Accepted Manuscript

2-thioxo- 3N-(2-methoxyphenyl) −5 [4′-methyl -3′N -(2′-methoxyphenyl)

thiazol-2′(3′H)-ylidene] thiazolidin-4-one: Synthesis, characterization, X-ray single
crystal structure investigation and quantum chemical calculations

Salem Yahiaoui, Anna Moliterni, Nicola Corriero, Corrado Cuocci, Khaled Toubal,
Abdelkader Chouaih, Ayada Djafri, Fodil Hamzaoui
PII: S0022-2860(18)31134-7
DOI: 10.1016/j.molstruc.2018.09.052
Reference: MOLSTR 25686

To appear in: Journal of Molecular Structure

Received Date: 18 May 2018

Revised Date: 19 August 2018
Accepted Date: 18 September 2018

Please cite this article as: S. Yahiaoui, A. Moliterni, N. Corriero, C. Cuocci, K. Toubal, A. Chouaih,
A. Djafri, F. Hamzaoui, 2-thioxo- 3N-(2-methoxyphenyl) −5 [4′-methyl -3′N -(2′-methoxyphenyl)
thiazol-2′(3′H)-ylidene] thiazolidin-4-one: Synthesis, characterization, X-ray single crystal structure
investigation and quantum chemical calculations, Journal of Molecular Structure (2018), doi: https://
doi.org/10.1016/j.molstruc.2018.09.052.

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 ACCEPTED MANUSCRIPT

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 ACCEPTED MANUSCRIPT
2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-methyl -3’N -(2’-methoxyphenyl)
thiazol-2’(3’H)-ylidene] thiazolidin-4-one: Synthesis, characterization, X-
ray single crystal structure investigation and quantum chemical
calculations

Salem Yahiaouia,b, Anna Moliternic, Nicola Corrieroc, Corrado Cuoccic, Khaled Toubald,e,

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Abdelkader Chouaiha, Ayada Djafrid, Fodil Hamzaouif

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a
Laboratory of Technology and Solid Properties (LTPS), Faculty of Sciences and Technology, Abdelhamid Ibn
Badis University, BP 227 Mostaganem 27000, Algeria.

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b
Ecole Normale Supérieure de Mostaganem, 27000 Mostaganem, Algeria.
c
CNR-IC Institute of Crystallography, Via Amendola 122/O, 70126 Bari, Italy.
d
Laboratory of Applied Organic Synthesis (LSOA), Department of Chemistry, Faculty of Sciences, University of

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Oran 1 Ahmed Ben Bella, 31000, Oran, Algeria.
e
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Département de Génie des Procédés, Faculté des Sciences et Technologie, Université Mustapha Stambouli de
Mascara, Algeria.
f
LPFM Académie de Montpellier, France
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Abstract: We report here the synthesis and a combined experimental and theoretical study on
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molecular structure of 2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-methyl -3’N -(2’-

methoxyphenyl) thiazol-2’(3’H)-ylidene] thiazolidin-4-one. The crystal structure has been
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determined by X-ray diffraction. Crystallographic data revealed that the compound

crystallizes in a monoclinic system with a space group of P21/c, with crystal cell parameters: a
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= 10.618 (3), b = 13.180 (5), c = 15.101 (3) Å, β = 97.766 (16), V = 2093.9(11) A3 and Z = 4.
The final R-value was 0.0405 based on 4801 observed reflections. From the dihedral angle
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values, the structure was found to be significantly non planar. Density functional theory
(DFT) calculation were carried out to obtain the ground state optimized geometry of the
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molecule using B3LYP and HSEH1PBE methods with 6-311G(d,p) basis set. The optimized
geometry of the title compound was found to be consistent with the structure determined by
X-ray diffraction. The stability of the title compound is due to the presence of a good number
of potential donor and acceptor groups establishing intermolecular interactions like C–H⋅⋅⋅O,
C–H⋅⋅⋅S and π-π stacking linking the molecules into dimers with C(6),  (18) and  (24)
graph sets. In addition, the solid state behaviors of molecules in the crystal were studied using
3D Hirshfeld surface analysis and associated 2D fingerprint plots. Calculated frontier
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molecular orbitals (FMOs) energies and chemical reactivity parameters indicated that the
molecule under investigation exhibits high first hyperpolarizability, typical of a NLO
material.

Keywords: Structure, thiazole, DFT, MEP, NLO.

