Synthesis, single crystal structure, spectroscopic characterization and?molecular properties of (2E)-3-(2,6-dichlorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one

Article abstract of DOI:10.1016/j.molstruc.2016.02.089

A novel (2E)-3-(2,6-dichlorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one (DCPDMP) compound has been synthesized and its single crystal has been grown by slow evaporation technique. The structure of the compound has been characterized by FT-IR, FT-Raman

Full text of DOI:10.1016/j.molstruc.2016.02.089

Accepted Manuscript
Synthesis, single crystal structure, spectroscopic characterization and molecular
properties of (2E)-3-(2,6-dichlorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one
C.S. Chidan Kumar, C.K. Quah, V. Balachandran, H.K. Fun, A.M. Asiri, S. Chandraju,
M. Karabacak
PII:
S0022-2860(16)30183-1
10.1016/j.molstruc.2016.02.089
MOLSTR 22298
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 9 November 2015
Revised Date: 24 February 2016
Accepted Date: 24 February 2016
Please cite this article as: C.S. Chidan Kumar, C.K. Quah, V. Balachandran, H.K. Fun, A.M. Asiri,
S. Chandraju, M. Karabacak, Synthesis, single crystal structure, spectroscopic characterization and
molecular properties of (2E)-3-(2,6-dichlorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one, Journal of
Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.02.089.
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Graphical abstract

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Synthesis, single crystal structure, spectroscopic characterization and molecular
properties of (2E)-3-(2,6-dichlorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one
C.S. Chidan Kumar1,2, C.K. Quah1, V. Balachandran3, H.K. Fun1,4#, A.M. Asiri5,6, S.
Chandraju7, M. Karabacak8,
1 X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, USM, Penang,
Malaysia
2 Department of Engineering Chemistry, Alva’s Institute of Engineering & Technology, Mijar,
Moodbidri, Mangalore (D.K), Karnataka, India
3 Centre for Research, Department of Physics, AA Government Arts College, Musiri, India
4 Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University,
Riyadh, Saudi Arabia
5 Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi
Arabia
6 Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah,
Saudi Arabia
7 Department of Sugar Technology and Chemistry, Sir M. Visvesvaraya PG Center,
University of Mysore, Tubinakere, Karnataka, India
8 Department of Mechatronics Engineering, H.F.T. Technology Faculty, Celal
Bayar University, Turgutlu, Manisa, Turkey
Corresponding author: mehmet.karabacak@cbu.edu.tr
Tel.: +90 236 314 10 10, Fax: +90 236 314 20 20
# Additional correspondence author: hkfun@usm.my ; hfun.c@ksu.edu.sa
Tel.: +91 9894253672; Fax: +91 4326 262630.

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Abstract
A novel (2E)-3-(2,6-dichlorophenyl)-1-(3,4-dimethoxyphenyl)prop-2-en-1-one (DCPDMP)
compound has been synthesized and its single crystal has been grown by slow evaporation
technique. The structure of the compound has been characterized by FT-IR, FT-Raman and
single-crystal X-ray diffraction techniques. The optimized molecular structure, vibrational
wavenumbers, corresponding vibrational assignments of the compound have been
investigated by means of the density functional theory. The molecule crystallizes in triclinic
system, space group P-1 with a = 7.6179 (7), b = 8.5023 (7), c = 12.1967 (10) Å, V = 764.39 (11)
Å3 and two molecules in the unit cell. The crystal structure is primarily stabilized through
intramolecular C–H…Cl and C–H…O hydrogen bonds and intermolecular C–H…O and
weak C–H…π interactions. These inter- and intramolecular interactions are analyzed.
Moreover, the molecular electrostatic potential surface of the molecule has been constructed.
Global and local reactivity descriptors and dipole moment (µ), static polarizability (α), first
order hyperpolarizability (β) and optical gap (∆E) have been also calculated to study the
nonlinear optical (NLO) property of the title compound.
Keywords: Crystal growth; FT-IR and FT-Raman spectra; DFT; NBO and NLO; HOMO-
LUMO.
1.
Introduction
The design and synthesis of organic molecules exhibiting nonlinear optical (NLO)
properties have been motivated by their potential for applications in optical communications,
optical computing, data storage, frequency mixing, and optical switching [1]. Chalcones are
interesting organic NLO materials with good crystallizability, high second harmonic
generation (SHG) efficiency compared to urea, and optical transparency extending down to
the blue region [2,3]. It has been generally understood that the second-order molecular
nonlinearity in chalcones can be enhanced by large delocalized π-electron systems with strong
donor and acceptor groups. The basic strategy of using electron-donor and electron-acceptor
substituents to polarize the π-electron system of organic materials has been illustrious for
developing the NLO chromophores possessing large molecular nonlinearity. Many
researchers suggested that the theoretical hyperpolarizability studies on these molecules that

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the carbonyl group present at the middle in these molecules splits the conjugated system into
relatively two independent parts and the electron donors, such as -OCH3, -CH3, -Cl and –Br,
are the best donor groups for enhancing SHG in chalcones [4,-6].
To the best of our knowledge, this compound has not been reported and studied as far
as its relevance is concerned. The aim of this paper is to describe the synthesis, molecular
structure and single-crystal growth of DCPDMP. The structure of the compound was
characterized by FT-IR and FT-Raman and confirmed by single crystal X-ray diffraction
techniques. Vibrational frequencies and geometric parameters of DCPDMP in the ground
state were calculated by using B3LYP/6-31G(d) and 6-31G(d,p) basis sets. A detailed
quantum chemical study will aid in making definite assignments to fundamental normal
modes of DCPDMP and in clarifying the experimental data for this important molecule. In
addition, Density Functional Theory (DFT) method in conjunction with the BLYP functional
using 6-31G(d) and 6-31G(d,p) basis sets was employed to predict the dipole moments,
polarizability, hyperpolarizability, frontier orbital energy, molecular electrostatic potential
surface, natural bond orbital and reactivity descriptors with molecular geometry. The findings
of these spectroscopic and theoretical studies are herein reported.
2.
Experimental methods
Synthesis
2.1.
The reagents and solvents for the synthesis were obtained from Aldrich Chemical Co.,
and were used without additional purification. New chalcones were designed and synthesized
by the reaction of 1-(3,4-Dimethoxyphenyl) ethanone with substituted 2,6-
dichlorobenzaldehyde in presence of catalytic amount of NaOH in methanol, as shown in
Scheme 1. 1-(3,4-Dimethoxyphenyl) ethanone (0.01 mol) and 2,6-dichlorobenzaldehyde
(0.01 mol) were dissolved in 20 ml methanol. A catalytic amount of NaOH was added to the
solution drop-wise with vigorous stirring. The reaction mixture was stirred for about 5-6
hours at room temperature. The progress of the reaction was monitored by TLC. The formed
crude products were filtered, washed successively with distilled water and recrystallized from
ethanol to get the title chalcone. Crystals suitable for X-ray diffraction studies were obtained
from acetone solution by slow evaporation technique at room temperature. Melting point
(384–386 K) was determined by Stuart Scientific (UK) apparatus. The purity of the
compound was confirmed by thin layer chromatography using Merck silica gel 60 F254
coated aluminum plates.

