Journal of Molecular Structure 1189 (2019) 8e20

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Journal of Molecular Structure

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

Synthesis, PXRD structural determination, Hirshfeld surface analysis

and DFT/TD-DFT investigation of 3N-ethyl-2N’-(2-ethylphenylimino)
thiazolidin-4-one
Nour El Houda Belkafouf a, Fayssal Triki Baara b, Angela Altomare c, Rosanna Rizzi c,
Abdelkader Chouaih a, *, Ayada Djafri b, Fodil Hamzaoui d
a
Laboratory of Technology and Solid Properties, Faculty of Sciences and Technology, Abdelhamid Ibn Badis University, BP 227, Mostaganem, 27000, Algeria
b
Laboratory of Applied Organic Synthesis (LSOA), Department of Chemistry, Faculty of Sciences, University of Oran-1 Ahmed Ben Bella, 31000, Oran, Algeria
c
CNR-IC Institute of Crystallography, Via G. Amendola 122/O, 70126, Bari, Italy
d
LPFM Acad
emie de Montpellier, France

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

Article history: The title compound, 3N-ethyl-2N’-(2-ethylphenylimino)thiazolidin-4-one (C13H16N2OS), was synthe-

Received 15 December 2018 sized and structurally studied by IR and (1H, 13C) NMR spectroscopy. The crystal structure of the title
Received in revised form compound was investigated using powder X-ray diffraction (PXRD) data via Direct Methods and refined
3 April 2019
by the Rietveld method. The compound crystallizes in the tetragonal system, space group I
4 with cell
Accepted 5 April 2019
constants: a ¼ 16.99742(15) Å, b ¼ 16.99742(15) Å, c ¼ 9.2663(2) Å, V ¼ 2677.15(7) Å3, Z ¼ 8. The molec-
Available online 6 April 2019
ular geometry was optimized using the density functional theory (DFT/B3LYP) method with the 6-
311G(d,p) basis set and compared to the experimental data. The experimental and theoretical structures
Keywords:
Powder X-ray diffraction
are found to be consistent. The molecular packing of the title compound exhibits CeH,,,O and OeH,,,N
FT-IR hydrogen bonds forming supramolecular network. The details of the intermolecular interactions were
UVeVisible studied through the Hirshfeld surface map and two-dimensional fingerprint plot. Detailed vibrational
Tauc plot assignments and NMR chemical shifts were explored by DFT computation, showing good agreement with
Thiazolidinones the experimental results. All the vibrational modes were assigned using the potential energy distribution
(PED). UVeVisible spectrum in chloroform solvent was analyzed and electronic transitions involved in
the title compound were predicted using the TD-DFT method. The direct and indirect band gaps were
estimated using Tauc Plots via UVeVis spectroscopy. Furthermore, the values of the highest occupied
molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy were calculated
by the DFT method and their distribution was confirmed by the determination of DOS spectra. The global
reactivity descriptors and the Fukui functions were evaluated. Mulliken population analysis and natural
bond orbital (NBO) theory were used to compute atomic charges and the outcomes are consistent with
the MEP map distribution.
© 2019 Published by Elsevier B.V.

1. Introduction biological field [2]. Thiazolidinone derivatives are also known to

Organic heterocyclic compounds containing five-membered
heterocycles with two heteroatoms, especially thiazole moieties,
have been commonly used as biologically active materials [1].
Among them, thiazolidinones represent an important class of five-
membered heterocycles, well known for their multiple applications
which have motivated their extensive study especially in the
* Corresponding author.
E-mail address: achouaih@gmail.com (A. Chouaih).
exhibit other interesting physicochemical properties such as op-
toelectronic and photovoltaic [3,4]. In addition, thiazole based li-
gands associated to transition metal are used in designing of
coordination chemistry compounds [5]. The development of new
organic compounds with good activity is one of the major chal-
lenges in organic synthesis. Recently, many studies have been
widely reported about thiazolidinones related compounds, using
both X-ray diffraction and quantum chemical calculations [6e10].
In this context, we have recently published the synthesis of a
thiazolidinone derivative and its structural determination [11].

https://doi.org/10.1016/j.molstruc.2019.04.028
0022-2860/© 2019 Published by Elsevier B.V.
 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20
Continuing in this field and considering the importance of this kind
of compounds, our interest has been focused on the study of the
relationship between the structure and the molecular properties of
a new synthesized organic compound containing thiazolidinone
moiety, using both powder X-ray diffraction (PXRD) and density
functional theory (DFT) calculations. In the present study, besides
the geometry optimization, the DFT method was used to calculate
vibrational frequencies, NMR spectra, frontier molecular orbitals,
global and local chemical reactivity indices, atomic charges and
molecular electrostatic potential of the investigated molecule.
Furthermore, the time-dependent density functional theory
method (TD-DFT) was employed to obtain the most important
electronic transitions from UVeVisible theoretical spectrum.
2. Experimental and computational details
2.1. Synthesis of 3N-ethyl-2N’-(2-ethylphenylimino)thiazolidin-4-
one
An equimolar solution of 1-ethyl-3-(2-ethylphenyl) thiourea
and ethyl bromoacetate, in 40 ml of absolute ethanol and in the
presence of acid catalyst, was refluxed for 10 h. The resulting solid
was isolated, washed with cold water, filtered, dried and recrys-
tallized from ethanol to yield 3N-ethyl-2N’-(2-ethylphenylimino)
thiazolidin-4-one as highlighted in Scheme 1.
Yield 95%, m.p. 79  C; IR (KBr, ncm
1): 3067(CeH), 1725 (C]O),
1635 (C]N), 1260 (CeN), 488(CeSeC); 1H NMR (500 MHz, CDCl3):
1.08 (t, 3H, CH3), 1.20 (t, 3H, CH3), 2.49 (q, 2H, CH2), 3.75 (q, 2H,
CH2), 4.01 (s, 2H, CH2thia), 7.25 (dd, 1H, H aromatic), 7.06 (td, 1H,
H aromatic), 7.16 (td, 1H, H aromatic), 6.81 (dd, 1H, H aromatic);
13
C NMR (125 MHz, CDCl3): 172.09(C]O), 154.77(C]N), 12.83,
33.05, 37.81, 14.99, 24.76, 146.72, 129.37, 120.20, 124.93, 129.37,
135.93.
2.2. Spectral measurements
The title compound was characterized by experimental (FT-IR,
NMR and UVeVis) techniques. FT-IR spectrum was recorded as KBr
pellets on an IR-Prestige-Shimadzu Fourier transform infrared
spectrophotometer equipped with a high-sensitivity DLATGS
(Deuterated Triglycine Sulfate Doped with L-alanine) detector from
the range of 4000e400 cm
1 in a solid phase at room temperature,
number of scans 8, resolution 4 cm
1 and the reported wave-
numbers are given in cm
1.1H and 13C NMR spectra in CDCl3 solu-
tion were measured on a Bruker AC250 instrument at 298 K.
Chemical shifts are reported as d (ppm) relative to TMS as internal
standard. UVeVis spectrum was recorded using a Unicam UV2
spectrophotometer in chloroform solution in the range from 200 to
700 nm.
2.3. Powder data collection
Powder X-ray diffraction experiment was performed at room
Scheme 1. Synthetic route for preparation of 3N-ethyl-2N’-(2-ethylphenylimino)thiazolidin-4-one.
9
temperature (293 K) by using an automated Rigaku RINT2500
laboratory diffractometer (50 KV, 200 mA), equipped with an
asymmetric Johansson Ge(111) crystal to select the monochromatic
CuKa1 radiation (l ¼ 1.54056 Å). The silicon strip Rigaku D/teX
Ultra detector was used. The measurement was scanned for
diffraction angles (2q) ranging from 7 to 70 with a step size of
0.02 and a time of 6 s/step. The experimental powder diffraction
pattern of 3N-ethyl-2N’-(2-ethylphenylimino) thiazolidin-4-one is
shown in Fig. 1. All the ab-initio crystal structure solution steps by
powder diffraction data were performed by using the EXPO soft-
ware [12].
2.4. Computational details
Computational approach is an effective way to design molecules
by analyzing their structure and molecular properties. In this
context, the theoretical density functional geometry optimization
of the title molecule in the gas phase was carried out using the
Gaussian 09 program [13]. The geometry calculation was fully
performed employing the B3LYP correlation functional [14,15]
supplemented with the 6-311G(d,p) basis set. Quantum-chemical
calculations have been successfully used to complement the
experimental PXRD data at several stages of the crystal structure
solution process [16]. GaussView 5.0.8 [17] was used to draw the
input molecular structure. The vibrational frequencies of the title
molecule in the gas phase were obtained by applying the same level
of theory. The scale factor was used to obtain results in the best
agreement with the experimental data. The scaling factor with the
standard value of 0.9679 was selected for B3LYP/6e311G(d,p) [18].
Furthermore, for the assignments of the vibrational modes, the
potential energy distribution was studied by the VEDA 4 software
[19]. In addition and using the optimized geometry parameters, the
excitation spectrum of the compound was calculated by the TD-DFT
method at 6-311G(d,p) level. The Multiwfn program [20] was uti-
lized to analyze the molecular orbital contributions and to compute
the density of state (DOS) spectra. The highest occupied molecular
orbital (HOMO) and the lowest unoccupied molecular orbital
(LUMO) analysis were carried out in order to explain the charge
transfer within the molecule. The global hardness (h), global soft-
ness (s), electronegativity (c) and chemical potential (m) were
computed using the HOMO-LUMO energies. Finally, atomic charges
and molecular electrostatic potential were theoretically
determined.
2.5. Hirshfeld surface analysis
Hydrogen bonds are the most important intermolecular in-
teractions for understanding the molecular packing in the solid
state. Hirshfeld surface (HS) analysis is an efficient tool to evaluate
the contribution of each intermolecular interaction [21e23]. The
dnorm (normalized contact distance) derived from de, di and van der
Waals radii of the atoms (r vdwi and r vdw
e ), is described by the
following equation:
10 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20