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Introduction
Thiazolidinones derivatives containing one or two five-membered rings are important class of

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synthetic organic materials. These heterocyclic compounds are extensively used for their
biological activities [1,2]. In addition, thiazolidinones are also known to exhibit a push-pull

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effects [3,4] and photovoltaic applications [5]. Recently, intramolecular charge transfer in
aromatic push-pull molecules has been a subject of interest in several experimental and
theoretical studies [6-10]. Moreover, the knowledge of the crystal structure of these

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compounds is crucial for understanding the related charge transfer phenomena. On the other
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hand, the interest for nonlinear optical (NLO) properties of π-conjugated and functionalized
organic compounds has greatly increased due to their potential applications in optoelectronics
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[11]. Indeed, incorporation of heteroatoms (N, O, S etc.) into the chromophore brings higher
thermal stability, chemical robustness and may also act as source of auxiliary donors or
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acceptors. From this perspective and among organic materials, thiazolidinones derivatives are
very promising molecules for the study of second order NLO properties [12,13].
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As described previously, the conjugated molecules consist of a skeleton containing

conjugated π-electrons; the conjugated bridge is linked to two end groups with electron donor
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(D) and electron acceptor (A) character, respectively. The electron acceptor group withdraws
electronic charge from the donor through the conjugated bridge: as a consequence the π-
electrons of the skeleton become polarized, giving rise to a relevant molecular dipole moment
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which defines a charge transfer axis roughly coincident with the chain axis of the conjugated
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system.
For this purpose, we have chosen 2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-methyl -3’N -(2’-
methoxyphenyl) thiazol-2’(3’H)-ylidene] thiazolidin-4-one, which appears a good candidate
for NLO applications. Besides investigating charge transfer within this molecule, we have
examined other molecular properties such as HOMO-LUMO orbitals, global reactivity
descriptors and molecular electrostatic potential of the title compound. The intercontacts in
crystal structure are analyzed using Hirshfeld surfaces method and the NLO activity of the
molecule is computed.
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Experimental procedure
Synthesis
The 3-N-2-methoxyphenyl thiazol-2 (3H)-thione (c) and the 2-thioxo-thiazolidin-4-one (e)
were synthesized from appropriate aromatic amines and CS2 under basic conditions followed
by ring closure with chloroacetic acid. S-methyl -3-N-2-methoxyphenylthiazolium (3H) salt

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(d) is prepared in high yield greater than 98% by alkylation from corresponding 3N-2-
methoxyphenylthiazol-2 (3H)–thione and methyl iodide by solvolyse. At a solution of

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equimolar amounts of 3-N (2-methoxyphenyl-2-thioxothiazolidinone (e) (0.1 Mole) and S-
methyl -3-N-2-methoxyphenylthiazolium(3H) salt (d) (0.1 mol) in 40 mL of aceconitril, was

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added triethylamine (0.15 mol). The solution was refluxed for 1 hour. The reactions were
monitored by thin-layer chromatography. The reaction mixture was cooled and poured on
crushed ice. The solid obtained was filtered and washed with acetone. Scheme 1 shows the

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chemical pathways of the title compound formation.
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Reagents and conditions: (I) CS2, NH4OH; (II) chloroacetone , EtOH ; (III) MeI, 24h ; (IV)
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Chloroacetic acide; (V) CH3CN, Et3N 62°C

Scheme 1. Preparation and chemical structure of 2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-

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methyl -3’N -(2’-methoxyphenyl) thiazol-2’(3’H)-ylidene] thiazolidin-4-one.

Physical measurements
All reagents and solvents for synthesis and spectroscopic studies were commercially available
and used as received without further purification. The IR spectrum was recorded on a JASCO
4200 FT-IR spectrometer as a KBr pellet. The 1H and 13
C NMR spectra were measured in
CDCl3 with a Bruker AC-DPX-200 (300 MHz) spectrometer at 25°C.
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Spectroscopic data of 4-methyl, 3-N-(2-methoxyphenyl),thiazol-2(3H)-2-thione (c ):
White solid; yield 38% ; mp =112°C ;Rf =0.64 (CH2Cl2/MeOH : 9 /1); IR (KBr, γmax cm−1) :
2981(C-H aromatic); 1590 ( C=N); 1391cm-1(C=S);1343 (C-N); 833-959 (subtarom ); UV
(λnm): 220; 239; 320 (C=S). 1H-NMR (CDCl3, 300MHz) δ(PPM) J(HZ): 7.40-7.10 (m, 4Haryl);
6.34 (q, 1H, H5thia, J=1); 3.80(s, 3H, O- CH3); 1.92 (d, 3H, C4thia -CH3; J=1 ). 13C-RMN(300
MHZ, CDCl3) δppm: 190,00 (C=S); 154.90 (Caryl-O); 141.71 (C4thia -CH3); 131.80(Caryl-N);