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2.2.
Instrumentation
The compound DCPDMP on powder form was synthesized and it is used to record the
FT-IR and FT-Raman spectra. The FT-IR spectrum for the compound was recorded on a UV–
VIS–NIR Perkin Elmer Lambda 900 spectrometer in the range of 4000-400 cm−1 without
using NaCl plates or KBr pellets (in solid form). The FT-Raman spectrum was recorded using
the 1064 nm line of a Nd:YAG laser as the excitation wavelength in the region 3500-100 cm−1
on a Nexus 670 spectrophotometer.
2.3.
Computational methods
Thorough information including structural attributes and vibrational modes of
DCPDMP has been presented in a comparative way using (DFT) strategy with different basis
sets. All the calculations were performed using Gaussian 09 program suite [7]. Geometry
optimization was carried out at DFT method by using 6-31G (d) and 6-31G (d,p) basis sets to
portray all stationary points as minima. Then, these optimized structural parameters were used
for frequency calculations ensuing IR and Raman frequencies. To obtain better agreement
with the experimental and theoretical results standard scale factors (correction factors) were
used. At B3LYP method with both the basis sets like 6-31G(d)/6-31G(d,p) a scaling factor of
0.98 has been recommended for all frequencies <1800 cm−1. A scaling factor of 0.96 was
utilized for C−H stretching modes due to large anharmonicities in higher wavenumber region
>2700 cm−1. However, for vibrational modes observed in lower wavenumber region <1500
cm−1 a scaling factor 1.0 has been prescribed. Correction factors for B3LYP is therefore much
more useful in bringing the experimental and theoretical results closer to each other. The
vibrational modes are assigned on the basis of Total Energy Distribution (TED) analysis using
Vibrational Energy Distribution Analysis (VEDA) program [8]. The Natural Bond Orbital
(NBO) calculations [9] were performed by using NBO 5.0 Program as implemented in the
Gaussian 09W [7] package at B3LYP/6-31G(d,p) method in order to understand various
second order interactions between the filled orbital of one subsystem and vacant orbital of
another subsystem, which are the measure of the intramolecular delocalization or hyper
conjugation. The highest occupied and lowest unoccupied molecular orbitals (HOMO and
LUMO) of the compound were analyzed.
3.
Results and Discussion
The geometrical parameters of the synthesized compound are reported and discussed

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with respect to the X-ray data. This is followed by discussion of the experimental and
theoretical vibrational frequencies and their intensities. The frontier molecular orbitals,
natural bond orbital (NBO) are also explored. Furthermore, in order to show nonlinear optics
activity of the molecule, the dipole moment, linear polarizability and first order
hyperpolarizability are analyzed.
3.1.
X-ray crystallographic studies
Yellow, block shaped single crystal of DCPDMP, with dimensions of 0.48 mm × 0.20
mm × 0.21 mm was selected and mounted on a BRUKER APEX-II CCD diffractometer with
a fine-focus sealed tube graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 294 K
in the range of 1.7 ≤ θ ≤ 26.0°. The data were processed with SAINT and corrected for
absorption using SADABS [10]. A total of 12215 reflections were collected, of which 2986
were independent and 2459 reflections with I > 2σ(I). The structures were solved by direct
method using the program SHELXTL [11] and were refined by full-matrix least squares
technique on F2 using anisotropic displacement parameters for all non-hydrogen atoms. All
the hydrogen atoms were positioned geometrically [C—H = 0.93−0.96 Å] and refined using
riding model with isotropic displacement parameters set to 1.2 or 1.5 (methyl group) times the
equivalent isotropic U values of the parent carbon atoms. A rotating group model was used
for methyl groups. The final full-matrix least squares refinement gave R = 0.043 and wR =
0.135 (w =1/[σ2(Fo2) + (0.0678 P)2 + 0.2837P] where P = (Fo2 + 2Fc2)/3, S = 1.09, (ꢀ/σ)max
= 0.001, ꢀρmax = 0.28 e Å−3 and ꢀρmin = −0.23 e Å−3. A summary of crystal data and
parameters for structure refinement details are given in Table 1.
The molecular structure of the title compound, C17H14Cl2O3, with atom labelling
scheme drawn at 50% probability displacement ellipsoid is depicted in Fig. 1. The interplanar
angle between the dimethoxyphenyl and 2, 6-dichlorophenyl rings is 0.90 (11)0. Both of these
phenyl rings are connected via central prop-2-en-1-one bridge. The molecule exist in trans
configuration with respect to the C8=C9 double bond of the central enone group, which is
confirmed by the C7—C8=C9—C10 torsion angle of 176.1 (3)0. In the structure, two weak
intramolecular C9—H9A•••Cl1 and C8—H8A•••Cl2 interactions (Table 2, Fig. 1) generate S
(5) and S (6) ring motif’s respectively [12]. These interactions contributed to the planarity of
the molecule. The methoxy group attached to C4 atom is close to planar with the C17—O2—
C4—C5 torsion angle of 0.2 (3)0 and another methoxy group attached to C3 atom is slightly
twisted with the C16—O1—C3—C2 torsion angle of −7.9 (4)0. Besides Cl atoms are planar

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to the ring. In the crystal structure, intermolecular C—H…O hydrogen bonds (Table 2) link
the molecule into chains in head-to-tail fashion. Further, the adjacent molecule of these chains
are connected via Cl…Cl (3.494 Å) short contacts producing one-dimensional sheets
extending along b axis direction. These molecular sheets are stacked into layers (Figs. 2 and
3) along ac plane by π—π interactions with Cg1…Cg1 and Cg2…Cg2 distance of 3.7123 (13)
and 3.5843 (14) respectively (where, Cg1 is the centroid of the C1—C6 benzene ring and Cg2
is the centroid of the C10—C15 benzene ring). In addition, crystal structure features for a
weak C—H••• π interaction (Table 2) involving the centroid of the C1—C6 benzene ring.
The bond length and bond angles agree with the literature values and are comparable with
those reported earlier [13-15].
The optimized parameters (bond lengths, bond angles, and dihedral angles) of the title
compound [Fig. 4] have been obtained using the B3LYP/6-31G(d) and 6-31G(d,p) method.
Some selected geometrical parameters experimentally obtained and theoretically calculated
are listed in Table 3. For example, the double C16 = O17 and C11 = C14 double bond lengths
were calculated as 1.23 and 1.34 Å, respectively, which are in a good agreement with
experimental values (1.21 and 1.30 Å). Most of the bond lengths and bond angles are slightly
deviating when comparing with the experimental data for both DFT functional. These
differences are probably due to the theoretical calculations belong to isolated molecule in
gaseous phase while the experimental results belongs to molecule in solid state.
3.2.
Vibrational spectral analysis
The observed and calculated vibrational frequencies along with assignments have been
summarized in Table 4. For visual comparison, the observed and calculated (simulated)
infrared and Raman spectra of the title compound were presented in Figs. 5 and 6, which is
convenient to discuss the vibrational spectra of the title molecule as described below:
C–Cl vibrations
The vibration belonging to the bond between the ring and halogen atoms is worth to
discuss here, since mixing of the vibrations is possible due to the lowering of the molecular
symmetry and the presence of heavy atom on the periphery of the molecule [16]. Generally,
stretching and bending vibrations of C–Cl bonds lie in the low wavenumber region of the
spectrum [17,18]. Compounds with more than one chlorine atom exhibit very strong bands