Fig. 1. X-ray powder diffraction pattern of 3N-ethyl-2N’-(2-ethylphenylimino)thiazolidin-4-one.

    Rpʹ ¼ 17.684, Rwpʹ ¼ 14.091, Rexpʹ ¼ 5.774, DW ¼ 0.248,

di
r vdw
i
de
r vdw
e RBragg ¼ 11.193, RF ¼ 7.497 and the agreement between the observed
dnorm ¼ þ and calculated patterns is shown in Fig. S1 (see supplementary
r vdw
i
r vdw
e
material).

where de and di represent the distances from the point to the

nearest nucleus external and internal to the surface, respectively. 3.2. Molecular and solid state structure description
The CrystalExplorer 17.5 program [24] was used to obtain the 3D-
HS map and 2D-fingerprint plot. The atomic labelled X-ray structure and the optimized molec-
ular geometry of the title compound are shown in Fig. 2. Experi-
mental and calculated bond lengths, bond angles and torsion angles
3. Results and discussion are provided in Table 2.
As reported in Table 2, the C9eO1 bond shows a typical double
3.1. Structural solution and refinement bond character. For the two CeS bond lengths, C7eS1 and C8eS1,
the experimental values are in the standard range of C(Sp3)eS
The PXRD pattern was successfully indexed using the N- single bond [1.81 Å] [29], while the theoretical values show
TREOR09 program [25] integrated in the EXPO software. The X-ray different bond lengths. All the CeN bonds, namely, C1eN1, C7eN2,
powder diffraction pattern revealed that the investigated com- C9eN2 and C12eN2 indicate a normal single bond character except
pound was single phase. A tetragonal unit cell, characterized by for C7eN1 which indicates a partial double bond character. The
values of M20 [26] and Fomnew [25] figures of merit equal to 44 C9eN2 bond, due to its neighbouring carbonyl group, is slightly
and 2.496 respectively, was obtained. The refined cell parameters shorter than the C12eN2 one. These bond length values wholly
are: a ¼ 16.99742(15) Å, b ¼ 16.99742(15) Å, c ¼ 9.2663(2) Å and agree with those reported in literature [30] for structures con-
V ¼ 2677.15(7) Å3. The space group I
4 was then identified. The taining the thiazolidinone moiety. The experimental and theoret-
crystallographic details are reported in Table 1. To perform the ical C7eS1eC8 bond angle values of the thiazole ring are 93.1(19)
structure solution of the title compound, the Le Bail algorithm [27] and 92.63 , respectively, consistent with previous studies on
was used to decompose the experimental X-ray powder diffraction similar compounds [3,10]. In general, no differences between the
pattern into single integrated intensities. Direct methods [28], calculated and observed results have been noticed for all bond
implemented in EXPO, were used in the ab-initio structure solution. angles of the title compound. Except for the two ethyl groups, the
At this stage, the hydrogen atoms were located, by geometric molecular structure consists of two planar moieties in which the
construction, at their theoretical positions according to the chem- aromatic cycle is in one plane and the thiazole ring in another one.
ical formula. The constraint Uiso(H) ¼ kUiso(C), where k ¼ 1.2 was The two rings are mostly perpendicular each other with a dihedral
applied. The Rietveld method, integrated in EXPO, was used to angle of 92.81. Mean deviations from planarity for benzene and
refine the structure. The Rietveld refinement yielded the following thiazole rings are 0.23 and 1.30 , respectively.
residual factors Rp ¼ 3.248, Rwp ¼ 4.843, Rexp ¼ 1.948, c2 ¼ 5.956, The supramolecular analysis of the title compound shows the
presence of several hydrogen bonds. The solid state structure ex-
hibits CeH,,,O and CeH,,,N strong hydrogen-bonding in-
Table 1
teractions in which the C8 atom acts as donor while O1 and N1 as
Crystallographic data for C22H17O6N3S.
acceptors. Some hydrogen bonds, as determined by X-ray diffrac-
Chemical formula C13H16N2OS tion technique, are reported in Table 3. These intermolecular in-
Mr 248.0
teractions contribute to the stabilization of the molecular packing
Crystal system Tetragonal
Space group (no.), Z I
4 (82), 8 in the unit cell.
a (Å) 16.99742(15)
b (Å) 16.99742(15)
c (Å) 9.2663(2) 3.3. Hirshfeld surface (HS) description
V (Å3) 2677.15(7)
l(Å) 1.540560 The molecular HS analysis was performed using X-ray diffrac-
2qmin, 2qmax( ) 7, 70 tion results in order to analyze the interactions in the title com-
Reflections (no.) 919
pound. The HS was described by three-dimensional dnorm surfaces
 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20 11

Fig. 2. Crystal structure of 3N-ethyl-2N’-(2-ethylphenylimino) thiazolidin-4-one with the labelled and numbered atoms. (a): X-ray structure, (b): Optimized by B3LYP/6-311G(d,p).

