Journal of Molecular Structure 1276 (2023) 134759

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Journal of Molecular Structure

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

Structural and theoretical insights towards the understanding of the

effect on the conformation of ligand by complexation process
B.S. Chethan a, H.R. Rajegowda b, Riyaz ur Rahaman Khan b, N.K. Lokanath a,∗
a
Department of Studies in Physics, University of Mysore, Manasagangotri, Mysuru, Karnataka 570006, India
b
Department of Chemistry, Acharya Institute of Graduate Studies, Soladevanahalli, Bengaluru, Karnataka 560107, India

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

Article history: The ligand and the palladium complex were synthesized and characterized by the single crystal X-ray
Received 10 October 2022 diffraction method. The Hirshfeld surface analysis quantified the intermolecular interactions stabilizing
Revised 1 December 2022
the crystal packing in both compounds. DFT (density functional theory) calculations were used to opti-
Accepted 5 December 2022
mize the geometric structures and calculate the electronic properties of the synthesized compounds. The
Available online 5 December 2022
ligand and complex’s electronic structure and UV-Vis spectrum are interpreted by DFT and TD-DFT (time
Keywords: dependent-density functional theory) calculations. The NBO (natural bond orbital) analysis was employed
Palladium complex to study the origin and nature of the hyperconjugation interactions. The intramolecular interaction ener-
DFT gies associated with different topologies were calculated using the QTAIM (Quantum Theory of Atoms in
Hirshfeld surface Molecules), and the non-covalent interactions revealed the type and nature of the interactions exhibited
QTAIM by the compound. The structural and theoretical analysis revealed the change in the properties of the
Non-covalent interactions
ligand due to the complexation process.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction The metal complexes with positively charged metal centers

Synthesis of the Schiff based ligand and its corresponding metal
complexes is one of the most intensively developing fields of in-
organic chemistry. The various properties exhibited by these com-
pounds, which are useful for various applications, stimulate further
research in the domain [1–5].
The Schiff base compounds exhibit significant biological activi-
ties, which play a key role in medicine and pharmaceutical fields
[6–8]. The Schiff bases are highly sorted as ligands in transition
metal chemistry due to their ability to stabilize the metals in
different oxidation states. The presence of the azomethine group
(CH=N) in the ligand is mainly responsible for the high biologi-
cal activity of the Schiff base ligands, as the nitrogen atom of the
azomethine group plays an important role in the formation of the
hydrogen bonds with the active centers of the biological molecules
[9,10]. In the formation of the metal complexes from the Schiff
based ligands, the consideration of the role of the non-covalent in-
teractions is essential as it plays a major role in the formation of
the solid phase architecture, and also, the theoretical analysis pro-
vides greater insights towards the understanding of the practical
application of the formation of various crystalline motifs [11].
∗
Corresponding author.
E-mail address: lokanath@physics.uni-mysore.ac.in (N.K. Lokanath).
favor binding to the negatively charged biomolecules (the con-
stituents of the proteins and nucleic acids) [12]. Hence, the phar-
maceutical use of such metal complexes has excellent poten-
tial. Due to the promising biological activity, such as anti-cancer
drugs, antimicrobial, antimycotic bacterial agents, and anti-HIV
activities [13], the metal complexes are of great importance in
the field of the drug. Hence, an extensive understanding of the
crystal structure is required for the purposeful synthesis of the
new drugs [14]. Many metal complexes with chelating ligands are
found to be promising candidates for the synthesis of single-phase,
stoichiometric-mixed, and hetero-metal-doped metal oxides [15],
metal oxide nanoparticles [16], metal sulfide thin films [17] and
metal sulfide nanoparticles through thermal decomposition path-
ways [18].
Theoretical investigations are important to explore the funda-
mental properties and to understand the physical and chemical
properties of the ligands and metal complexes. Various compu-
tational chemistry tools, such as density functional theory (DFT),
have proven vital in biological and chemical research. The under-
standing of compounds is further enhanced by the experimental
and theoretical investigations of the structure, spectroscopic, and
Hirshfeld surface analysis.
In this regard, it is interesting to consider the cases where the
azomethine group acts as an important factor in creating non-
covalently bound supramolecular architectures. Thus, in this as-