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due to the asymmetric and symmetric stretching modes. The vibrations of C–X group (X; F,
Cl, Br) in the frequency range give generally strong bands in the region 1292-485cm−1
[19,20]. Based on the above literature values the strong band is observed at 767 cm−1 in FT-
IR. The theoretically calculated values of C−Cl stretching vibrations are found to be 771 and
764 cm−1 by B3LYP/6-31G(d) and B3LYP/6-31G(d,p), respectively. The C–Cl in-plane
bending modes have strong to medium intensity generally in the region 550–250 cm−1. In the
present study, C–Cl in plane bending and out-plane-bending vibrations are found and the TED
values are shown in Table 4.
Carbonyl and ethylenic bridge vibrations
The carbonyl bands are most characteristic bands of infrared and Raman spectra [21–
23]. The carbonyl vibration bands in ketones normally having a strong intensity are expected
in the region 1715–1680 cm−1 [23]. The carbon–oxygen double bond is formed by Pπ –Pπ
between carbon and oxygen atoms and the lone pair of electron on oxygen also determines the
nature of carbonyl group. The C=O stretching vibration band can be easily identified from the
IR and Raman spectra, and because of the degree of conjugation the strength and polarizations
are increasing. The C16=O17 stretching is observed in FT-Raman as a strong band at 1661
cm−1, which is confirmed by the TED values. The deviation from the calculated wavenumber
for this mode can be attributed to the under estimation of π-electron delocalisation due to
conjugation and hydrogen bonding network inside the crystal. In DCPDMP, the C=C
stretching vibrations of ethylenic bridge overlaps with vibrations of C16=O17 stretching
mode. The intense band at 1650 cm−1 in IR spectrum has been assigned to C11=C14
stretching mode which is coupled with C16=O17 stretching.
C−H vibrations
Normally, the aromatic ring C−H stretching vibrations occurs in the region 3100–3000
cm−1 [16,24-27]. In this region, the bands are not affected appreciably by the nature of the
substituent. For the C−H stretching vibrations, we have observed the FT-IR bands at 3109,
3078, 3005 cm−1 and 3113 and 3081 cm−1 in FT-Raman spectrum. These modes are stretching
modes as evident from the TED column shown in Table 4. The calculated values of these
modes are good agreement with maximum contribution of TED. The C−H in plane bending
vibrations usually occur in the region 1400–1050 cm−1 and the C−H out of plane bending
vibrations observe in the range of 1000–675 cm−1 [25,28]. In our study, the C−H in plane

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bending vibrations have been observed at 1418, 1309, 1253 and 1183 cm−1 in FT-IR and
1419, 1161 and 1096 cm−1 in FT- Raman and their corresponding theoretical values are quite
compatible. Also the C−H out of plane vibrations have been observed at 978 and 841 cm−1 in
FT-IR and 774 cm−1 in FT-Raman. These vibrations also show good agreement with
theoretically scaled harmonic wavenumber values.
C−C vibrations
The C−C ring stretching vibrations are expected within the region 1650–1200 cm−1. In
general, the bands of variable intensity are observed at 1625–1590, 1575–1590, 1470–1540,
1430–1465 and 1280–1380 cm−1 from the frequency ranges given by Varsanyi [25] for the
five bands in the region. The frequency bands at 1650, 1591, 1575, 1350 and 1305 cm−1 in
FT-IR and at 1613, 1581 and 1565 cm−1 in FT-Raman were assigned to the C−C stretching
vibrations for our molecule. The theoretical computed C−C−C in plane and out of plane
bending vibrations by the B3LYP/6-31G(d,p) shows good agreement with the recorded
spectral data. The other wavenumbers of the ring groups such as; torsional and rocking modes
are also assigned, and presented in Table 4. All these calculated values are in good agreement
with the experimental data.
Methoxy group vibrations
The methoxy group has two C−H stretching vibrations: symmetric and asymmetric
stretching. The asymmetric stretch is usually at higher wavenumber than the symmetric
stretch. The methoxy C−H symmetric stretching modes usually appear in the region 2825–
2870 cm−1 where as asymmetric mode lie in the range of 2925–2985 cm−1 [22,24,29]. The FT-
IR band at 2937and 2841 cm−1 and the corresponding FT-Raman band at 2936 and 2839 cm−1
are assigned to CH3 symmetric stretching vibration. The FT-IR band at 3000 and 2962 cm−1
are assigned to CH3 asymmetric stretching modes. The asymmetric and symmetric bending
vibrations of methyl group are expected in the region 1465–1440 cm−1 and 1390–1370 cm−1,
respectively [22,24]. The contribution of intermolecular interactions on methoxy stretching
modes is confirmed by the better coincidence of band position in the solution spectrum with
the computed vibrational wavenumbers. The methyl asymmetric bending appears as a strong
band in FT-IR at 1458 cm−1. The methyl frequencies are to some extent sensitive to the
electronegativity of the attached atom and the symmetric deformation is particularly sensitive
and it appears at 1435 in FT-IR and 1436 cm−1 in FT-Raman. The strong band in FT-IR at

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1151 cm−1 and 1177 cm−1 in FT-Raman are assigned to CH3 in plane rocking mode. The CH3
out of plane rocking mode are appeared with mixed modes which are found by TED values
shown in Table 4. The C=O stretching vibration of the compound is observed at 1661 and
1650 cm−1 in FT-Raman and FT-IR spectra and calculated at 1660 and 1650 cm−1 coupled
with CC stretching mode. The torsion mode of the O–CH3 group was observed at 228 and 148
cm−1 in FT-Raman.
The remainder of the observed and calculated wavenumbers and their assignments of
the compound are shown in Table 4.
3.3.
Frontier molecular orbitals (FMOs)
The frontier molecular orbital determine the way in which the molecule interacts with
other species. HOMO (highest occupied molecular orbital), which can be thought the
outermost orbital containing electrons, tends to give these electrons such as an electron donor.
On the other hand, LUMO (lowest unoccupied molecular orbital) can be thought the
innermost orbital containing free places to accept electrons [30]. Therefore, while the energy
of the HOMO is directly related to the ionization potential, LUMO energy is directly related
to the electron affinity. Energy difference between HOMO and LUMO orbital is called as
energy gap that is an important stability for structures [31]. HOMO–LUMO helps to
characterize the chemical reactivity and kinetic stability of the molecule [32]. A molecule
with a small gap is more polarized and is known as soft molecule. Recently, the energy gap
between HOMO and LUMO has been used to prove the bioactivity from intramolecular
charge transfer (ICT) [33,34] because it is a measure of electron conductivity. The frontier
orbital (HOMO, LUMO) of DCPDMP, with B3LYP/6-31G(d,p) method are plotted in Fig. 7.
The HOMO and LUMO energy gap of DCPDMP calculated by B3LYP/6-31G(d) and
631G(d,p) methods are given in Table 5. According to B3LYP/6-31G(d,p) calculation, the
energy band gap (∆E) (translation from HOMO to LUMO) of the molecule is about 6.0162
eV. The highest occupied molecular orbital is localized mainly on both the rings, while
LUMO is localized carbonyl, methoxy, ethylenic bridge groups and benzene ring.
3.4.
Global and local reactivity descriptors
Quantum chemical methods have been proven a very useful tool to study chemical
systems stabilized by hydrogen bonds. By using HOMO and LUMO energy values for a

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molecule, the global chemical reactivity descriptors of molecules such as hardness, chemical
potential, softness, electronegativity and electrophilicity index as well as local reactivity have
been defined [35-37]. Pauling introduced the concept of electronegativity as the power of an
atom in a molecule to attract electrons to it. Hardness (g), chemical potential (l) and
electronegativity (v) and softness are defined follows.
µ
=
(∂E ∂N
)
v(r )
η
=1 2
(
δ
2E
δ
N 2
)
v(r)
Operational schemes for the calculation of chemical hardness are based on a finite difference
method and thus:
µ ≈1 2
(
EHOMO + ELUMO
)
η
≈ −1 2
(
I.P + E.A
)
where I.P = Ionization Potential and E.A = Electron Affinity.
These global quantities, as well as the mean polarizability values (α), have been found
very useful and complementary tools for the description of chemical reactivity in connection
with minimum polarizability and maximum hardness principles. Considering the chemical
hardness, large HOMO–LUMO gap means a hard molecule and small HOMO– LUMO gap
means a soft molecule. One can also relate the stability of the molecule to hardness, which
means that the molecule with least HOMO–LUMO gap means, it is more reactive.
Recently Parr et al. [37] have defined a new descriptor to quantify the global
electrophilic power of the molecule as electrophilicity index (ω), which defines a quantitative
classification of the global electrophilic nature of a molecule. The defined electrophilicity
index (ω) as follows:
µ2
ω
=
2
Using the above equations, the chemical potential, hardness and electrophilicity index have
been calculated for DCPDMP and their values are shown in Table 5. The calculated values of
the hardness, electronegativity, chemical potential, and electrophilicity index of our molecule
in gas phase is 1.9243, 4.0919, -4.0919 and 4.3506, respectively.