Table 2 hydrogen bonds.

Bond lengths (Å), bond angles ( ) and torsion angles ( ) for the non-hydrogen atoms, The two-dimensional (2D) fingerprint plot is illustrated in
as determined by X-ray diffraction technique and DFT calculations. Fig. 3(b) using de and di distances. As shown in the figure, the H,,,H
Atoms X-ray DFT Atoms X-ray DFT interactions contribute with an overall HS of 61.2% and appear in
Bond lengths (Å)
the center of the scattered points. Except for H,,,H interactions,
C1eC2 1.410(6) 1.403 C9eN2eC12 119.0(3) 117.7 representing the majority of contacts of the title molecule, the most
C1eC3 1.410(7) 1.411 N2eC9eC8 114.1(3) 112.4 important contributions to the HS come from C,,,H ǀ H,,,C (7.3% ǀ
C1eN1 1.400(6) 1.405 N2eC9eO1 121.3(4) 124.1 6%) and O,,,H ǀ H,,,O (5.9% ǀ 5%) contacts. Other intermolecular
C2eC4 1.390(5) 1.391 N2eC12eC13 112.1(3) 112.6
interactions, contributing to HS, are S,,,H ǀ H,,,S (4.6% ǀ 2.4%) and
C3eC5 1.383(6) 1.398 C8eC9eO1 125.0(4) 123.5
C3eC10 1.492(5) 1.513 Torsion angles ( ) N,,,H ǀ H,,,N (1.8% ǀ 1.7%) contact regions.
C4eC6 1.391(6) 1.393 C3eC1eC2eC4 3.0(15)
1.9
C5eC6 1.390(6) 1.393 N1eC1eC2eC4 174.2(9)
174.9
3.4. Infrared spectroscopy
C7eN1 1.261(7) 1.264 C2eC1eC3eC5
4.0(2) 2.6
C7eS1 1.820(5) 1.794 C2eC1eC3eC10 175.2(11)
175.3
C8eS1 1.830(4) 1.820 N1eC1eC3eC5
175.3(11) 175.6 In this study, the infrared spectroscopy is used to identify the
C7eN2 1.420(6) 1.401 N1eC1eC3eC10 4.(2)
2.3 functional groups present in the molecule. 93 possible vibrational
C9eN2 1.410(5) 1.388 C2eC1eN1eC7 85.1(17)
67.1 modes were assigned by the percentage of PED contributions and
C12eN2 1.463(5) 1.478 C3eC1eN1eC7
103.6(17) 119.9
the results are reported in Table 4. The FT-IR and simulated IR in gas
C8eC9 1.492(5) 1.516 C1eC2eC4eC6 0.6(17) 0.1
C9eO1 1.210(5) 1.212 C1eC3eC5eC6 1.5(19)
1.5 phase spectra are shown in Fig. 4. The predicted vibrational fre-
C10eC11 1.530(4) 1.539 C10eC3eC5eC6
177.6(11) 176.4 quencies are compared with the experimental ones. A scaling factor
C12eC13 1.511(4) 1.527 C1eC3eC10eC11 91.9(12) 81.4 of 0.9679 was used to reduce frequency differences between the

Bond angles ( ) C5eC3eC10eC11
89.0(12)
96.5
experimental and theoretical vibration values.
C2eC1eC3 120.0(4) 119.8 C2eC4eC6eC5
3.1(17) 1.0
C2eC1eN1 120.1(4) 120.3 C3eC5eC6eC4 2.0(14)
0.3
Usually, the vibrational modes in the region 1650 - 1550 cm
1
C1eC2eC4 120.0(4) 120.7 C1eN1eC7eS1
4.9(16) 170.6 are attributed to the stretching vibration bands of the imine group
C3eC1eN1 120.1(4) 119.5 C1eN1eC7eN2 175.5(11)
10 (C]N) while in the region 1750 - 1650 cm
1 are attributed to the
C1eC3eC5 119.2(4) 118.1 N1eC7eS1eC8
177.2(9)
178.6 carbonyl group (C]O), indicating the presence of the iminothia-
C1eC3eC10 120.3(4) 121.1 N2eC7eS1eC8 2.5(8) 1.8
zolidinone fragment [31e34]. For the title compound, these two
C1eN1eC7 128.5(4) 130.6 N1eC7eN2eC9 175.5(14)
179.6
C2eC4eC6 121.1(3) 119.9 N1eC7eN2eC12 2.0(2)
8.5 vibrational modes are clearly identified experimentally at 1726 and
C5eC3eC10 121.2(4) 120.7 S1eC7eN2eC9
4.2(14)
0.1 1636 cm
1, indicating the presence of imine and carbonyl groups,
C3eC5eC6 122.1(4) 122.0 S1eC7eN2eC12
177.4(9) 171.0 respectively. In addition, the PED analysis shows a vibrational
C3eC10eC11 113.0(3) 112.6 C7eS1eC8eC9
0.4(8)
2.8 contribution of imine group with 72% (mode 76) and carbonyl
C4eC6eC5 119.0(4) 119.3 C7eN2eC9eC8 4.1(13)
2.1
N1eC7eS1 118.1(3) 117.2 C7eN2eC9eO1
177.1(9) 177.6
group with 76% (mode 77). Furthermore, it is known that n(CeS)
N1eC7eN2 134.0(4) 132.5 C12eN2eC9eC8 177.6(7)
173.9 and n(CeN) vibrations of a thiazolidinone moiety are identified at
S1eC7eN2 109.5(3) 110.3 C12eN2eC9eO1
3.6(15) 5.9 1035e245 and around 1300 cm
1, respectively [35]. For our mole-
C7eS1eC8 93.1(19) 92.6 C7eN2eC12eC13
63.1(13)
80.2 cule, the n(CeS) vibrations were observed at 644, 488 and 463 cm
1
(calculated at 641, 484 and 462 cm
1). For the n(CeN) vibration
C7eN2eC9 117.0(3) 117.1 C9eN2eC12eC13 123.8(9) 90.9
C7eN2eC12 124.2(3) 124.6 S1eC8eC9eN2
1.9(13) 3.3
S1eC8eC9 107.1(3) 107.41 S1eC8eC9eO1 179.4(11)
176.5 bands of the thiazolidinone ring, a stretching vibration, with a PED
of 40%, was observed at 1260 cm
1 and calculated at 1279 cm
1.
Moreover, the presence of thiazolidinone ring is confirmed by the
Table 3
angular deformation vibration d(C8C9N2) observed at 774 cm
1
Selected hydrogen bonds by X-ray diffraction (Å,  ). and calculated at 764 cm
1, and also is confirmed by the out-of-
plane g(O1C8N2C9) mode which appears at 574 cm
1 and calcu-
DeH$$$A DeH H$$$A D$$$A DeH$$$A Symmetry
lated at 576 cm
1. These results are comparable with those found in
C8eH8A$$$O1 0.98 2.50 3.20(2) 128.1 -x þ 1/2, -y þ 1/2, z þ 1/2 literature [3].
A broad signal at ~3400 cm
1 related to OH group is assumed to
C8eH8B$$$N1 0.98 2.45 3.28(2) 143.3 xþ1/2, -yþ1/2, -zþ1/2