https://doi.org/10.1016/j.molstruc.2022.134759
0022-2860/© 2022 Elsevier B.V. All rights reserved.
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al.
pect, we report the synthesis and in-depth studies of the lig-
and synthesized from the condensation reaction between ethyl
2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate and 2-
hydroxy-1-napthaldehyde and the corresponding palladium com-
plex through the single-crystal X-ray crystallography and various
computational methods. The main objective of this work is to
study the structural property changes during the complexation
process with the synthesized Schiff-base ligand.
2. Experiments
2.1. Materials
2-Hydroxy-1-naphthaldehyde, ethyl 2-amino-4,5,6,7-tetra-
hydrobenzo[b]thiophene-3-carboxylate and sodium tetrachloropal-
ladate (Na2 PdCl4 ) were purchased from Sigma Aldrich Ind. Ltd,
and they were used as received. The NMR spectra were recorded
using the Agilent NMR spectrometer at 400 MHz for 1 H NMR
and 100 MHz for 13 C NMR. The signals are abbreviated: s, singlet;
d, doublet; t, triplet; dd, doublet-doublet; m, multiplet and the
chemical shifts (δ ) are reported in ppm (parts per million). FTIR
characterization was carried out on a PerkinElmer 100 FTIR spec-
trometer. UV-visible spectra were recorded using a PerkinElmer
Lambda 35 spectrometer with 20 μg mol−1 concentration so-
lutions for all the compounds. Single crystal X-ray diffraction
intensity measurement using Mo-Kα radiation (λ = 0.71073 Å) at
room temperature.
2.2. Synthesis
2.2.1. Preparation of the Schiff-base ethyl (E)−2-
(((2-hydroxynaphthalen-1-yl)methylene)amino)−4,5,6,7-
tetrahydrobenzo[b]thiophene-3-carboxylate (LH)
The solution of ethyl 2-amino-4,5,6,7-tetrahydrobenzo[b]-
thiophene-3-carboxylate (0.225 g, 1 mmol) in ethanol (15 mL) was
added drop-wise to a magnetically stirred solution of 2-hydroxy-
1-naphthaldehyde (0.172 g, 1 mmol) in ethanol (15 mL) at room
temperature. The resulting orange-red mixture was refluxed with
stirring for 3 h, during which the progress of the reaction was
monitored by TLC. After completion of the reaction, the solvent
was distilled under reduced pressure on a rotary evaporator. The
solid obtained is then dried at room temperature in a desicca-
tor over anhydrous calcium chloride to afford ligand (LH) as an
orange-red crystalline solid. This solid was recrystallized in a 1:1
mixture of dichloromethane and n-hexane, giving needle shape
crystals of ligand (0.36 g, 95%); (Melting point: 170 °C). 1 H–NMR
(CDCl3 , 399.82 MHz) δ : 0.628–0.663 (t, 3H, –CH3 ), 1.02–1.039
(t, 2H, 16–H2 ), 1.052–1.082 (t, 2H, 17–H2 ), 1.939–1.967 (t, 2H,
18–H2 ), 2.016–2.045 (t, 2H, 15–H2 ), 3.635–3.688 (q, 2H, –OCH2 –),
6.390–6.413 (d, 1H, ArH, 3–H), 6.577–6.595 (d, 1H, ArH, 6–H),
6.739–6.760 (d, 1H, ArH, 7–H), 6.948–6.968 (d, 1H, ArH, 5–H),
7.021–7.044 (d, 1H, ArH, 8–H), 7.314–7.336 (d, 1H, ArH, 4–H),
8.514 (s, 1H, CH=N); 13 C{1 H}-NMR (CDCl3 , 100.54 MHz) δ : 14.7
(–CH3 ), 25.89 (C–16), 26.67 (C–17), 27.26 (C–18), 31.51 (C–15),
61.13 (–OCH2 –), 109.94 (C–1), 119.62 (C–8), 119.85 (C–3), 120.69
(C–6), 123.59 (C–12), 123.89 (C–7), 128.09 (C-5), 129.72 (C-13),
131.16 (C-10), 132.97 (C-4), 136.09 (C-9), 136.25 (C-14), 153.38
(C-11), 154.01 (C=O), 163.86 (CH=N), 165.62 (C-2).
2.2.2. Preparation of the palladium complex [PdLCl]
To a stirred solution of Na2 PdCl4 (0.147 g, 0.5 mmol) in wa-
ter (10 mL) added, a solution of LH (0.190 g, 0.5 mmol) pre-
pared in acetone (20 mL) under vigorous stirring. The resulting
mixture was stirred for 3 h at room temperature. After complete
consumption, the ligand was monitored by TLC and poured into
2
Journal of Molecular Structure 1276 (2023) 134759
100 mL of distilled water. The complex was extracted into chlo-
roform (100 mL × 2) from the reaction mixture. The organic layer
that separated was dried over anhydrous sodium sulfate. This chlo-
roform extract was concentrated to 10 mL on a rotary evaporator
and then treated with n-hexane (15 mL). The resulting precipitate
of [PdLCl] was filtered, washed with n-hexane (2 × 10 mL), and
dried. The orange-red single crystals of [PdLCl] suitable for X-ray
diffraction study were grown by slow evaporation of a mixture of
chloroform and n-hexane solution of [PdLCl] (0.23 g, 88%); (Melt-
ing point: 253 °C). 1 H–NMR (DMSO-d6 , 399.82 MHz) δ : 0.824–
0.859 (q, 3H, –CH3 ), 1.415 (bs, 2H, 16–H2 ), 2.149 (s, 2H, 17–H2 ),
2.329–2.386 (d, 2H, 18–H2 ), 2.983 (s, 2H, 15–H2 ), 3.814–3.849 (q,
2H, –OCH2 –), 6.862–6.885 (d, 1H, ArH, 3–H), 6.961–6.996 (d, 1H,
ArH, 6–H), 7.117–7.136 (d, 1H, ArH, 7–H), 7.444–7.464 (d, 1H, ArH,
5–H), 7.594–7.618 (d, 1H, ArH, 8–H), 7.714–7.735 (d, 1H, ArH, 4–
H), 8.412 (s, 1H, CH=N); 13 C{1 H}-NMR (DMSO-d6 , 100.54 MHz) δ :
14.282 (–CH3 ), 22.205 (C–16), 22.6 (C–17), 24.2 (C–18), 26.5 (C–
15), 60.065 (–OCH2 –), 110.295 (C–1), 122.680 (C–8, C–3), 123.3 (C–
6), 123.7 (C–12), 126.846 (C–7), 128.933 (C-5, C-13), 130.178 (C-10,
C-4), 133.259 (C-9), 133.813 (C-14), 157.285 (C-11), 160.237 (C=O),
162.195 (CH=N), 165.337 (C-2).
2.3. Structural analysis
A suitable single crystal of the ligand and the palladium com-
plex was carefully selected under a polarizing microscope. It was
mounted at the tip of the goniometer head using adhesive. The
single crystal intensity data of the ligand (LH) and palladium com-
plex ([PdLCl]) were collected using Rigaku Xta-lab mini diffrac-
tometer equipped with sealed-tube X-ray source (Mo-Kα radia-
tion = 0.71073 Å) operating at 50 kV and 12 mA. The data were
collected for different settings of φ (0°−90°), with a scan width of
0.5° and an exposure time of 3 s, by keeping the sample to a de-
tector distance of 50 mm. The complete data were processed using
the d∗ trek program [19], and the absorption correction was per-
formed using the multi-scan employed in CrystalClear-SM Expert
[20]. Using the OLEX2 software [21], the crystal structure of the
compounds was solved by direct methods (SHELXS) [22], and the
position of all the non-hydrogen atoms was identified and refined
on F2 by a full-matrix least-squares procedure using anisotropic
displacement parameters as provided in the SHELXL program pack-
age [23]. The non-hydrogen atoms are refined anisotropically, and