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3.5.
Natural Bond Orbital analysis
NBO analysis provides the most accurate possible ‘natural Lewis structure’ picture of
φ, because all the orbital details are mathematically chosen to include the highest possible
percentage of the electron density. A useful aspect of the NBO method is that it gives
information about interactions in both filled and virtual orbital spaces that could enhance the
analysis of intra- and inter-molecular interactions. The second-order Fock matrix was carried
out to evaluate the donor–acceptor interactions in NBO analysis [38,39]. The interactions
result is the loss of occupancy from the localized NBO of the idealized Lewis structure into an
empty non-Lewis orbital. For each donor (i) and acceptor (j), the stabilization energy E(2)
associated with the delocalization i → j is estimated as
F(i, j) 2
E(2) = ∆Eij = qi
ε j
− εi
where qi is the donor orbital occupancy, ɛi and ɛj are diagonal elements and F(i,j) is the off
diagonal NBO Fock matrix element. Some electron donor orbital, acceptor orbital and the
interacting stabilization energy resulting from the second-order micro-disturbance theory are
reported [40,41]. The larger the E(2) value, the more intensive is the interaction between
electron donors and electron acceptors, i.e., the more donating tendency from electron donors
to electron acceptors and the greater the extent of conjugation of the whole system.
Delocalization of electron density between occupied Lewis-type (bond or lone pair) NBO
orbital and formally unoccupied (anti-bond or Rydberg) non-Lewis NBO orbital correspond
to a stabilizing donor–acceptor interaction. NBO analysis has been performed on the molecule
at the B3LYP/6−31G(d,p) level in order to elucidate the intra-molecular, re-hybridization and
delocalization of electron density within the molecule.
The strong intramolecular hyperconjugative interaction of the s and p electrons of C−
C to the anti C−C bond of the ring leads to stabilization of some part of the ring as evident
from Table 6. There occurs a strong intramolecular hyperconjugative interaction of the π(C4–
C5) orbital with the π*(C2–C3) orbital which leads to the stabilization of 21.10 kcal/mol. This
enhanced π*(C2–C3) NBO further conjugates with π*(C4–C5) resulting in an enormous E(2)
energy of 228.76 kcal/mol. The hyperconjugative interaction is maximum between lone pair
of LP(2) O31 and antibonding orbital of the π*(C22–C23). The intramolecular
hyperconjugative interactions result in ICT causing stabilization of the system. These
interactions are observed as an increase in ED that weakens the respective bonds.

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3.6.
Nonlinear Optical Features
The computational approach allows the determination of molecular NLO properties as
an inexpensive way to design molecules by analyzing their potential before synthesis and to
determine high order hyperpolarizability tensors of molecules. The simplest polarizability (α),
characterizes the ability of an electric field to distort the electronic distribution of a molecule.
The first hyperpolarizability (β) of this novel molecular system, and the related
properties (β, α0 and ∆α) were calculated 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.
Polarizability and hyperpolarizability characterize the response of a system in an applied
electric field [42]. They determine not only the strength of molecular interactions (long-range
interaction, dispersion force, etc.) and the cross sections of different scattering and collision
process but also the NLO properties of the system [43,44]. 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 the Kleinman symmetry [45], and can be given in the
lower tetrahedral format. It is obvious that the lower part of the 3x3x3 matrices is tetrahedral.
The components of are defined as the coefficients in the Taylor series, with expansion of the
energy in the external electric field. When the external electric field is weak and
homogeneous, this expansion becomes:
1
2
1
6
E = E 0 −
µ
α Fα −
α
αβ Fα Fβ −
βαβγ Fα Fβ Fγ + K
where E0 is the energy of the unperturbed molecules Fα is the field at the origin, µα, ααβ and
βαβγ are the components of the dipole moment, polarizability and the first
hyperpolarizabilities, respectively.
The total static dipole moment, the mean polarizability, the anisotropy of the
polarizability and the mean first-order hyperpolarizability of the title compound has been
calculated using B3LYP/6-31G(d) and 6-31G(d,p) levels. The conversion factor α, β and
HOMO and LUMO energies in atomic and cgs units: 1 atomic unit (a.u.) =0.1482 x 10-24
electrostatic unit (esu) for α; 1 a.u. = 8.6393 x 10-33 esu for β; 1 a.u. = 27.2116 eV (electron
volt) for HOMO and LUMO energies.
This title compound has a larger dipole moment (Table 7), and that the stronger dipole

ACCEPTED MANUSCRIPT
moment of DCPDMP leads to increased polarity. The different charge distributions result in
completely different orientations of the (calculated) dipole moments. In Table 7, the results of
the electronic dipole moment polarizabilities (α and ∆α) and the first hyperpolarizability (β)
are listed. The dipole polarizability indirectly provides a measure of the extent of distortion of
the electron density, and hence the response of the system under the effect of an external static
electric field. As shown in Table 7, the calculated polarizability figures αij, have non-zero
values and are dominated by the diagonal components. The calculated polarizability of
DCPDMP is equal to 3.52x10-23 and 3.46x10-23 esu by B3LYP with the basis sets 6-31G(d)
and 631G(d,p) levels of DFT theory. The calculated dipole moment and hyperpolarizability
values obtained from B3LYP with the basis sets 6-31G (d) and 6-31G(d,p) method are
collected in Table 7. Urea is one of the prototypical molecules used in the study of the NLO
properties of the molecular systems. Therefore, it is used frequently as a threshold value for
comparative purposes. The first order hyperpolarizability of DCPDMP with B3LYP/6-31G(d)
basis set is 44.19x10-30 esu which is 119 times greater than the value of urea (βtot = 0.372 x 10-
30
esu). From the computation, the high values of the hyperpolarizability of DCPDMP are
probably attributed to the nonlinear optical (NLO) property of the molecule. In addition, it is
evident that the extent of charge transfer in terms of the HOMO–LUMO gap or the optical
gap ∆E, which, in turn, can be used to understand its effect on the β values. ∆E is directly
proportional to the extent of charge transfer. For a small optical gap, the charge transfer
occurs easily, thus, giving a higher value of β. The source of charge transfer is thus controlled
by the energy of the HOMO, whereas the acceptance of the charge is dominated by the
LUMO energy. Small optical gap enhances the charge transfer, which, in turn, is reflected in
the larger values of α and β. There is an inverse relationship between the HOMO–LUMO
energy gap and the first hyperpolarizability values for DCPDMP as expected.
3.7.
Molecular electrostatic potential (MEP)
Molecular electrostatic potential has been found to be a very useful tool in the
investigation of the correlation between molecular structures with its physiochemical property
relationship, including biomolecules and drugs [46,47]. The MEP has been plotted for
DCPDMP molecule at the B3LYP/6-31G(d,p) basis set as shown in Fig. 8. The MEP
superimposed on top of the total energy density as a shell. Because of the usefulness feature to
study reactivity given that an approaching electrophile will be attracted to negative regions
(where the electron distribution effect is dominant). The different electrostatic potential values