be due to adsorbed atmospheric water as FTIR is very sensitive to

moisture. This band was treated as background. The computed IR
mapped from
0.2071 to 1.4807 and the map is shown in Fig. 3(a). bands in the range 3060
3026 cm
1 are assigned to the n(CeH)
The red spots in the dnorm surfaces indicate the regions of donor- stretching vibrations of the phenyl group, whereas the corre-
acceptor interactions related to CeH,,,O and CeH,,,N weak sponding observed bands in the FT-IR spectrum are in the range
12 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20
Fig. 3. HS view of 3N-ethyl-2N’-(2-ethylphenylimino) thiazolidin-4-one (a) 3D HS and (b) 2D fingerprint plot.
3067
3024 cm
1. These results are in good agreement with the
n(CeH) stretching vibrations of aromatic groups occurring in the
region 3100
3000 cm
1 [36]. Furthermore, the existence of ethyl
group associated to the aromatic cycle can be confirmed by the
symmetric bending modes in the range 2986
2906 cm
1 which
are assigned to the n(CeH) stretching vibrations.
The methylene group connected to the thiazolidinone moiety
exhibits pure stretching vibrations with a contribution of 99%. From
the PED contribution, the nine vibration modes of CH3 group and
the six vibration modes of CH2 group were easily assigned.
Commonly, when both CH3 and CH2 groups are present in a mo-
lecular system, only one band can be observed in the range
3000
2865 cm
1 [37,38]. In our present work, as observed in
Table 4, the calculated stretching vibrations are predicted in the
range 2999
2907 cm
1. The corresponding experimental stretch-
ing vibrations are observed in the range 3015
2869 cm
1.
For the CH3 groups, the expected deformation modes were
assigned to the bands between 1503 and 1488 cm
1, while the
twisting and rocking modes occurred in the expected range [39].
However, the expected deformation modes for the CH2 groups are
associated with the IR bands in the range 1503
1448 cm
1.
Furthermore, the wagging modes are assigned between 1399 and
1080 cm
1, and, as expected, the rocking modes are assigned in the
range 922
226 cm
1, as shown in Table 4.
From the above results, good agreement can be noted between
the experimental and theoretical vibrational wavenumbers, the
small differences are probably due to the strong intermolecular
interactions in the solid state since theoretical calculations were
carried out on isolated molecules in gas phase.
3.5. NMR spectral studies
In the present study, the 1H and 13C isotropic chemical shifts for
the title compound, with respect to TMS [40], were calculated by
using the GIAO [41] method and B3LYP functional with 6-311G(d, p)
basis set. Experimental and theoretical 1H and 13C NMR isotropic
chemical shifts (ppm) are gathered in increasing order in Table 5
and the corresponding experimental spectra are presented in
Fig. S2 (see supplementary material). The title molecule has 16
hydrogen atoms, four are attached to the phenyl ring, two are
connected to the thiazol ring and ten hydrogen atoms are associ-
ated to the two ethyl moieties. As reported in Table 5, the 1H
isotropic chemical shifts are observed in the range 1.08e7.25 ppm.
The chemical shifts of aromatic protons in organic molecules are
usually observed in the range 6.00e8.00 ppm [42]. However, the
electronic environment of the proton can have a huge effect on the
chemical shift. For the title compound, the calculated isotropic
chemical shifts of the aromatic protons (H2, H4, H5 and H6) appear
in the range 6.71e7.32 ppm and the corresponding experimental
values are between 6.81 and 7.25 ppm. In the 1H NMR spectrum,
the singlet signal at 4.01 ppm (3.6 ppm with DFT) is due to meth-
ylene protons attached to the thiazolidinone ring. Another singlet
signal is displayed at 3.75 ppm (3.36e3.72 ppm with DFT) which is
assigned to the protons of the NeCH2 group. These values are
different from those of H10A and H10B (2.49 ppm experimentally
and 2.28e2.74 ppm with DFT) due to the directly attached elec-
tronegative nitrogen atom. The methyl protons (H11A, H11B and
H11C) and (H13A, H13B and H13C) are observed at 1.20 and
1.08 ppm and calculated at 0.82e1.76 ppm and 0.35e0.86 ppm,
respectively.
For 13C NMR of organic molecules, it is well known that the
chemical shift range of aromatic carbon atoms is generally
>100 ppm [43,44]. In the title compound, thirteen different carbon
atoms are present, constituting the phenyl and thiazole rings and
two ethyl groups. As shown in Table 5, the 13C NMR chemical shifts
in the two rings are >100 ppm except for the C8 atom. Because of
hydrogen bonds of methylene and methyl groups, the chemical
shifts of the C8, C10, C11, C12 and C13 atoms are observed at 33.05,
24,76, 14.99, 37.81 and 12.83 ppm, respectively. For these atoms,
also the theoretical values are less than 100 ppm. For the C]O
group of carboxylic acids and derivatives, the 13C chemical shifts
vary from 150 to 185 ppm [45]. In the present investigation, the C9
atom of the carbonyl group has an experimental and theoretical
chemical shift of 172.09 and 176.55 ppm, respectively. In general,
the theoretical and experimental 1H and 13C NMR data show good
correlations.
3.6. UVevis spectral analysis
The electronic transitions in the title compound were investi-
gated by using the TD-DFT computation and described by vertical
excitation energies, oscillator strength (f), transition wavelength
and contributions. The results are reported in Table 6. Only the
electronic transitions with contributions greater than 10% are
considered. The experimental and theoretical UVeVisible absorp-
tion spectra are shown in Fig. 5(a). The UVevisible experimental
spectrum displays two large bands at 238 and 272 nm attributed to
the p- p* and n- p* transitions [46,47], respectively. In the same
way, the electronic spectrum calculated by the TD-DFT method
using chloroform as solvent, displays two strong peaks at
lmax ¼ 233 and 294 nm, attributed to the p-p* and n- p* transitions,
respectively. In chloroform, the calculated excitation (electronic
 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20 13

Table 4
Comparison of the experimental FTeIR and theoretical wavenumbers (cm
1) for the title compound by the B3LYP/6e311G(d,p) method.