the hydrogen atoms were treated as horse-riding atoms using the
SHELXL default parameters. The geometrical calculations and the
crystal packing diagrams were prepared by the crystallographic
program PLATON and MERCURY 4.2.0 software, respectively [24].
2.4. Hirshfeld surface analysis
The Hirshfeld surface analysis and its associated two-
dimensional fingerprint plots for both the ligand and the
corresponding palladium complexes were generated using the
CrystalExplorer 17.5 software [25] with the help of the inalter-
able refined crystallographic information file (CIF) as input. The
Hirshfeld surfaces were mapped over dnorm , shape index, and
curvedness. The dnorm (normalized contact distance) is described
in terms of the van der Waals radii (vdW) of atoms, di (distance
between the Hirshfeld surface and the closed nucleus inside
the surface), and de (distance from the Hirshfeld surface to the
nearby nucleus outside the surface) parameters are represented
by the color gradient from red to blue. The dark red spots on the
dnorm surface indicate the short interatomic contacts, whereas the
other intermolecular interactions appear as light-red spots. The
blue color indicates the presence of non-interaction regions. The
various intermolecular interactions exhibited by both compounds
can be understood by the dnorm surface, and the quantifying of
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al.
Fig. 1. Scheme of the synthesized ligand and its palladium complex.
these interactions was done using the 2D fingerprint plots [26,27].
Through the Hirshfeld surface analysis, all the close contacts of
the ligands and the palladium complex can be visualized, provid-
ing valuable insights toward a better understanding the crystal
packing behavior in the solid state.
2.5. Computational studies
Quantum computational techniques are highly useful for theo-
retically investigating the compounds’ physical and chemical prop-
erties. The geometry optimization was accomplished within the
framework of the density functional theory (DFT) [28], using the
hybrid functional with non-local exchange due to Becke and the
correlation functional due to Lee, Yang, and Parr (B3LYP) [29], as
implemented in the Gaussian 16 package [30]. The calculations
were performed with the mixed basis set 6-311+G(d,p) [31] for
non-metal atoms and LanL2DZ [32] for the Pd(II) metal center
without any symmetry constraint. The atomic coordinates of the
crystal structure were used as the initial guess for electronic
structure optimization. The corresponding vibrational analyses per-
formed for the optimized geometries revealed the achievement of
the local minima on the potential energy surface.
Using Koopmans’ approximation, the highest occupied and low-
est unoccupied molecular orbitals (HOMO-LUMO), their energy
gap, and the related global and local indices revealing the chemical
properties of the molecules were calculated [33]. To investigate the
charge distribution and the possible reactive sites, molecular elec-
trostatic potential (MEP) were carried out. Furthermore, the natu-
ral bond orbital (NBO) calculations were performed to understand
various hyperconjugative interactions that stabilize the molecular
structures. All the results for the DFT calculations were visualized
using the GaussView 5 software [34].
The obtained geometries were used at the same level of the-
ory for the calculations for QTAIM [35], NCI [36], reactivity descrip-
tors, and aromaticity. The QTAIM topological properties of the elec-
tron densities at the bond critical points (BCPs) were computed.
Furthermore, the RDG (reduced density gradient) based NCI anal-
ysis was carried out, and the corresponding color-filled isosurfaces
graphs were drawn using the VMD (Visual Molecular Dynamics)
visualizer [37].
3
Journal of Molecular Structure 1276 (2023) 134759
3. Results and discussion
3.1. Synthesis of ligand (LH) and its Pd(II) complex [PdLCl]
The Schiff base ligand and its complex [PdLCl] were synthe-
sized, as shown in Fig. 1. The LH is freely soluble in chloroform,
dichloromethane, methanol, ethanol, acetone, acetonitrile, DMSO,
and DMF but insoluble in n-hexane, diethyl ether, THF, toluene, and
water. The orange-red solid of [PdLCl] was synthesized by a 1:1
stoichiometric reaction of the ligand with Na2 PdCl4 at room tem-
perature. The complex [PdLCl] showed solubility in polar solvents
such as chloroform, dichloromethane, acetone, acetonitrile, DMSO,
and DMF. The complex is stable to air and moisture in both solid
and solution state. The synthesis scheme of the ligand and the pal-
ladium complex is given in Fig. 1.
3.2. 1 H and 13 C{1 H} NMR spectral data
The 1 H and 13 C{1 H} NMR spectra of ligand (LH) were recorded
in CDCl3 and the spectra are shown in Figs. S1 and S2 (supplemen-
tary file), respectively. In the 1 H NMR spectrum of LH, the signal
for methylene protons (–OCH2 ) appeared as a quartet at δ , 3.64–
3.69 ppm, and the methyl protons signal observed at an upfield
region of δ , 0.63–0.66 ppm as a triplet and the other four methy-
lene protons gave peaks at δ , 1.02–1.04 (16–H2 ), 1.05–1.08 (17–H2 ),
1.94–1.97 (18–H2 ), 2.02–2.04 (15–H2 ) ppm as a triplet. The azome-
thine (CH=N) proton signal appeared as a singlet at downfield re-
gion δ , 8.51 ppm as reported earlier in the similar Schiff base lig-
ands [38]. In 13 C{1 H} NMR spectra of LH, the methylene carbon
(–OCH2 ) gave a peak at δ , 61.1 ppm, and the other four methy-
lene carbons gave peaks at δ , 25.9 (C–16), 26.7 (C–17), 27.3 (C–18),
31.5 (C–15) ppm. The carbon signal for –CH3 appears at the upfield
region of δ , 14.7 ppm, but the -C=N (imine) and –C=O (ester) car-
bon signals observed at the downfield field chemical shift region
of δ , 163.9 and 154 ppm, which are in agreement with the chem-
ical shifts of those carbons reported for related Schiff base ligands
[39]. The 1 H and 13 C{1 H} NMR spectra of [PdLCl] were recorded in
DMSO–d6 and are shown in Figs. S3 and S4, respectively. In the 1 H
NMR spectrum of [PdLCl], the signal for–OCH2 appeared as a quar-
tet at δ , 3.81–3.85 ppm, and the methyl protons signal observed at
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 2. ORTEP plot of the synthesized ligand.