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of the surface are represented by different colors: red represents regions of most negative
electrostatic potential, blue represents regions of most positive electrostatic potential, and
green represents regions of zero potential. Potential increases in the order:
red<orange<yellow<green<blue. In all cases, the shape of the electrostatic potential surface is
influenced by the structure and charge density distributions in the molecule with sites close to
the oxygen atom, showing regions of most negative electrostatic potential. In the present
work, as can be seen from the Fig. 8, the calculated result shows that the negative potentials
are mainly over the electron negative oxygen atoms (O17, O26 and O31). In addition,
negative electrostatic potential regions are observed around the chlorine atoms (Cl7 and
Cl12). Positive potentials are over the nucleophilic reactive hydrogen atoms. This result gives
information for the region from where the compound can have intermolecular interaction. The
MEP provides a visual representation of the chemically active sites and comparative reactivity
of atoms. As we have mentioned earlier, the electrostatic potential has been used primarily for
predicting sites and relative reactivity towards electrophilic attack, and in studies of biological
recognition and hydrogen bonding interactions [48,49].
Conclusion
Optimized geometrical parameters of the title compound were studied by density functional
method and in agreement with the XRD data. Molecular structure and vibrational
wavenumbers of the title compound were studied using vibrational spectra and density
functional method. The DFT based calculations for the title compound is reproduced its
experimental geometry and vibrational wavenumbers excellently. The wavenumbers proposed
by the TED analysis are in good agreement with the observed wavenumbers. The NBO
analysis reveals the reasons for hyper-conjugative interaction and stability of the molecule. A
computation of the first hyperpolarizability of the compound indicates that this class of
derivatives may be a good candidate as a NLO material. The HOMO and LUMO analysis is
used to determine the charge transfer within the molecule. From the MEP, it is evident that
the negative charge covers the C=O and C−O groups and the positive region is over the C−Cl
group. To summarize, the following conclusions can be drawn:
(1) The compound crystallizes in the triclinic space group P-1 with a = 7.6179 (7), b =
8.5023 (7), c = 12.1967 (10) Å, V = 764.39 (11) Å3 and two molecules in the unit cell.
(2) The HOMO is localized mainly on both the rings, while LUMO is localized carbonyl,
methoxy, ethylenic bridge groups and benzene ring.

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(3) The first order hyperpolarizability of DCPDMP with B3LYP/6-31G(d) basis set is
44.19x10-30 esu which is 119 times greater than the value of urea (βtot = 0.372 x 10-30
esu). Therefore, we conclude that the title compound is an attractive object for future
studies of nonlinear optical properties.
(4) As can be seen from the MEP Figure, the negative potential surfaces are mainly over
the electron negative oxygen atoms (O17, O26 and O31).
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Table 1. Crystal data and parameters for structure
refinement of the title compound.
Compound
Molecular formula
Molecular weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
(I)
C17H14Cl2O3
337.18
Triclinic
P-1
7.6179 (7)
8.5023 (7)
12.1967 (10)
93.2313 (19)
98.0150 (17)
101.2475 (18)
764.39 (11)
2
γ (°)
V (Å3)
Z
Dcalc. (g cm-3)
1.465
Crystal dimensions (mm) 0.48 × 0.20 × 0.12
ꢀ (mm-1)
0.43
Radiation λ (Å)
Reflections measured
Ranges/ indices (h, k, l)
θ limit (°)
Unique reflections
Observed reflections
(I > 2σ(I))
0.71073
12215
-9, 9; -10, 10; -15, 15
1.7-26.0
2986
2459
Parameters
201
1.09
0.043; 0.135
Goodness of fit on F2
R1, wR2 (I ≥ 2σ(I))

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Table 2. Hydrogen-bond geometry of the title compound
D—H···A
D—H H···A
D···A
D—H···A
115
C9—H9A···Cl1
C8—H8A···Cl2
C13—H13A···O1i
C(17)—H(17C)···Cg(1)ii
0.93 2.46 2.982 (3)
0.93 2.51 3.146(2)
0.93 2.45 3.338(3)
0.96 2.83 3.714(3)
125
160
153
Symmetry codes: (i) x+1, y+1, z+1; (ii) −x, −y+1, −z.

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Table 3. Comparison of the geometrical parameters of DCPDMP, bond length (Ǻ) in angstrom and bond angles (ᵒ) in degrees by using B3LYP/6-31G(d) and
B3LYP/6-31G(d,p) level.
Bond Lengths
Exp 6-31G(d) 6-31G(d,p) Bond Angles
Exp 6-31G(d)
6-31G(d,p) Bond Angles (dihedral)
120.5 C3−C4−C5−H10
Exp
6-31G(d)
179.1
179.9
-0.6
6-31G(d,p)
179.1
179.8
-0.6
C1−C2
C1−C6
C1−C11
C2−C3
C2−Cl7
C3−C4
C4−C5
C5−C6
1.41
1.41
-
1.38
1.74
1.37
1.37
1.38
-
0.93
1.30
0.93
1.49
1.21
1.49
1.38
1.40
1.39
1.38
1.41
1.35
1.37
1.37
0.93
1.43
1.42
0.93
0.96
1.42
1.41
1.47
1.39
1.83
1.40
1.40
1.39
1.83
1.09
1.35
1.08
1.48
1.26
1.49
1.41
1.41
1.39
1.40
1.42
1.38
1.39
1.39
1.08
1.47
1.45
1.08
1.09
1.42 C16−C18−C19
1.41 C16−C18−C23
1.47 C19−C18−C23
1.39 C18−C19−C20
1.76 C18−C19−H24
1.39 C20−C19−H24
1.39 C19−C20−C21
1.39 C19−C20−H25
1.76 C21−C20−H25
1.09 C20−C21−C22
1.34 C20−C21−O26
1.08 C22−C21−O26
1.49 C21−C22−C23
1.23 C21−C22−O31
1.50 C23−C22−O31
1.40 C18−C23−C22
1.41 C18−C23−H36
1.39 C22−C23−H36
1.39 C21−O26−C27
1.42 O26−C27−H28
1.37 O26−C27−H29
1.39 O26−C27−H30
1.37 H28−C27−H29
1.08 H28−C27−H30
1.43 H29−C27−H30
1.42 C22−O31−C32
1.08 O31−C32−H33
1.10 O31−C32−H34
120.0
120.2
119.7
120.1
124.3
117.0
118.7
120.0
121.4
118.5
121.3
121.3
117.3
118.9
115.5
125.5
119.6
116.8
123.6
121.5
117.0
121.6
122.1
104.2
111.1
110.7
111.1
110.1
109.6
118.4
111.0
-
-
-
120.2
120.0
124.5
116.8
118.7
120.9
119.5
119.5
119.9
119.5
120.1
119.7
114.6
125.7
119.7
114.9
125.3
121.2
119.4
119.4
118.2
109.5
109.5
109.5
109.5
109.5
-
119.2 H9−C4−C5−C6
120.3 H9−C4−C5−H10
124.3 C4−C5−C6−C1
116.7 C4−C5−C6−Cl12
119.1 H10−C5−C6−C1
-0.7
178.8
0.1
0.1
177.8
-179.4
-1.7
177.9
-179.5
-1.7
-
-
-
119.9 H10−C5−C6−Cl12
121.3 C1−C11−C14−H15
118.6 C1−C11−C14−C16
121.2 H13−C11−C14−H15
121.2 H13−C11−C14−C16
117.6 C11−C14−C16−O17
119.3 C11−C14−C16−C18
118.0 H15−C14−C16−O17
122.7 H15−C14−C16−C18
119.3 C14−C16−C18−C19
116.2 C14−C16−C18−C23
124.5 O17−C16−C18−C19
121.3 O17−C16−C18−C23
117.0 C16−C18−C19−C20
121.7 C16−C18−C19−H24
117.4 C23−C18−C19−20
105.7 C23−C18−C19−H24
111.7 C16−C18−C23−C22
110.6 C16−C18−C23−H36
109.9 C19−C18−C23−C22
109.2 C19−C18−C23−H36
109.6 C18−C19−C20−C21
117.9 C18−C19−C20−H25
111.4 H24−C19−C20−C21
0.1
0.1
C6−Cl12
C11−H13
C11−C14
C14−H15
C14−C16
C16−O17
C16−C18
C18−C19
C18−C23
C19−C20
C20−C21
C21−C22
C21−O26
C22−C23
C22−O31
C23−H36
O26−C27
O31−C32
C-H Ring average
C-H Methyl average
Bond Angles
176.1
179.0
-177.0
1.9
178.6
-176.7
1.8
-
-
-5.9
173.3
2.9
2.9
-176.8
-178.2
2.1
-176.7
-178.6
1.8
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-1.6
-2.7
178.0
178.7
-1.7
-179.6
-0.5
177.0
177.6
-2.7
-179.5
-0.4
0.7
0.8
179.9
-179.6
-0.4
0.1
179.2
-0.4
179.9
-179.6
-0.5
0.1
179.2
-0.6
Exp 6-31G(d) 6-31G(d,p) O31−C32−H35
114.4 115.2 H33−C32−H34
-
-
179.4
-179.6
179.6
-179.7
C6−C1−C11
-