Mode FT-IR Theoretical Vibrational assignments from B3LYP/6-311G(d,p) (PED (10)%)

Unscaled Scaled Int Raman

93 3067 3188 3061 23.42 317.49 ns C6eH6 (89)

92 3040 3176 3049 18.63 72.83 ns C4eH4 (76)þ nas C2eH2 (15)
91 3033 3163 3036 4.16 93.03 nas C2eH2 (75) þ ns C5eH5 (11)þ nas C4eH4 (10)
90 3158 3031 1.48 23.94 ns CH2 (C12) (78) þ nas CH2 (C12) (13)
89 3025 3153 3027 11.63 68.22 ns C5eH5 (81)þ ns C4eH4 (13)
88 3015 3123 2999 0.46 106.67 nas CH2 (C8) (99)
87 3116 2991 20.80 33.64 nas CH3 (C13) (83)þ ns CH2 (C12) (11)
86 3111 2986 28.44 21.63 ns CH3 (C11) (80)
85 2983 3106 2982 17.87 74.99 nas CH3 (C13) (91)
84 2972 3093 2969 0.90 93.08 nas CH2 (C12) (10) (76) þ ns CH3 (C13) (11)
83 3091 2967 42.32 97.73 nas CH3 (C11) (82)
82 3076 2953 10.50 240.29 ns CH2 (C8) (99)
81 2947 3065 2942 14.71 77.33 nas CH2 (C10) (87)
80 2929 3040 2918 14.79 125.11 ns CH3 (C13) (97)
79 3032 2911 26.79 117.00 ns CH2 (C10) (81)
78 2869 3028 2907 41.48 142.85 ns CH3 (C11) (87)
77 1726 1803 1731 139.84 106.31 ns C9eO1 (76) þ nas C7¼N1 (12)
76 1636 1727 1657 1232.65 153.83 ns C7¼N1 (72)þ nas C9eO1 (11)
75 1595 1634 1569 61.75 120.69 ns C3eC5 (62) þ d C5eH5 (14)
74 1562 1610 1545 25.86 29.09 ns C4eC6 (56) þ d C1C2C4 (12)
73 1484 1515 1454 35.89 26.57 b C2eH2 (38) þ d C1C2C4 (21)
72 1512 1451 3.22 4.16 d CH2 (C10) (68)
71 1446 1504 1444 10.54 2.09 d CH2 (C12) (71)þ t CH3 (C13) (16)
70 1499 1439 10.13 8.10 d CH2 (C10) (74)
69 1434 1498 1438 5.84 8.76 d CH3 (C11) (68)
68 1491 1431 16.70 19.30 d CH2 (C12) (65) þ nas C7eN2 (13)
67 1424 1489 1429 1.89 15.29 d CH2 (C10) (63)
66 1415 1475 1416 10.37 8.66 b C6eH6 (47) þ nas C1eC2 (29)
65 1385 1462 1403 4.63 28.16 d CH2 (C8) (91)
64 1374 1420 1363 9.65 0.61 g CH2 (C8) (80)
63 1405 1349 4.84 2.97 g CH3 (C11) (94)
62 1402 1346 6.31 5.99 t CH2 (C12) (40) þ d CH2 (C12) (23)
61 1338 1385 1329 90.77 7.57 g CH3 (C11) (35) þ nas C8eC9 (11) þ t CH2 (C12) (12)
60 1355 1301 1.54 10.66 g CH2 (C10) (11) þ t C1eC3 (50)
59 1344 1290 1.71 10.00 t CH2 (C10) (33) þ ns C1eC2 (24)þ b C4eH4 (13)
58 1260 1333 1279 301.87 3.29 ns C9eN2 (40)
57 1240 1297 1245 3.38 1.50 nas C1eC2 (42) þ b C5eH5 (26)
56 1278 1227 12.57 27.45 ns C1eN1 (11) þ d C11C10H10 (20)
55 1218 1263 1212 40.69 19.17 d C11C10H10 (11) þ t C7S1C8H8 (11)
54 1208 1253 1203 40.17 10.81 t CH2 (C8) (41)
53 1182 1220 1171 25.47 42.31 nas C3eC5 (14) þ ns C3eC10 (18)þ d C6C5H5 (11)
52 1157 1202 1154 14.28 1.35 ns C3eC5 (12) þ nas N1eC1 (10)þ ns C3eC10 (12)þ d C1C2C4 (12)
51 1181 1134 0.37 9.96 d C5eH5 (80) þ nas C4eC6 (12)
50 1116 1150 1104 1.27 3.86 d S1C8H8 (36) þ t C7S1C8H8 (42)
49 1089 1141 1095 6.02 2.57 d C4C6H6 (15) þ d C6C5H5 (16)
48 1122 1078 85.49 2.48 nas C8eC9 (32) þ t N2C12C13H13 (15)
47 1103 1059 28.93 1.53 g CH3 (C13) (29) þ nas C8eC9 (14)þ d C13C12N2 (13)
46 1049 1084 1041 2.78 1.52 g CH3 (C11) (19) þ nas C10eC11 (10)þ d C3C10C11 (13)
45 1028 1071 1029 12.41 25.79 ns C1eC2 (16)þ ns C10eC11 (10) þ d C6C5H5 (13)
44 1051 1009 1.40 7.09 ns C3eC5 (32)
43 1029 988 27.62 5.06 nas N2eC12 (68)
42 946 980 941 0.02 0.54 g C6eH6 (75)þ t C1C2C4C6 (16)
41 972 933 1.32 8.68 ns C10eC11 (63)
40 959 921 8.39 10.76 ns C8eC9 (45)
39 905 949 911 3.69 0.26 g C2eH2 (74)
38 874 923 886 9.46 1.36 r CH2 (C8) (48) þ t C7S1C8H8 (17) þ g O1C8N2C9 (11)
37 867 898 862 46.77 10.52 ns C12eC13 (46) þ d S1C7 ¼ N1 (13)
36 838 873 838 5.05 0.88 g C5eH5 (72)
35 820 852 818 2.14 4.63 ns C1eN1 (14) þ d C1C2C4 (41)
34 774 796 764 2.93 5.92 d C1C3C5 (10) þ d C8C9N2 (34) þ t N2C12C13H13 (18)
33 791 760 6.42 1.69 r CH2 (C10) (39) þ t CH2 (C10) (10)þ
32 752 783 752 8.79 6.88 d C8C9N2 (20) þ t N2C12C13H13 (24)
31 740 770 739 25.08 7.66 t C1C2C4C6 (12) þ g N1C3C2C1 (14)
30 764 733 48.69 0.99 g C4eH4 (72)
29 712 746 716 1.29 7.32 ns C3eC10 (13) þ d C3C5C6 (14)
28 644 667 641 5.08 16.64 nas C7eS1 (11) þ g S1N2N1 ¼ C7 (20)
27 628 644 618 5.28 3.62 d C6C4C2 (16) þ g S1N2N1 ¼ C7 (29)
26 585 606 582 13.15 2.80 d C1C2C4 (40)
25 574 600 576 2.02 2.01 r CH2 (C8) (11) þ t C8C9N2C7 (11)þ g O1C8N2C9 (39)
24 568 590 567 6.78 0.95 g O1C8N2C9 (19) þ t C1C2C4C6 (15) þ t C7S1C8H8 (11)þ
23 533 552 530 4.90 2.61 d C3C10C11 (12) þ g C10C1C5C3 (11)
22 523 546 525 1.21 4.84 d C3C5C6 (24) þ t C1C2C4C6 (14)
(continued on next page)
14 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20

Table 4 (continued )

Mode FT-IR Theoretical Vibrational assignments from B3LYP/6-311G(d,p) (PED (10)%)