Table 1
Analysis of intramolecular hydrogen interactions exhibited by the ligand.

Donor-
H···Acceptor D···H (Å) H···A (Å) D···A (°) D-H···A (°)

O1-H1···O2 0.82 2.55 3.174(3) 134.17

O1-H1···N1 0.82 1.84 2.57(3) 146.78
C11-H11···S1 0.93 2.64 3.065(3) 108.36

δ , 0.82–0.86 ppm as a triplet. The azomethine (CH=N) proton sig-

nal appeared as a singlet at downfield region δ , 8.41 ppm [39,40].
In the 1 H and 13 C NMR spectra of LH, the methylene carbon (–
OCH2 ) peaked at δ , 60.06 ppm, and the carbon signal for –CH3 ap-
peared at the upfield region of δ , 14.3 ppm. The -C=N (imine) and
ester (–C=O) carbon signals were observed at the downfield field
chemical shift region of δ , 162.2, and 160.2 ppm [39,40]. The other
proton and carbon signals in LH and [PdLCl] appeared at their char-
Fig. 3. The strong intramolecular interactions lead to the formation of the various
acteristic δ ppm.
synthons (S(6) and S(5)).

3.3. Crystal structure analysis

The X-ray structure determination details of the ligand and its
palladium complex are given in Table S1 (supplementary file).
3.3.1. Crystal structure of the ligand
The ORTEP plot of the Schiff base ligand formed by the
condensation reaction between the ethyl 2-amino-4,5,6,7-
tetrahydrobenzo[b]thiophene-3-carboxylate and 2-hydroxy-1-
naphthaldehyde is given in Fig. 2. The Schiff base ligand is planar
with a dihedral angle of 15.06°, as shown in Fig. S5. The C11=N1
bond lengths are consistent with a double bond (1.292 Å), while
the C9-O1 bond length (1.335 Å) is consistent with that of a single
bond.
The hydroxy group of the 2-hydroxy-1-naphthaldehyde
interacts with the nitrogen of the ethyl 2-amino-4,5,6,7-
tetrahydrobenzo[b]thiophene-3-carboxylate through strong intra
O1-H1···N1 interactions resulting in the formation of the S(6)
synthon as shown in Fig. 3. Further, due to the interaction be-
tween C11-H11···S1 and C15-H15···O3 resulted in the formation
of synthon S(5) (Fig. 3). The various intra molecular interactions
exhibited by the compound responsible for forming the synthons
are given in Table 1, along with its corresponding distances and
angles. The molecules are interconnected with each other along
the crystallographic c-axis through C15-H15B···O3 and C3-H3···O3
atoms resulting in the formation of a 1D molecular sheet and
supramolecular ring motif of R2 2 (10) as shown in Fig. 4. Further,
due to the weak intermolecular interactions of the C11 atom with
the five-membered ring (C12/S1/C13/C17/C18) and six-membered
ring (C7/C8/C9/C10/C5/C6) results in the formation of 2D architec-
ture along the crystallographic b-axis, which further stabilizes the
crystal structure (Fig. S6). The tabulation of the π ···π interactions
exhibited by the ligand is given in Table 2. The torsional angle of
C12-N1-C11-C10 is found to be −174.71(2)°, indicating an anti-
periplanar arrangement. The conformational assignments across
the bonds are given in Table S2. The hydrogen bonds were found
to participate in the short inter/intramolecular interactions, and
further, the van der Waals (π ···π ) interactions also contribute to
the crystal packing (Tables 1 and 2).
3.3.2. Crystal structure of the [PdLCl] complex
The synthesized Pd complex crystallizes in the triclinic space
group P1̄ with Z = 2. The ORTEP of the compound is given in
Fig. 5. The coordination sphere around the central Pd-atom consists
of two O- atoms and one N- and Cl- atom. The coordination dis-
tances for Pd1 case of Pd1-O3 = 1.996(3) Å, Pd1-O1 = 1.961(3) Å,
Pd1-Cl1 = 2.304(15) Å and Pd1-N1 = 2.027(3) Å was observed. The
different Pd1-O1 and Pd1-O2 distance results in the polyhedron
distortion closer to a tetragonal flattening rather than the elonga-

4
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 4. The intermolecular interactions result in the formation of a 1-D molecular sheet along the c-axis.

Table 2
The geometric features (distances in Å) of the π ···π interactions obtained for the ligand.

Cg(ring I)···Cg(ring J) Cg···Cg (Å) α (°) β (°) γ (°) Cg(I) ···perp (Å) Cg(J) ···perp (Å)

Cg(1)···Cg(3)i 3.866(2) 12.07(12) 15.0 26.9 −3.446(10) −3.7344

Cg(3)···Cg(3)ii 3.997(2) – 29.4 29.4 3.482(11) 3.482(11)

Symmetry transformations: i = 2-x, -y, 2-z

ii = 3-x, -y, 2-z. Cg(1) = Center of gravity of the ring (S1/C12/C13/C7/C18); Cg(3) = Center of gravity of the ring
(C5/C6/C7/C8/C9/C10).

Table 3
Various intra-molecular and inter-molecular hydrogen bond interactions result
in the formation of synthons.

Donor-
H···Acceptor D···H (Å) H···A (Å) D···A (Å) D-H···A (°)

C11-H11···S1 0.93 2.35 2.897(4) 117.00

C22-H22A···O2 0.97 2.39 2.782(8) 103.22
C23-H23···Cl1 0.98 2.44 3.407(11) 169.38

H23···Cl1 interaction. This CHCl3 solvent connects the other two

solvent molecules by Cl2 and Cl3 atoms along the (110) and (111)
directions respectively (Fig. 6). These solvent molecules act as a
bridge interconnecting two complex molecules resulting in the for-
mation of wave-like nature along the a-axis (Fig. S8). Further, the
Cg···Cg interaction results in the generation of another molecule
along the bc-plane resulting in the formation of a 2-D structure
which stabilizes the crystal structure (Fig. S9). Due to the rotation
of the C13-C14 bond, modification in the intramolecular interac-
tions in the complex was observed with the formation of two ad-
ditional S(5) synthons compared to that of the ligand, as shown in
Fig. 7. Various intramolecular interactions and the π ···π interac-
tions contributing towards the stabilization of the crystal structure
are given in Tables 3 and 4, respectively.
Fig. 5. ORTEP of the palladium complex drawn at 50% probability.

3.4. Fourier transform infrared spectra analysis

tion of the octahedra. Hence, the palladium coordination polyhe-
dron adopts the square planar structure [41].
The internal angles in the coordination of Pd complex
are N1-Pd1-O3 = 93.00(13)°, N1-Pd1-O1 = 92.79(13)°, O3-Pd1-
Cl1 = 87.18(10)° and O1-Pd1-Cl1 = 87.31(11)°. The dihedral angle
formed by the mean planes through the two six-membered rings
is 1.85° (Fig. S7).
Interestingly, it is worth noting that compared to the ligand in
its uncoordinated state, a rotation about the C13-C14 bond by 180°
was observed to allow the oxygen (O3) atom to chelate with the
palladium metal. Interestingly the crystallization solvent (CHCl3 )
also crystallizes bound with the palladium metal complex by C23-
The experimental IR spectra of the Pd(II) complex exhibited the
characteristic absorption bands around 1542–1569 cm−1, which is
attributed to the v(C=N) and the absorption band observed in the
region 1546.64 cm−1 corresponds to the C=N vibration. A shift was
observed in the absorption for the metal complex 1589.32 cm−1 ,
indicating the coordination of the Palladium to the imine nitro-
gen [42]. The C=N stretching band in the Schiff base ligand was
observed at 1691.92 cm−1 . In comparison, this peak was shifted
to a lower frequency for the palladium complex (1589.32 cm−1 ),
indicating the coordination of the nitrogen atom to the central
Pd(II) atom [43,44]. The stretching of the phenolic OH group was
observed at 3666.75 cm−1 . This band is absent in the spectra of

5
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 6. Intermolecular interactions of the complex via solvent molecule along (110) and (111) directions.