ACCEPTED MANUSCRIPT
C1−C2−C3
C1−C2−Cl7
C3−C2−Cl7
C2−C3−C4
C2−C3−H8
C4−C3−H8
C3−C4−C5
C3−C4−H9
C5−C4−H9
C4−C5−C6
C4−C5−H10
C6−C5−H10
C1−C6−C5
C1−C6−Cl12
C5−C6−Cl12
C1−C11−H13 121.1
C1−C11−C14 116.4
H13−C11−C14 112.9
C11−C14−H15
C11−C14−C16 112.9
H15−C14−C16 120.1
C14−C16−O17 119.9
118.7
126.9
123.5
120.0
116.5
-
120.4
120.4
-
120.0
120.0
120.2
119.9
119.9
122.6
119.6
126.0
123.9
119.6
116.5
119.1
119.8
121.1
119.8
120.1
120.1
119.6
120.7
119.5
123.3
121.4
115.3
115.8
127.9
116.2
121.3
119.8
118.9
-
119.3 H33−C32−H35
125.5 H34−C32−H35
123.2 Bond Angles
-
-
111.2
105.0
111.6 H24−C19−C20−H25
105.8 C19−C20−C21−C22
6-31G(d,p) C19−C20−C21−O26
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0.2
-0.7
-177.7
179.5
2.4
0.5
-0.6
-176.9
179.3
2.9
Exp 6-31G(d)
119.7 C6−C1−C2−C3
117.1 C6−C1−C2−Cl7
119.3 C11−C1−C2−C3
119.6 C11−C1−C2−Cl7
121.2 C2−C1−C6−C5
120.0 C2−C1−C6−Cl12
120.0 C11−C1−C6−C5
120.0 C11−C1−C6−Cl12
119.8 C2−C1−C11−H13
-1.6
178.5
178.2
-1.7
-0.8
-179.6
-179.1
2.1
-0.9 H25−C20−C21−C22
-179.5 H25−C20−C21−O26
-178.9 C20−C21−C22−C23
2.5 C20−C21−C22−O31
0.5 O26−C21−C22−C23
-177.1 O26−C21−C22−O31
178.4 C20−C21−O26−C27
0.7 C22−C21−O26−C27
34.8 C21−C22−C23−C18
-142.0 C21−C22−C23−H36
-142.9 O31−C22−C23−C18
40.2 O31−C22−C23−H36
0.6 C21−C22−O31−C32
-179.2 C23−C22−O31−C32
179.3 C21−O26−C27−H28
-0.6 C21−O26−C27−H29
0.1 C21−O26−C27−H30
179.8 C22−O31−C32−H33
179.9 C22−O31−C32−H34
-0.3 C22−O31−C32−H35
-0.5
1.5
1.5
-177.6
178.2
-0.8
-148.8
34.3
-177.6
177.6
-1.5
-122.3
61.6
-1.3
179.7
177.8
-1.3
178.1
-0.9
1.8
0.5
-177.7
-177.9
2.5
-177.1
178.7
1.1
-
32.8
-1.2
120.9 C2−C1−C11−C14 -168.9
-144.3
-145.3
37.6
179.7
177.8
-1.2
178.8
-0.2
165.5
-74.9
47.2
-60.6
61.7
119.3 C6−C1−C11−H13
122.6 C6−C1−C11−C14
121.4 C1−C2−C3−C4
116.0 C1−C2−C3−H8
116.0 Cl7−C2−C3−C4
127.9 Cl7−C2−C3−H8
116.1 C2−C3−C4−C5
121.2 C2−C3−C4−H9
119.4 H8−C3−C4−C5
119.4 H8−C3−C4−H9
-
10.9
-
-
0.5
-179.3
179.4
-0.5
-179.8
-
-
-
1.1
-
-
-
-65.5
57.0
-60.0
62.2
-178.9
0.2
179.8
-180.0
-0.3
C14−C16−C18
O17−C16−C18 120.1
Numbering of atoms is adopted from Gaussian in Fig. 4
-
-179.4
-
C3−C4−C5−C6
-0.8
-0.5

ACCEPTED MANUSCRIPT
Table 4. Comparison of the experimental (FT-IR and FT-Raman) and theoretical wavenumbers (cm-1) of DCPDMP calculated by B3LYP/6-31G(d) and
B3LYP/6-31G(d,p) level.
Unscaled
Scaled
No. FT-IR FT-Raman 6-31G(d) 6-31G(d,p) 6-31G(d) 6-31G(d,p) TED (%) among types of internal coordinates
3254
3239
3231
3226
3223
3207
3204
3188
3157
3154
3122
3092
3034
3026
1741
1671
1645
1632
1621
1603
1553
1527
1518
1504
1501
3275
3253
3252
3247
3243
3226
3223
3200
3197
3184
3163
3118
3068
3044
1709
1656
1641
1628
1602
1599
1563
1544
1538
1533
1525
νC14-H15(91)
νC23-H36(99)
νC3-H8(47), νC5-H10(36), νC4-H9(16)
νC5-H10(55), νC3-H8(45)
νC19-H24(68), νC20-H25(24)
νC20-H25(75), νC19-H24(24)
νC4-H9(83)
νC11-H13(99)
νC27-H28(59), νC27-H29(40)
νC32-H35(89)
νC27-H29(45), νC27-H28(27), νC27-H30(26)
νC32-H33(52), νC32-H34(47)
νC27-H30(72), νC32-H34(47), νC27-H28(13)
νC32-H34(47), νC32-H33(41), νC32-H35(10)
νO17-C16(60), νC11-C14(19)
νC11-C14(45), νO17-C16(21)
νC22-C23(28), νC20-C21(11)
νC2-C3(28), νC5-C6(20)
1
2
3
4
5
6
7
8
3113
3081
3166
3135
3113
3107
3091
3080
3047
3026
3018
3007
2996
2983
2955
2867
1683
1671
1653
1618
1593
1586
1547
1531
1508
1490
1481
3115
3110
3088
3079
3076
3036
3014
3005
3001
2989
2981
2960
2935
2842
1660
1650
1627
1593
1574
1565
1515
1514
1485
1470
1459
3109
3078
3005
9
3000
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
2962
2937
2841
2936
2836
1661
1650
1591
1575
νC18-C19(20), νC21-C22(20), δH9-C4-C5(15), νC20-C21(15)
νC3-C4(29), νC4-C5(20), νC1-C2(20), νC1-C6(10)
δH25-C20-C19(13), νC21-C22(20), δH36-C23-C18(11), νO26-C21(10), νO26-C21(10)
δH29-C27-H30(73), γC27-H28-O26-H29(12)
δH33-C32-H34(61), δH34-C32-H35(15), γC32-H33-O31-H34(11), δH33-C32-H35(10)
δH34-C32-H35(42), γC32-H34-O31-H35(14)
γC27-H28-O26-H30(19), δH28-C27-H30(15), δH33-C32-H35(11), δH33-C32-H34(10)
1565
1516
1511
1487
1458