Unscaled Scaled Int Raman

21 488 505 484 10.02 5.27 nas C8eS1 (13) þ d S1C7 ¼ N1 (17)
20 463 481 462 13.34 2.77 nas C8eS1 (10) þ d C9N2C7 (17)þ d C13C12N2 (12)
19 435 449 431 5.07 0.95 d N1C1C2 (23) þ d C5C3C10 (12)
18 423 438 420 7.28 1.51 d C5C3C1 (39)
17 388 373 4.97 5.44 ns C7eS1 (23) þ d C13C12N2 (31)
16 366 351 2.71 0.80 r CH2 (C12) (48) þ t N2C12C13H13 (16)
15 339 326 3.48 3.47 d C3C10C11 (20) þ t C1C2C4C6 (30)
14 333 320 2.34 3.59 d N1C1C2 (13) þ d C5C3C1 (13) þ t C3C10C11H11 (15)
13 249 239 0.09 3.82 r CH3 (C11) (20) þ d S1C7 ¼ N1 (14) þ t C3C10C11H11 (13)
12 226 217 0.06 0.37 r CH3 (C13) (26) þ t C1C2C4C6 (13)
11 214 206 0.59 1.25 r CH3 (C11) (45)
10 205 197 1.08 1.29 d C5C3C10 (19)þ t C1C2C4C6 (17)
9 143 138 0.39 2.02 d C13C12N2 (14) þ g C12C7C9N2 (52)
8 135 130 0.41 3.84 d C3C10C11 (16) þ t C1C2C4C6 (11) þ g C10C1C5C3 (35)
7 101 97 10.21 0.15 r CH2 (C8) (12) þ t C8C9N2C7 (62)
6 94 90 0.63 1.34 g C12C7C9N2 (52)
5 79 75 0.22 3.26 t C1C2C4C6 (10) þ t C7N2C12C13 (30) þ g C12C7C9N2 (18)
4 66 63 0.04 4.49 d C7¼N1C1 (25) þ t C7N2C12C13 (13) þ t C7N2C12C13 (17)
3 55 53 0.16 0.85 t C11C10C3C1 (10) þ t C11C10C3C1 (32) þ g N1C3C2C1 (11)
2 39 38 0.01 3.29 t C1N1 ¼ C7N2 (60)
1 27 26 0.01 4.68 t C3C1N1 ¼ C7 (75)
n, stretching; s, symmetric; as, antisymmetric; d, scissoring; t: twisting; g, wagging or out-of-plane deformation; b, deformation in the plane; r, rocking.

Table 5
Experimental (in CDCl3 solution) and calculated 1H and13C isotropic chemical shifts
(ppm) for the title compound using the B3LYP/6e311G(d,p) level of theory.
1 13
Atoms H chemical shifts Atoms C chemical shifts

Experimental Calculated Experimental Calculated

H13A 1.08 0.3491 C13 12.83 15.2325

H13B 1.08 0.7321 C11 14.99 15.8849
H13C 1.08 0.8550 C10 24.76 32.9722
H11A 1.20 1.1061 C8 33.05 40.3479
H11B 1.20 0.8237 C12 37.81 42.8796
H11C 1.20 1.7690 C2 120.20 124.7334
H10A 2.49 2.7497 C4 124.93 131.3990
H10B 2.49 2.2873 C6 127.01 128.4350
H12A 3.75 3.7276 C5 129.37 135.9468
H12B 3.75 3.3601 C3 135.93 142.0161
H8A 4.01 3.6205 C1 146.72 152.7584
H8B 4.01 3.6713 C7 154.77 154.6004
H2 6.81 6.7139 C9 172.09 176.5464
H6 7.06 7.0841
H4 7.16 7.2079
H5 7.25 7.3180
Fig. 4. Comparison of experimental and simulated at 6-311G(d,p) level IR spectra of
3N-ethyl-2N’-(2-ethylphenylimino) thiazolidin-4-one.

obtain the direct and indirect optical gaps [49e51] according to the
transition from the ground state to the first excited state) for the following relations [52]:
title compound is at 294.23 nm with an oscillator strength of 0.0758
and excitation energy of 4.2139 eV, corresponding to the electronic

transition HOMO-LUMO with a contribution of 94%. This excitation ðahnÞ2 ¼ A hn
Eg for allowed direct transition
is produced by a single electronic transition S0/S1 as can be seen
in Table 6. The calculated l value at 294.23 nm assigned to HOMO-
LUMO electronic transition is due to the n-p* transition which may

be attributed to the excitation of carbonyl group. In addition, the ðahnÞ1=2 ¼ A hn
Eg for allowed indirect transition
most intense absorption band centered at l ¼ 233 nm was gener-
ated by the five most dominant electronic transitions S0/S1, where a is the absorption coefficient, A is the absorption constant
S0/S4, S0/S6, S0/S7 and S0/S9. Fig. 5(b) shows the calculated and Eg is the optical band gap.
electronic transitions for the title compound. Based on the above Using the data of the experimental UV Visible spectrum, the
results, a good agreement was noticed between experimental and Tauc [ðahnÞ2 and ðahnÞ1=2 versus ðhnÞ] diagram was performed for
theoretical results. direct and indirect transitions. The extrapolation of the linear part
Two types of electronic transitions are observed in the title of this diagram to the zero point, allows the determination of the
molecule: direct and indirect, depending on the nature of the op- optical gap values as shown in Fig. 6. The optical band gap energy
tical gap (direct or indirect). These types are determined via the for the title compound was estimated by two values: 4.07 eV and
Tauc method [48], used to characterize several materials in order to 4.86 eV for the direct transitions and 3.7 and 4.26 eV for indirect
transitions.
 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20 15

Table 6
Absorption data obtained by the TD-DFT method with B3LYP/6-311G(d,p) basis set.

Electronic transitions labs (nm) Eex (eV) f Contribution (%) MO/Character

S0/S1 294.23 4.2139 0.0758 94 HOMO/LUMO

S0/S2 256.14 4.8405 0.0148 18 HOMO-1/LUMO
65 HOMO/LUMOþ1
S0/S3 244.93 5.0619 0.0500 21 HOMO-2/LUMO
11 HOMO-1/LUMO
19 HOMO/LUMOþ2
28 HOMO/LUMOþ3
S0/S4 238.13 5.2065 0.0802 39 HOMO-2/LUMOþ3
14 HOMO-1/LUMO
35 HOMO/LUMOþ3
S0/S5 233.93 5.3000 0.0437 16 HOMO-4/LUMO
26 HOMO-1/LUMO
30 HOMO/LUMOþ2
S0/S6 230.15 5.3871 0.0657 22 HOMO-2/LUMO
29 HOMO-1/LUMO
14 HOMO/LUMOþ1
10 HOMO/LUMOþ2
S0/S7 229.26 5.4079 0.0606 44 HOMO-4/LUMO
22 HOMO/LUMOþ2
15 HOMO/LUMOþ3
S0/S8 224.76 5.5164 0.0072 19 HOMO-2/LUMOþ2
41 HOMO-2/LUMOþ3
13 HOMO-1/LUMOþ3
S0/S9 214.80 5.7721 0.0721 19 HOMO-3/LUMO
10 HOMO-1/LUMOþ1
63 HOMO/LUMOþ4
S0/S10 211.15 5.8719 0.0132 60 HOMO-2/LUMOþ1
14 HOMO-1/LUMOþ1

Fig. 5. (a) Theoretical and experimental UVeVis spectra and (b) Electronic transitions spectra for 3N-ethyl-2N’-(2-ethylphenylimino) thiazolidin-4-one.