Fig. 7. Intramolecular interactions of the complex (the solvent molecule is omitted for clarity).

Table 4
The Cg···Cg interactions contribute towards the stability of the crystal structure.

Cg(I)···Cg(J) Cg···Cg (Å) α (°) β (°) γ (°) Cg(I)···perp (Å) Cg(J)···perp (Å)

Cg(1)···Cg(3) 3.972(3) 4.5(2) 31.0 31.5 3.386(2) 3.4050

Cg(1)···Cg(4) 3.654(3) 3.8(3) 22.0 20.2 −3.428(2) −3.387
Cg(1)···Cg(5) 3.777(3) 3.3(3) 21.6 24.8 −3.427(2) −3.512
Cg(2)···Cg(1) 3.927(3) 4.5(2) 31.5 31.0 3.4052(16) 3.3806
Cg(2)···Cg(3) 3.674(2) 1.85(16) 20.0 21.4 3.4207(16) −3.437
Cg(4)···Cg(3) 3.594(3) 3.1(3) 17.1 19.7 −3.384(3) −3.5182

the palladium complex, indicating the deprotonation of the pheno-
lic OH followed by the coordination to the palladium ion. Further,
these results were found to be in collaboration with that the the-
oretical FTIR results. The theoretical and experimental FTIR spectra
of the ligand and the palladium complex are given in Figs. 8 and
S10, respectively.
3.5. UV-Vis spectral analysis
The UV-visible absorption spectra of both the ligand and the
complex were recorded at room temperature with 20 μg ml−1
concentration solutions in DMSO for the wavelength range of 300–
700 nm. The electronic spectra of the compounds were also cal-
culated using TD-DFT (Time Dependent Density Functional The-
ory) approach with the CPCM (Conductor-like Polarizable Contin-
uum Model) to simulate the presence of the solvent. The wave-
length (λ), oscillator strength (f), excitation energies (E), and as-
signment for the electronic transitions are given in Table 5. The
UV–Visible spectra of the ligand showed a major absorption peak
at 431.50 nm (theoretical: 455.16 nm), which is mainly due to
the π → π ∗ transitions. Further, the theoretical spectra showed a
shoulder at 314.32 nm, which is attributed to the n→π ∗ transi-
tions. A shift in the absorption peak was observed for the metal
complex, and a major absorption peak at 529.91 nm (theoretical:
513.36 nm) can be ascribed to the π → π ∗ transitions. For the pal-
ladium complex, the electronic spectral results indicated that the
complex had diamagnetic behavior exhibiting square planar geom-
etry [45,46]. The theoretical and experimental UV-absorption spec-

6
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 8. Theoretical FTIR spectra of the ligand and the complex obtained using the same level of theory.

Table 5 electron density and conformational changes in the complex com-

Assignment of the UV absorption bands of the ligand and the com-
pared to that of the ligand molecule. The 2D fingerprint plots of
plex obtained from the TD-DFT calculations.
the Hirshfeld surface of the ligand, palladium complex, and its rel-
Wavelength (λ) E (eV) Configuration ative contributions of different interactions overlapping in the full
(nm)
fingerprint plots are shown in Fig. 12. The fingerprint plots can
Ligand be decomposed to highlight particular atoms pair close contacts,
455.16 2.724 H→L (98.99%) where the complementary regions of one molecule act as a donor
353.05 3.5118 H-2→L (92.52%)
(de > di ) and the other as an acceptor (de < di ).
339.53 3.6516 H-3→L (40.35%)
Complex In both the ligand and its palladium complex, the H···H interac-
575.85 2.1531 H→L (23.28%) tions are found to have the highest contribution to the total Hir-
575.85 2.1531 H→L+1 (64.37%) shfeld surface. A decrease in the percentage of hydrogen interac-
483.80 2.5627 H→L (30.11%)
tions was observed for the complex (32.7%) compared to that of
the ligand (55.3%), this is due to the chelation of the palladium
metal with the ligand molecule. Similar results were observed for
tra of the ligand and the complex are given in Figs. 9 and S11, re- the C···H interactions (ligand: 16.3% and Pd complex: 8.0%) and
spectively. O···H interactions (ligand: 10.6% and Pd complex: 4.8%), where the
contribution of these contact types are found to be decreased, as
compared to that of the metal complex. Interestingly, the C···C in-
3.6. Hirshfeld surface analysis
teractions are found to be increased in the metal complex (7.2%)
compared to that of the ligand (6.8%) (Fig. 13).
The significant intermolecular interactions in the crystalline ar-
Due to the complexation of the palladium chloride with the
rangements of the ligands and the metal complex are evaluated
ligand and the presence of the chloroform (CHCl3 ) as a solvent
by the Hirshfeld surface (HS) analysis. The Hirshfeld surfaces of
molecule, leading to the formation of the H···Cl interaction con-
the ligand and its palladium complex are shown in Fig. 10, re-
tributing about 31.8% to the total Hirshfeld surface of the molecule.
vealing the surfaces that have been mapped over dnorm [(−0.0522
to 1.4154 Å) in a1 and (−0.1151 to 1.5663 Å) in a2], shape index
[(−1.00 to 1.00 Å) in b1 and (−1.00 to 1.00 Å) in b2] and curved- 3.7. Structure properties study based on the density functional theory
ness [(−4.00 to −0.40 Å) in c1 and (−4.00 to −0.40 Å) in c2]. A (DFT)
significant change in the position of the blue and red triangles,
which indicates the C–H···π interactions, was observed between Theoretical calculations were performed to optimize the molec-
the shape index plot of the ligand and the palladium complex, as ular structures of the ligand and the complex to evaluate the phys-
shown in Fig. 10(b1) and 10(b2) respectively. Further, the flat re- ical and chemical properties of the synthesized compounds. The
gions on the curvedness plot validate the existence of the π ···π in- absence of the imaginary frequencies of the compounds confirmed
teractions in both the ligand and the complex. These findings were the existence of optimized structures to their ground state (mini-
found to be in accordance with the structural analysis results. The mum energy).
de and di mapped Hirshfeld surface of the ligand and the palla- The primary research objective is to study the complexation
dium complex is shown in Fig. 11. Significant changes were ob- process of the ligand with Pd2+ cation and the resulting structural
served in the surface, which is attributed to the changes in the and energetic variations. The structures of both the ligand and the

7
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 9. UV-visible spectra of the ligand and the complex were obtained using TD-DFT calculations.