ACCEPTED MANUSCRIPT
1496
1480
1472
1463
1452
1368
1360
1341
1315
1308
1298
1264
1249
1223
1211
1206
1193
1178
1178
1176
1157
1107
1091
1075
1064
1040
1021
979
1506
1495
1490
1480
1464
1398
1383
1370
1341
1328
1308
1285
1269
1231
1222
1204
1199
1194
1169
1165
1158
1115
1092
1090
1042
1028
1019
996
δH28-C27-H30(52), δH34-C32-H35(12), δH29-C27-O26(11)
δH29-C27-O26(27), γC27-H28-O26-H30(26), δH28-C27-H30(14)
δH10-C5-C4(30), νC1-C6(19), δH9-C4-C5(14)
26
27
28
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
1469
1451
1446
1435
1371
1358
1333
1318
1290
1286
1266
1260
1237
1231
1217
1208
1191
1188
1169
1158
1131
1093
1083
1051
1037
1028
1016
991
1443
1435
1428
1420
1355
1328
1310
1293
1274
1260
1251
1245
1224
1210
1195
1182
1175
1160
1153
1144
1095
1066
1053
1030
1025
1015
1002
975
1435
1418
1436
δH8-C3-C2(30), νC1-C2(15), δH9-C4-C5(10)
1419
1355
νC22-C23(22), νC19-C20(11), δH24-C19-C18(15)
νC18-C19(17), νC21-C22(15), δH15-C14-C11(13), νC20-C21(12)
δH15-C14-C11(29), δH13-C11-C1(13), νC20-C21(12), νC11-C14(11)
δH13-C11-C1(36), δH15-C14-C11(11)
1327
1309
1296
νO31-C22(52), δH36-C23-C18(13)
νO26-C21(21), νH24-C19-C18(11), νH25-C20-C19(16)
δH36-C23-C18(17), δ H24-C19-C18(12), δH13-C11-C1(10)
νO26-C21(14), δH36-C23-C18(11), δO31-C22(10)
νC5-C6(30), δH10-C5-C4(28), νC1-C11(16)
γC32-H33-O31-H34(53), νC16-C18(10)
γC27-H28-O26-H30(23), γC27-H28-O26-H29(21), νC1-C2(13), νC2-C3(10)
δH8-C3-C29(35), νC1-C2(13), νC2-C3(10)
γC32-H33-O31-H34(16), δH36-C23-C18(10), νC16-C18(11)
δH9-C4-C5(43), νC16-C18(10)
γC32-H34-O31-H35(78), δH33-C32-H35(14), νC4-C5(10)
γC27-H28-O26-H29(38), δH29-C27-O26(36)
δH25-C20-C19(29), δH24-C19-C18(24), νC19-C20(17)
νC3-C4(32), ν C4-C5(31), δH10-C5-C4(10), δH8-C3-C2(10)
δC1-C6-C5(24), δC4-C5-C6(17), δC3-C4-C5(13)
νC18-C23(16), νC14-C16(15), δH36-C23-C18(13), νC18-C19(10)
νO31-C32(54)
1258
1253
1242
1226
1210
1194
1183
1177
1161
1151
1145
1096
1065
1052
1032
1000
919
1026
1014
νO26-C27(69), τH15-C14-C11-C1(12)
γC11-C1-C14-H13(73), τH15-C14-C11-C1(22)
τH9-C4-C5-H10(79), τH8-C3-C2-Cl7(11)
τH25-C20-C21-O26(58), τH24-C19-C18-C16(25)
νC14-C16(21), δC11-C14-C16(13)
τH36-C23-C18-C16(83)
978
917
884
940
937
918
908
975
960
947
946
970
937
906
893
956
920
893
880
τH8-C3-C2-Cl7(50), γC5-C4-C6-H10(38)

ACCEPTED MANUSCRIPT
887
879
833
790
789
779
772
753
729
702
653
610
588
581
558
539
538
517
501
452
420
397
393
352
333
320
303
273
252
238
213
201
929
887
855
820
795
779
758
755
742
712
662
616
590
579
566
549
544
528
489
451
413
391
384
346
328
324
313
267
250
237
215
202
τH15-C14-C11-C1(47), γC11-C1-C14-H13(10)
νC3-C4-C5(17)
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
871
855
888
871
864
831
783
771
764
758
746
693
653
606
588
570
561
544
530
495
468
430
410
359
352
343
328
316
310
230
216
196
184
168
870
856
842
815
775
764
758
740
733
684
640
600
581
562
553
530
522
490
462
421
403
355
347
333
320
311
306
226
212
193
180
166
τH24-C19-C18-C16(51), τH25-C20-C21-O26(30)
δC19-C18-C23(14), δC3-C4-C5(11)
γC5-C4-C6-H10(41), τH8-C3-C2-Cl7(24)
νCl7-C2(24), νC4-C5-C6(22), νCl12-C6(17)
νC21-C22(11), νO31-C22(11)
γO17-C14-C18-C16(22), τC1-C6-C5-C4(11), γC19-C16-C23-C18(10)
τC19-C20-C21-C22(24), τ O26-C21-C22-O31(22)
γO17-C14-C18-C16(22), τC1-C6-C5-C4(15), τC1-C2-C3-C4(12)
δC19-C20-C21(27)
δC14-C16-O17(22)
γC19-C16-C23-C18(49), τO26-C21-C22-O31(10)
δC20-C21-O26(19), δ C16-C18-C23(10)
δC18-C19-C20(18), δC14-C16-C18(11), τC3-C4-C5-C6(10)
τC1-C6-C5-C4(26), γCl7-C1-C3-C2(19), τC2-C1-C6-Cl12(10)
γCl7-C1-C3-C2(17), τC1-C6-C5-C4(11)
841
813
774
767
758
742
734
685
645
599
601
584
565
532
557
521
491
463
τC3-C4-C5-C6(37), δC2-C1-C11(12)
γO31-C21-C23-C22(46), δC21-O26-C27(11), τC19-C20-C21-C22(13)
δC22-O31-C32(21), δC14-C16-C18(19)
νCl7-C2(26), δC4-C5-C6(18), δC1-C6-C5(12)
δC5-C6-Cl12(23), νCl12-C6(17)
δC21-O26-C27(15), τC19-C20-C21-C22(11), τC16-C18-C19-C20(10)
466
420
404
356
δC1-C2-Cl7(19), δ C11-C14-H15(10)
δC22-O31-C32(24), δC20-C21-O26(17), δC18-C19-C20(11)
τC1-C11-C14-C16(19), τC5-C6-C1-C11(19), δC1-C2-Cl7(14)
δC21-O26-C27(11), τH33-C32-O31-C22(10), τC16-C18-C19-C20(10)
τH33-C32-O31-C22(51)
δC1-C2-Cl7(17), δC5-C6-Cl12(15), δC11-C14-C16(11), τH33-C32-O31-C22(10)
δC5-C6-Cl12(19), δC21-O26-C27(11)
308
228
δC23-C22-O31(21), δC20-C21-O26(14), δC22-O31-C32(10)
τC1-C2-C3-C4(46), τC2-C1-C6-Cl12(26), τC3-C4-C5-C6(10)