3.7. Frontier molecular orbitals and density of state
The Frontier Molecular Orbital (FMO) and density of states
(DOS) are extensively used to predict the electronic behavior of
molecular materials [53e58]. The FMO and DOS investigations
show the electron density localization of the molecular orbitals and
the contribution percentage of the electronic states of each mo-
lecular fragment, respectively. As commonly known HOMO and
LUMO show the ability of donating and accepting an electron in any
molecule, respectively [59]. Furthermore, the charge transfer in-
teractions within a molecule can be deduced from the HOMO and
LUMO energy gaps [60].
The FMO's of the title molecule are calculated by using B3LYP/6-
311G(d,p). Fig. 7 shows the distribution of the HOMO and LUMO
energies for the title compound. The molecular orbitals HOMO
1,
HOMO and LUMOþ1 are located mainly on the ethyl-benzene
fragment whereas the LUMO orbital is distributed over the thia-
zolidinone fragment indicating that the charge transfer occurred
from ethylbenzene group to the thiazolidinone group. The kinetic
stability of the title compound is highlighted by the energy gap
between HOMO and LUMO, which is found to be 5.04 eV.
The FMO distribution was confirmed by the partial DOS spectra
performed by the Multiwfn program [20] using the molecular or-
bitals output of the Gaussian 09 software [13], and shown in Fig. 8.
The molecular orbital contributions obtained by the DOS study are
reported in Table 7. From these results, the electron density of
HOMO is mainly concentrated on the aromatic moiety with a
contribution of 55% while LUMO is concentrated on ethyl-
16 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20

Fig. 6. Tauc spectra, direct and indirect band gaps.

Fig. 7. Calculated orbital pictures of HOMO and LUMO energies with FMO contributions.

Fig. 8. Partial DOS spectra of the title compound using the B3LYP/6-311G(d,p) level.
 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20 17

Table 7 Dual [67] and multiphilic [68] descriptors are other parameters
Molecular orbital contributions with DOS for the title compound. used to distinguish between electrophilic and nucleophilic attack
MO Energy (eV) Ethylbenzene (%) Imine (%) Ethylthiazolidinone (%) sites. These parameters can be calculated using the following
H-4
7.8228 7.32 8.22 84.45
equations:
H-3
7.5317 3.66 17.00 79.34  
H-2
6.9439 46.7 15.05 38.25 Df ¼ f þ
þ

k
f k ; and Du ¼ u f k
f k ¼ uDf
H-1
6.8405 57.36 11.94 30.70
H
6.0351 54.98 35.66 9.36
L
0.9958 13.10 32.74 54.15 When Df and Du > 0 the reactive site has an electrophilic character,
Lþ1
0.3428 75.84 8.66 15.50 while if Df and Du < 0 the reactive site has a nucleophilic character.
Lþ2
0.1795 44.66 13.13 42.21 The results related to the Fukui functions, local electrophilicity
Lþ3
0.0653 27.97 13.83 58.19
Lþ4 0.5850 15.78 35.86 48.36
indices, dual and multiphilic descriptors for atomic sites of the title
molecule are reported in Table 8.
From the calculated values at B3LYP/6-311G(d,p) level summa-
rized in Table 8 and according to the condition for multiphilic
thiazolidinone moiety with a contribution of 54% as discussed
descriptor, it is concluded that the nucleophilic sites are the N1, C6,
above. As can be clearly seen in Table 7, the molecular orbital
C1, C3, C2, N2, C4, S1, C12, C5 and C10 atoms, while the electrophilic
contributions indicate that the five-membered ring is the major
sites are the C9, C7, O1, C11, C13 and C8 atoms.
active part of the molecule.

3.8. Global reactivity descriptors and fukui indices 3.9. Atomic Net charges

The global chemical reactivity descriptors (GCRD) are system- Mulliken charges of atoms have been considered for a long time
atically used to determine the global reactivity tendency of a the most popular population analysis able to give information
chemical specie. These parameters describe the electronic behavior about charge repartition along the chemical bonding [69].
of a molecular system. By using HOMO and LUMO energy values, Furthermore, it is well known that charge repartition over the
the GCRD parameters can be evaluated according to the following molecule can affect vibrational spectra [70]. The atomic charges for
equations [61,62]: the title compound by Mulliken population and natural bond
orbital (NBO) analysis, using the B3LYP/6e311G(d,p) level in gas
ðI
AÞ ðI þ AÞ 1 ðI þ AÞ m2
h¼ ; m¼
; S¼ ; c¼ ; u¼ phase, are summarized in Table 9. As shown in Table 3, all hydrogen
2 2 2h 2 2h atoms in the molecule have positive charges. Otherwise, all the
other atoms in the molecule have negative charges except C1, C7, C9
where h is the chemical hardness, m is the chemical potential, S is and S1 atoms, which possess positive charges because attached to
the chemical softness, c is the electronegativity and u is the elec-
trophilicity index. The ionization potential (I) and the electron af-
finity (A) can be obtained from I ¼
EHOMO and A ¼
ELUMO . The Table 8
calculated values of the GCRD parameters are h ¼ 5.04 eV, Fukui indices by the DFT/B3LYP method with 6-311G(d,p) basis set.
m ¼
3.52 eV, c ¼ 0.2 eV, u ¼ 1.22 eV and S ¼ 3.52 eV. The structure Atoms f

k fþ f 0k Dfk w

k wþ Dw k
k k
stability of the title compound is confirmed by the negative value of
C1 0.1388 0.0299 0.0844
0.1089 0.1703 0.0367
0.1336
the chemical potential (m ¼
3.52 eV). The chemical hardness value
C2 0.0733 0.0170 0.0452
0.0563 0.0899 0.0209
0.0690
(h ¼ 5.04 eV) indicates that the charge transfer within the molecule C3 0.1194 0.0399 0.0796
0.0795 0.1465 0.0490
0.0975
is favorable. C4 0.0406 0.0240 0.0323
0.0166 0.0498 0.0294
0.0204
Furthermore, the chemical reactivity and selectivity of favorable C5 0.0105 0.0028 0.0067
0.0077 0.0129 0.0035
0.0094
molecular sites for electrophilic or nucleophilic attack are deter- C6 0.1665 0.0356 0.1010
0.1310 0.2043 0.0436
0.1607
C7 0.0319 0.2160 0.1240 0.1840 0.0392 0.2650 0.2258
mined by local descriptors of reactivity, the so-called Fukui indices. C8 0.0058 0.0078 0.0068 0.0020 0.0071 0.0096 0.0025
These parameters are of interest in studying molecular regiose- C9 0.0038 0.1978 0.1008 0.1940 0.0047 0.2428 0.2381
lectivities [63,64]. For molecular organic compounds, Fukui indices C10 0.0081 0.0036 0.0059
0.0046 0.0100 0.0044
0.0056
are calculated by using the following relations [65]: C11 0.0129 0.0178 0.0154 0.0049 0.0159 0.0218 0.0059
C12 0.0087 0.0003 0.0045
0.0084 0.0107 0.0004
0.0103

fþ
C13 0.0005 0.0028 0.0016 0.0024 0.0006 0.0035 0.0029
k ¼ qk ðN þ 1Þ
qk ðNÞ for nucleophilic attack N1 0.2578 0.1167 0.1872
0.1410 0.3163 0.1432
0.1731
N2 0.0392 0.0010 0.0201
0.0383 0.0482 0.0012
0.0470
f