Fig. 10. Hirshfeld surface plot of the ligand (dnorm : (a1), shape index: (b1), curvedness: (c1)) and the palladium complex (dnorm : (a2), shape index: (b2), curvedness: (c2)).

8
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al.
Fig. 11. The Hirshfeld surface is generated using the surface property de (ligand: d1, e1) and di (palladium complex: d2, e2).
complex were optimized at the B3LYP/6-311+G(d,p) level of theory.
The comparison of the bond length, bond angles, and torsional an-
gles of the crystal structure and the optimized structures are given
in Table S3. An excellent correlation coefficient was observed be-
tween the experimental and theoretical structures (Ligand: bond
length – 0.999, bond angle – 0.9999, torsion angle – 0.999, palla-
dium complex: bond length – 0.988, bond angle – 0.9941, torsion
angle – 0.988).
3.8. Study of the electronic properties
To analyze and understand the chemical activity of the com-
pounds, the frontier molecular orbitals (FMO) are essential. The
FMO of the ligand and the complex were computed using the func-
tional B3LYP and 6-311+G(d,p) basis set.
The frontier molecular orbitals and the energy diagrams of the
synthesized ligand and the palladium complex are given in Figs.
14 and 15, respectively. The highest occupied molecular orbitals
(HOMO) have the electron donating tendency, whereas the lowest
unoccupied molecular orbitals (LUMO) have the electron accept-
ing tendency [47]. From Fig. 14, the plot of the HOMO and LUMO
of the ligand indicates that the orbitals are spread over the en-
tire ligand molecule. In contrast, for the metal complex, the HOMO
and LUMO orbitals are shifted and mainly concentrated on the C–N
bond, where the electrons are partially transferred from the ni-
trogen and the oxygen of the ligand to the central metal atom
(Fig. 15) [48]. The HOMO-LUMO orbital energies, their energy gaps,
and the compound’s other local and global parameters are listed in
Table 6.
From Table 6, it is observed that the energy gap of the com-
plex (2.8822 eV) is less compared to the ligand (3.1258 eV) [49,50].
This decrease in the energy gap of the complex is attributed to
the increased conjugated system compared to the ligand [51]. The
synthesized palladium complex showed less energy gap compared
to other reported palladium complexes [52–55]. The global hard-
9
Journal of Molecular Structure 1276 (2023) 134759
ness (η) value indicates the molecular reactivity and the high value
of the ligand compared to that of the complex is in accordance
with the energy gap values. The chemical potential (μ) value re-
flects the charge transfer of the system from a higher chemical
potential to one of the lower chemical potentials confirming the
charge transfer happening from the ligand (−4.0963 eV) to the
complex (−4.6355 eV). This is further substantiated by the higher
electronegativity (χ ) of the complex (4.6355 eV) compared to that
of the ligand (4.0963 eV), as electronegativity value refers to the
power to attract the electrons from a donor.
3.9. Molecular electrostatic potential (MEP)
The MEP studies were performed to understand the extent of
the chemical reactivity and to explore the molecular structures’ re-
lationship with the compounds’ physicochemical properties. With
the help of the color scheme employed in the MEP diagram, the
electrophilic (positive regions) and nucleophilic sites (negative re-
gions) are identified, as represented by the blue and red colors,
respectively. Identifying these reactive regions provides significant
information regarding the charge distribution in the compounds
[56]. The MEP map of the ligand and the complex, along with the
values, are given in Fig. 16. Significant changes in the electrostatic
potential between the ligand and the complex were observed. In
the MEP plot of the ligand, the red region was found to be around
the oxygen atom of the carboxylate group, signifying it to be a nu-
cleophilic site. As the metal approached the ligand, a conforma-
tional change was observed as the oxygen atom in the carboxylate
group coordinated with the metal atom. Further, the absence of
the red region on the oxygen atom of the carboxylate group in the
metal complex substantiates the significant changes in the elec-
tron density distribution in the complex compared to that of the
ligand. Further, the interaction of the chloroform (CHCl3 ) solvent
with the chlorine atom coordinated with the metal atom resulted
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 12. 2D fingerprint plots of the synthesized ligand and its corresponding palladium complex.

Table 6
Electronic properties of the ligand and the Pd-complex.

Eg (eV) I (eV) A (eV) χ (eV) η (eV) σ (1/eV) μ (eV) ω (eV)

Ligand
HOMO-LUMO 3.1258 5.6592 2.5334 4.0963 1.5629 0.6398 −4.0963 5.3681
HOMO-1- 5.2798 6.5873 1.3075 3.9474 2.6399 0.3788 −3.9474 2.9513
LUMO+1
Pd complex
HOMO-LUMO 2.8822 6.0766 3.1943 4.6355 1.4411 0.6939 −4.6355 7.4552
HOMO-1- 3.9857 6.6736 2.6879 4.6808 1.9928 0.5018 −4.6808 5.4971
LUMO+1
Where, Eg – Energy gap, I - Ionization energy, A – Electron affinity, χ – Electronegativity, η -Global hardness, σ - Global softness, μ - Chemical
potential, and ω - Global electrophilicity.

in the formation of the electrophilic region, as shown by the red
colored area in the metal complex.
4. NBO analysis
The natural bond orbital (NBO) analysis helps to investigate
the charge transfer in the molecular system and their interactions
among various bonds. The NBO calculations were carried out by
investigating all the possible interactions between filled Lewis-type
NBOs and empty non-Lewis NBOs, along with estimating their en-
ergy by second-order perturbation theory. The NBO analysis pro-
vides better insight into the chemical concepts regarding the bond-
ing involved in the structure from the wave functions with high
accuracy [57]. The synthesized compounds’ second-order stabiliza-
tion energies (E2) are given in Table S4.
The hyperconjugative interaction energies were described using
the second-order perturbation approach, and the possible intensive
interactions are given in Table S4.
The NBO analysis of the metal complex indicated a consider-
able donor-acceptor type of delocalization between the lone pair
of oxygen/nitrogen orbitals and the anti-lone pair of the palladium
orbital. Due to the interactions of the bonding and anti-bonding