ACCEPTED MANUSCRIPT
90
91
92
93
94
95
166
154
149
130
115
95
163
151
145
126
110
93
190
181
161
136
113
97
194
180
162
141
119
97
τC16-C18-C23-C22(26)
τC16-C18-C23-C22(13)
τH28-C27-O26-C21(52)
τC6-C1-C11-C14(16), δC16-C18-C23(14), δC23-C22-O31(10)
τC6-C1-C11-C14(22), τC11-C14-C16-C18(17), τO26-C21-C22-O31(11)
τC21-C22-O31-C32(57)
148
96
86
85
93
96
τ C1-C11-C14-C16(47), δC2-C1-C11(12)
97
98
99
79
63
42
78
60
40
79
62
57
87
63
40
τC6-C1-C11-C14(16), τC16-C18-C19-C20(15), τO26-C21-C22-O31(12)
τC5-C6-C1-C11(31), τC2-C1-C6-Cl12(15), τC1-C11-C14-C16(16)
τC22-C21-O26-C27(48), τC5-C6-C1-C11(12)
100
101
102
34
16
9
33
15
8
36
18
9
36
20
12
δC1-C11-C14(33), δC11-C14-C16(20), τC5-C6-C1-C11(12), γC14-C16-C18(10)
τC14-C16-C18-C23(35), τC11-C14-C16-C18(32), τC6-C1-C11-C14(13)
τC14-C16-C18-C23(48), τC11-C14-C16-C18(33), τC5-C6-C1-C11
ν-stretching; δ-in-plane deformation; γ-out-of-plane deformation; τ-torsion

ACCEPTED MANUSCRIPT
Table 5. The HOMO and LUMO energy gap ionization potential, Electron
affinity, Chemical Hardness, Electronegativity, Softness, Chemical potential,
Global electrophilicity index values of DCPDMP at the B3LYP/6-31G(d)
and B3LYP/6-31G(d,p) level
Parameters
EHOMO
ELUMO
EHOMO – ELUMO gap
Ionization potential(I.P, eV)
Electron affinity(E.A, eV)
Chemical Hardness(η, eV)
Electronegativity(χ, eV)
Softness(S,eV-1)
6-31G(d)
5.9179
2.3178
3.6001
5.9179
2.3178
1.8001
4.1179
0.5555
-4.1179
4.7101
6-31G(d,p)
6.0162
2.1676
3.8485
6.0162
2.1676
1.9243
4.0919
0.5197
-4.0919
4.3506
Chemical potential(ꢀ, eV)
Global electrophilicity index(ω)

ACCEPTED MANUSCRIPT
Table 6. The second order perturbation energies E(2) (kcal/mol) corresponding to the most
important charge transfer interactions (donor-acceptor) for DCPDMP by B3LYP/6-
31G(d,p) method.
Donor
ED(i)e
1.9879
1.9879
1.6537
1.6537
1.9880
1.9880
1.9657
1.9657
1.6562
1.6562
1.6562
1.6822
1.6822
1.9249
1.9694
1.9274
1.8834
1.8834
1.9538
1.8876
1.8876
1.9618
1.8443
1.8443
1.8443
0.0380
0.0380
0.3742
0.2089
0.2089
Acceptor(j)
σ*(C1-C6)
σ*(C3-C4)
π*(C1-C6)
π*(C2-C3)
σ*(C1-C2)
σ*(C4-C5)
π*(C11-C14)
π*(C18-C19)
π*(C16-O17)
π*(C20-C21)
π*(C22-C23)
π*(C18-C19)
π*(C20-C21)
π*(C2-C3)
ED(j)e
0.0380
0.0167
0.0380
0.3742
0.0357
0.0168
0.0762
0.3859
0.2089
0.2089
0.3499
0.3859
0.3531
0.3742
0.0380
0.0380
0.0590
0.0625
0.0424
0.2089
0.0171
0.0248
0.3499
0.0188
0.0189
0.3309
0.0762
0.3309
0.0762
0.3859
E(2)
2.56
2.55
21.45
21.10
2.46
2.65
4.18
E(i)-E(j)
1.24
1.28
0.27
0.27
1.24
1.28
0.40
0.39
0.27
0.28
0.28
0.30
0.29
0.33
0.85
0.32
0.69
0.70
1.02
0.38
0.79
1.13
0.34
0.75
0.75
0.02
0.05
0.01
0.02
0.01
F(i,j)
0.051
0.051
0.069
0.068
0.050
0.052
0.037
0.044
0.068
0.066
0.065
0.067
0.067
0.061
0.056
0.062
0.105
0.104
0.080
0.068
0.063
0.080
0.095
0.058
0.058
0.080
0.059
0.084
0.072
0.073
σ(C2-Cl7)
σ(C2-Cl7)
π(C4-C5)
π(C4-C5)
σ(C6-Cl12)
σ(C6-Cl12)
π(C16-O17)
π(C16-O17)
π(C18-C19)
π(C18-C19)
π(C18-C19)
π(C22-C23)
π(C22-C23)
LP(3)Cl7
4.98
20.08
19.62
19.18
18.28
18.86
12.01
4.60
12.35
19.27
18.87
7.82
13.44
5.90
7.13
29.35
5.25
5.27
LP(2)Cl2
LP(3)Cl2
σ*(C1-C6)
π*(C1-C6)
LP(2)O17
LP(2)O17
LP(1)O26
LP(2)O26
LP(2)O26
LP(1)O31
LP(2)O31
LP(2)O31
LP(2)O31
π*(C1-C6)
π*(C1-C6)
π*(C2-C3)
π*(C16-O17)
π*(C16-O17)
σ*(C14-C16)
σ*(C16-C18)
σ*(C21-C22)
π*(C20-C21)
σ*(C27-H30)
σ*(C22-C23)
π*(C22-C23)
σ*(C32-H33)
σ*(C32-H34)
π*(C4-C5)
169.32
23.10
228.76
39.59
146.86
π*(C11-C14)
π*(C4-C5)
π*(C11-C14)
π*(C18-C19)
ED; Electron density
a E(2) means energy of hyper conjugative interaction (stabilization energy).
b Energy difference between donor and acceptor i and j NBO orbitals.
c F(i,j) is the Fock matrix element between i and j NBO orbitals.

ACCEPTED MANUSCRIPT
Table 7. The mean polarizability (α), anisotropic polarizability (∆α), dipole
moment (µ), first-order hyperpolarizability (β) and optical gap (∆EH-L) values of
DCPDMP by B3LYP/6-31G(d) and 6-31G(d,p) method.
Parameters
α (x10-23 esu)
∆α (x10-23 esu)
µ (Debye)
6-31G(d)
3.52
6-31G(d,p)
3.46
4.25
0.8936
44.19
3.48
1.5648
21.9
β (x10-30 esu)
∆EH-L (eV)
3.6001
3.8485