k ¼ qk ðNÞ
qk ðN
1Þ for electrophilic attack
O1 0.0067 0.1148 0.0608 0.1080 0.0083 0.1408 0.1325
S1 0.0547 0.0406 0.0477
0.0141 0.0672 0.0498
0.0174
H2 0.0005 0.0006 0.0005 0.0001 0.0006 0.0007 0.0001
f 0k ¼ ðqk ðN þ 1Þ
qk ðN
1ÞÞ=2 for radical attack H4 0 0.0016 0.0008 0.0016 0 0.0020 0.0020
H5 0 0.0002 0.0001 0.0002 0 0.0003 0.0003
qk is the atomic charge of the kth atom site in the neutral ðNÞ, H6 0.0001 0.0001 0.0001
0.0001 0.0001 0.0001 0
H8B 0.0022 0.0662 0.0342 0.0640 0.0027 0.0813 0.0786
anionic ðN þ 1Þ, cationic ðN
1Þ chemical species, respectively.
H8A 0.0061 0.0499 0.0280 0.0438 0.0075 0.0613 0.0538
In addition, Fukui indices (f þ

k and f k ) are employed together H10 0.0008 0.0024 0.0016 0.0016 0.0010 0.0029 0.0019
with global electrophilicity indices (u) to determine the local H10A 0.0062 0.0040 0.0051
0.0022 0.0076 0.0049
0.0027
indices of electrophilicity uþ
k
and u

k
according to the following H11 0.0007 0.0014 0.0011 0.0007 0.0009 0.0017 0.0008
relations [66]: H11A 0.0015 0.0018 0.0016 0.0003 0.0018 0.0022 0.0004
H11B 0.0001 0.0009 0.0005 0.0008 0.0001 0.0011 0.0010
H12 0.0001 0.0009 0.0005 0.0008 0.0002 0.0012 0.0010
uþ
k
¼ u fþ
k for nucleophilic attack H12A 0.0022 0.0002 0.0012
0.0020 0.0027 0.0002
0.0025
H13 0 0.0011 0.0006 0.0011 0 0.0014 0.0014

H13A 0 0.0001 0.0001 0.0001 0 0.0001 0.0001
u

k ¼ u f k for electrophilic attack H13B 0 0.0002 0.0001 0.0002 0 0.0002 0.0002
18 N.E.H. Belkafouf et al. / Journal of Molecular Structure 1189 (2019) 8e20

Table 9 while the preferred sites for an electrophilic attack correspond to

Atomic charges distribution of the title compound calculated by Mulliken and the hydrogen atoms.
natural bond orbital (NBO) methods using the B3LYP/6e311G(d,p) level in gas phase.

Atoms MPA NPA Atoms MPA NPA 4. Conclusion

C1 0.029 0.142 H2 0.097 0.207
C2
0.076
0.239 H4 0.093 0.202 A novel thiazolidinone derivative (C13H16N2OS) was synthesized
C3
0.064
0.034 H5 0.083 0.199
and its experimental solid state structure was determined on the
C4
0.087
0.194 H6 0.090 0.201
C5
0.076
0.192 H8 0.185 0.235 basis of PXRD data at room temperature. This compound belongs to
C6
0.086
0.213 H8A 0.183 0.235 the tetragonal system with the I
4 space group. The geometry was
C7 0.231 0.372 H10 0.107 0.194 validated by FT-IR and (1H, 13C) NMR spectroscopy. The molecular
C8
0.403
0.582 H10A 0.113 0.200 structure was determined using the DFT/B3LYP method with 6-
C9 0.389 0.713 H11 0.127 0.204
311G(d,p) basis set. Experimental and theoretical geometrical pa-
C10
0.186
0.388 H11A 0.102 0.192
C11
0.278
0.554 H11B 0.102 0.189 rameters were consistent. In the molecular packing CeH,,,O and
C12
0.130
0.173 H12 0.157 0.214 CeH,,,N hydrogen bonds were observed. The investigation of the
C13
0.279
0.576 H12A 0.146 0.219 intermolecular interactions reveals that H,,,H interactions are the
N1
0.359
0.531 H13 0.118 0.200
most important intercontacts. This investigation was performed
N2
0.394
0.510 H13A 0.117 0.206
O1
0.333
0.583 H13B 0.125 0.199
using HS analysis and 2D-fingerprint plot. The PED was calculated
S1 0.157 0.247 in order to assign the vibrational modes. A good agreement was
noted between the experimental and theoretical vibrational
wavenumbers. Using the GIAO method and B3LYP functional with
the electronegative N atom. The NBO analysis shows that the C9 6-311G(d, p) basis set, 1H and 13C isotropic chemical shifts were
atom of the carbonyl group has a large positive atomic charge, computed. In general, the theoretical and experimental (1H, 13C)
which can be explained by the strong electronegative character of NMR data show good correlations. The UVevis spectra displayed
the O1 atom. In summary, all atomic charge values are similar in two large bands corresponding to p
p* and n
p* transitions.
sign compared to the results obtained by Mulliken population Furthermore, the electronic and optoelectronic behaviors of the
analysis. title compound were predicted by FMO, DOS and Tauc studies. The
HOMO-LUMO transition clearly explicates charge transfer interac-
tion involving donor and acceptor groups in the title compound.
3.10. Molecular electrostatic potential (MEP) The DOS spectra clearly explicate the molecular orbital composi-
tions and their contributions to the chemical bonding. The molec-
MEP is associated to the electronic density and is a useful graph ular orbital contributions indicate that the five-membered ring is
to identify the nucleophilic and electrophilic reaction sites for the major active part of the molecule. The HOMO and LUMO energy
hydrogen bonding interactions in a molecule [71,72]. Both experi- gaps were calculated as 5.04 eV. Whereas, using the Tauc method,
mental X-ray diffraction and theoretical methods are used to obtain the direct and indirect optical band gaps were evaluated as (4.07
MEP values [73e75]. In addition, the chemical reactivity of the and 4.86 eV) for direct transitions and (3.7 and 4.26 eV) for indirect
molecules can be predicted by using the MEP details [76]. In the transitions. Therefore, the charge transfer within the molecule is
MEP drawing, the regions of negative potential are expected to be dominated by indirect transitions. The GCRD parameters were
sites of protonation or nucleophilic attack, whereas the regions of computed and the results confirmed that the charge transfer, taking
positive potential are submitted to electrophilic attack. In this work, place within the molecule, is favorable. The molecular reactive sites
the MEP map clearly shows different values of electrostatic po- were determined using dual and multiphilic descriptors according
tential in the title molecule (Fig. 9). As indicating by Fig. 6, negative to the Fukui functions. The MEP surface and the atomic charge
regions are associated with O, N and S atoms and the maximum values indicate clearly the reactive sites for electrophilic and
positive regions are localized on the hydrogen atoms of the mole- nucleophilic attacks in the molecule.
cule. Consequently, it can be suggested that the most preferred
regions for nucleophilic attack are around electronegative atoms, Appendix A. Supplementary data

Supplementary data to this article can be found online at

https://doi.org/10.1016/j.molstruc.2019.04.028.

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