10
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al.
Fig. 13. Percentage contribution to the Hirshfeld surface by various intermolecular contacts present in the synthesized compounds.
Fig. 14. Frontier molecular orbital distribution among the ligand molecule.
orbitals, the delocalization effects play a crucial role in the coordi-
nation environments of the Pd(II) ions.
The interactions energies present in the coordination envi-
ronment are found to be LP(4)Cl1 →LP∗ (1)Pd1 , LP(1)N1 →LP∗ (5)Pd1 ,
LP(2)O1 → LP∗ (5)Pd1 , LP(4)Cl1 → LP∗ (6)Pd1 associated with the ener-
11
Journal of Molecular Structure 1276 (2023) 134759
gies 147.47, 73.91, 50.91 and 50.29 kcal/mol, respectively. From Ta-
ble S4, it is clear that the stabilization of the system due to the
overlap of the bonding and anti-bonding orbitals also results in
charge transfer interactions.
4.10. Natural hybrid orbital analysis
The symmetrically orthogonalized hybrid orbital obtained from
the natural atomic orbital (NAO) centered on a particular atom un-
der investigation through unitary transformation results in the nat-
ural hybrid orbitals (NHOs). The direction of each hybrid is speci-
fied in terms of the spherical polar angles theta (θ ) and phi (ϕ )
from the nucleus, and the bending of the bond from the direction
of the line joining the nuclei centers is expressed as the deviation
angle (Dev) [58]. Table S5 summarises the bending of the different
bonds in both the ligand and the complex. In ligand, the oxygen of
σ C14-O3, σ C15-O2, and σ C9-O1 is more bent away from the C–O
line of centers by 8.6, 2.5 and 3°, respectively. As the approach of
the palladium metal resulted in the conformational changes in the
complex compared to that of the ligand. The deviation of the se-
lected atoms in the complex is given in Table S5. The deviation
of the σ C14-O3 and σ C9-O1 in the complex is found to be de-
creased (Dev. 1.8 and 1.9°), whereas a little change in the deviation
was observed for the σ C15-O2 group (Dev. 2.8°). This indicates that
the natural hybrid orbitals are influenced by the approaching group
(palladium metal), which causes the conjugative effect of the steric
effect.
4.11. QTAIM and NCI analysis
The QTAIM analysis has proved to be an efficient technique to
visualize and study the nature of bondings in molecular systems
based on the topology of the electron density at specific points
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 15. Changes in the frontier molecular orbital distribution of the ligand due to the formation of the complex.

Fig. 16. The molecular electrostatic potential map of the ligand and the complex with the color range and the scale.

12
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Table 7
QTAIM properties of the synthesized ligand and its complex.

Interactions ρ BCP  2 ρ BCP VBCP GBCP

(ligand) (a.u.) (a.u.) ε (a.u.) (a.u.) HBCP |V|/G

C13-H13···H19 0.01371 0.04966 0.40906 −0.00777 0.0101 −0.0023 0.7693

O3-H3···N5 0.05594 0.11655 0.03429 −0.05468 0.04191 0.01277 1.3047
C27-H27C···O3 0.00737 0.02427 0.03066 −0.00444 0.00525 0.81116 0.8457

Interactions ρ BCP  2 ρ BCP ε VBCP GBCP HBCP |V|/G

([PdLCl]) (a.u.) (a.u.) (a.u.) (a.u.)

C11-H11···S1 0.16461 0.06067 0.92565 −0.01148 0.01332 0.00184 0.8618

C11-H11···H4 0.01530 0.05931 0.45081 −0.00925 0.01204 0.00278 0.76827
C23-H23···Cl1 0.01841 0.05708 0.02322 −0.01097 0.01262 0.00165 0.86925
C23-Cl2···H15B 0.00469 0.01536 0.06012 −0.00208 0.00296 0.00088 2.3636

Electron density (ρ ), Laplacian of electron density ( 2 ρ BCP ), ellipticity (ε ), electron potential energy density (VBCP ), Lagrangian kinetic energy (GBCP ), total
electron energy density (HBCP ) at the corresponding bond critical point (BCP) with the estimated interaction energy (Eint ).

Fig. 17. Molecular graph of the ligand and the complex, indicating the changes of the critical points (CPs).

called bond critical points (BCPs). It allows the possibility of divid-
ing the system into subsystems based on the zero-flux in the elec-
tron density gradient field. The QTAIM data helps to classify the
bond/interaction types, characterized the bond/interaction nature,
and distinguish the bond/interaction strengths. A typical covalent
(shared shell) bond is characterized by ρ (r) > 0.1,  2 ρ (r) < 0, and
H(r) < 0 (a.u.), an ionic (closed shell) interaction given by ρ (r) >
0,  2 ρ (r) > 0 and H(r) > 0 (a.u.) and regarding the 0 < ρ (r) <
0.1,  2 ρ (r) > 0 and H(r) < 0 suggests a dative or electron-transfer
bond [59,60].
The Schiff base ligand scaffold coordinate to the Pd(II) metal ion
results in the electron density redistribution at many critical points
in the ligand scaffold due to the polarizing effect of the Pd(II) ions.
The QTAIM properties of the ligand and the complex is given in
Table 7.
A significant change in the intermolecular interactions was ob-
served in both the ligand and the metal complexes, which pro-
moted us to explore the contributions of the weak non-covalent
forces in the crystal assembly and the importance of the C–H···π
and C–H···Cl interactions establish the organization of the extended
structure (Fig. 17).
4.12. NCI isosurface analysis of ligand and the complex
4.12.1. Ligand
The red region in the middle of the aromatic and cyclohexane
ring indicates steric repulsion. Interestingly a blue region is ob-
served between the O2-H3···N5 (ligand), indicating a strong hydro-
gen bond interaction due to the high concentration of the elec-
tron density. This results in the formation of a red region (C14-
C7-C10-O2-H3···N5). Due to the presence of the C16-O48 group in
close proximity to the O2-H3···N5 results in the formation of van
der Waals type of interactions, as indicated by the green region in
Fig. 18. Further, the NCI isosurface analysis found a few interactions
that were not identified by the AIM analysis.
The presence of the small greens patches in between the re-
gions of C44-H47···O2 and C44-H46···O2 indicates the small elec-
tron density regions. Further, the reddish green region present in
between the region C38-H40···O4 indicates both attractive and re-
pulsive interactions due to ring closure. The peaks in the region
−0.05 a.u. are associated with strong, attractive interactions (O2-
H3···N5). The peaks in the region −0.01 to 0.005 a.u. and from 0.01
to 0.038 a.u. are due to the weak attractive (van der Waals) and re-
pulsive interactions [61].
4.12.2. Pd complex
Due to the coordination of the metal with the ligand, a major
shift in the electron density of the ligand was observed (Fig. 18).
The chelation of the metal with the coordinating atoms resulted
in the formation of two chelating rings (Pd1-N1-C11-C10-C9-O1
and Pd1-N1-C12-C13-C14-O3), which are associated with the pres-
ence of the red region in the ring critical point (RCP) due to the
steric repulsion. The blue circular disc formed along the coordinate
bond between the Pd1-Cl1 indicates the presence of high electron
density (Fig. 18). Further, the green region present between the
C23-H23···Cl1, C15-H15B···Cl2, and C23-Cl3···O3 indicates the exis-
tence of weak van der Waals interaction which is attractive in na-
ture. The C23-H23···Cl1 and C15-H15A···Cl2 interactions show the
presence of the hydrogen halogen interactions exhibited by the
compound. The 2D NCI plot of the complex is associated with a
large number of peaks compared to that of the ligand 2D NCI plot
(Fig. 18).

