending, vw: very week, w:week, m:medium, s:strong, vs:very strong, Scaling factor: 0.9608 [17], Relative IR absorption intensities normalized with highest peak absorption equal to 100,
c
d
Relative Raman intensities calculated by Equation (1) and normalized to 100. Total energy distribution calculated at B3LYP/6-311++G(d,p) level.

Table 3. The Non-linear measurements of FMPVH.
Parameters
Hyperpolarizability
-2048.67
479.46
βxxx
βxxy
βxyy
-39.85
βyyy
-56.77
βxxz
87.45
βxyz
-32.03
βyyz
-7.20
βxzz
60.29
βyzz
-24.64
βzzz
β0
-13.73
17.866x10-30 esu
Dipole moment
-0.4860
Parameters
μx
μy
μz
μ
-0.9188
-0.1872
1.0561 Debye
Standard value for urea μ=1.3732 Debye, β0=0.3728x10-30esu.