13
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al. Journal of Molecular Structure 1276 (2023) 134759

Fig. 18. 3D Isosurface and 2D scatter NCI plots of the ligand and the complex reveals various interactions.

Fig. 19. Electron localization function plot of the ligand and the complex, drawn with contour lines.

4.13. Electron localization function (ELF) analysis
The electron localization function is used to evaluate the elec-
tron localization between chemically bonded atoms [62]. The ELF
analysis provides an idea regarding the chemical structure, molec-
ular bonding, reactivity, and the possibility of finding an electron
with the same spin in the neighborhood of a reference electron can
be studied. The color scheme of red to blue, along with the color
codes (0.9–1.0), indicates the localization and delocalization of the
electrons, respectively. The electron localization function contour
map of the compounds is given in Fig. 19. The red regions are asso-
ciated with hydrogen atoms indicating that the electrons are highly
localized. In contrast, the atomic regions of other atoms (C, N, and
Cl) are represented by the blue color indicating the delocalization
of the electrons.
4.13.1. Independent gradient model (IGM) analysis
The IGM is another electron-density based computational
method which helps in revealing the qualitative and quantita-
tive study of the non-covalent interactions. The key feature of the
IGM is that it furnishes an uncoupling scheme that automatically
extracts the signature of the interactions between two different
molecules (δ ginter ), or inside these molecules (δ gintra ), or between
two atoms (δ gpair ). The δ ginter term indicates the study of inter-
molecular interactions [63].
From Fig. 20, it can be observed that the presence of the green
regions indicates the presence of the vdW nature of the weak in-
teractions. On the other hand, the IGM analysis of the complex
showed the presence of a blue isosurface between the coordina-
tion bonds (O, N, O, Cl-Pd), revealing the presence of high electron
density and strong bonding interactions in this region [64].

14
B.S. Chethan, H.R. Rajegowda, R.u.R. Khan et al.
Fig. 20. 3D isosurfaces of the ligand and the complex obtained by the IGM analysis.
5. Conclusion
The synthesized ligand and its palladium complex were struc-
turally characterized in this study. The Schiff base ligand was coor-
dinated as a tridentate ligand through O (O1 and O2) and N (N1)
donor atoms to the palladium metal atom.
The ligand is observed to be exhibiting a dihedral angle of
15.06°, and due to the complexation with the palladium atom, a
conformational change was observed in the ligand resulting in the
decrease of dihedral angle in the complex (1.85°). Interestingly, a
rotation of the ligand by 180° was observed about the C13-C14
bond, allowing the oxygen (O3) atom to chelate with the palladium
metal, resulting in the formation of the additional S(5) synthon.
Hydrogen-halogen interactions (C23-H23···Cl1) were observed be-
tween the crystallization solvent (CHCl3 ) and the complex. A sig-
nificant change in the electrostatic potential in the molecular elec-
trostatic potential of the ligand was observed as the metal ap-
proached the ligand leading to a conformational change. The struc-
tural conformational change was further corroborated by the de-
creased deviation of the chelating atoms’ nuclei centers compared
to that of the ligand from the natural hybrid orbital analysis.
The QTAIM analysis revealed the importance of the C–H···π and
C–H···Cl interactions in establishing the organization of the ex-
tended structure. The non-covalent interactions revealed the im-
portance of the various interactions towards the crystal packing.
The blue isosurface between the coordinating bonds with the pal-
ladium metal indicated strong bonding interactions. This study em-
phasizes understanding the effects on the conformation of the lig-
and due to the complexation process and the importance of struc-
tural techniques, theories, and computational tools in achieving the
goal. The study of the changes in the conformation of the ligand
and also the changes in the intermolecular interactions due to the
approach of the metal atom by experimental and theoretical may
lead in the direction of the crystal packing pattern modification,
which in turn facilitates the tuning of the physicochemical and
thermophysical properties of the compounds.
Declaration of Competing Interest
There are no conflicts to declare.
CRediT authorship contribution statement
B.S. Chethan: Writing – original draft, Conceptualization,
Methodology, Visualization, Software, Formal analysis, Data
curation. H.R. Rajegowda: Formal analysis, Methodology.
15
Journal of Molecular Structure 1276 (2023) 134759
Riyaz ur Rahaman Khan: Formal analysis, Methodology. N.K.
Lokanath: Resources, Visualization, Writing – review & editing,
Supervision, Project administration.
Data Availability
Data will be made available on request.
Acknowledgments
The authors Chethan B. S. and Lokanath N. K. are thankful to
the DST-FIST (SR/FST/PSI-119/2019), National Single Crystal Diffrac-
tometer Facility, DoS in Physics, CPEPA, IOE and DST-PURSE, Vij-
nana Bhavan, University of Mysore, Mysuru for providing the in-
strumentation facility.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.molstruc.2022.134759.
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