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129.86(Cthia-H5); [127.18;121.34;112.9; 105.73] (4Caryl); 56.07(O-CH3); 15.34(C4-CH3).
Spectroscopic data of iodide of 4-methyl, 3-N (2-methoxyphenyl),-2-methyl-sulfanyl, thiazol-

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2(3H)-ium (d):
Grey powder ;Yield=87 %; mp =148°C; IR (KBr, γmax cm−1) : 3500; 2963 (C-H
aromatic);1596 ( C=C);1391cm-1(C=S);1343 (C-N); 820-966(subtarom );U V (λnm): 220; 239.

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H-NMR, (CDCl3, 300MHz) δ (PPM) J (HZ): 7.83-7.25 (m, 4Haryl); 6.34 (q, 1H, H5thia, J=1);
3.89(s, 3H, O- CH3); 2.94(s, 3H, S-CH3); 2.21(d, 3H, C4thia -CH3; J=1Hz).

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Spectroscopic data of 2-thioxo-3-n-(2-methoxyphenyl) thiazolidin-4-one (e).
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White Solid, Yield: 38%, mp: 142°C, IR (KBr, cm−1): 1753 (C=O), 1257 (C=S). 1H-NMR,
(CDCl3, 250MHz) δ(ppm) J(HZ): 3.80(s, 3H), 4.180,4.164(AB, 2H, JAB = 18.136), 7.45-7.01
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(m, 4H). C-NMR, (CDCl3, 75MHz) δ(ppm): 36.27 (CH2), 55.84 (OCH3), 112.36, 121.22,
123.39, 131.47, 129.87, 154.17 (aryl), 172.99(C=S), 200.99(C=O).
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Spectroscopic data of 2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-methyl -3’N -(2’-

methoxyphenyl) thiazol-2’(3’H)-ylidene] thiazolidin-4-one (f ):
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Yellow powder; Yield = 62%; Rf = 0.74 (CH2Cl2/Methyl-OH: 8 /2); mp>260°C. 1H-NMR,

(CDCl3, 300MHz) δ(ppm): 7,42-7,05. (m, 8Haryl); 6.35 (s, 1H.); 3.86 (s, 3H, O-CH3); 3.77(s,
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3H, O-CH3thione); 1.90 (d, 3H, CH3thia, J=1.06); 1.91 (d,3H,CH3thia, J=1.06). 13C-NMR (CDCl3,
30MHz) δ(ppm): 189.51 (C=S); 156.48 (C=O); 155.82 (C=C); 103.62 (C=C); (133.46;
133.40) (Cthia-H5); 125(C4thia-CH3) ; 137.78; 130.78; 128.14; 125.02; 123.36; 121.61; 120.95;
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112.82; 112.4; 103.62 (77.04;76.62); (O-CH3); (56.15; 55.94) (Cthia -CH3); (14.73; 13.85
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(CH3)).

Structure determination and refinement

A yellow prismatic crystal of appropriate size was chosen for the crystallographic study. X-
ray diffraction experiment was carried out at room temperature by a Bruker-Nonius
KappaCCD single crystal diffractometer, equipped with a charge-coupled device (CCD
detector), using monochromatized MoKα radiation. The automatic data collection was
preformed by COLLECT [14], cell determination and refinement by DIRAX [15,16] and data
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reduction by EVAL [14,17]. Absorption effects were corrected by SADABS [18] via a semi-
empirical approach. The structure was solved by SIR2014 [19] and refined by a full-matrix
least-squares technique on F2 using SHELXL-2014 [20] with anisotropic thermal parameters
for the non-H atoms. The H atoms bonded to C atoms were positioned geometrically with C-
H = 0.96 and 0.93 for methyl and aromatic H atoms, respectively, and constrained to ride on
their parent atoms. The constraint Uiso(H) = kUiso(C), where k = 1.5 for methyl and 1.2 for

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aromatic H atoms. The final least-squares cycle gave R = 0.0405 for the observed reflections
with (∆ρ) min = -0.279 e/Å3 and (∆ρ) max = 0.212 e/Å3. The software used to prepare material

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for publication: WinGX [21] and publCIF [22]. The molecular structure graphics of the title
compound were done using Diamond [23] and Mercury [24]. Atomic scattering factors for

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heavy atoms were taken from International Tables for X-ray Crystallography [25] while the
factors for H were those supplied by Stewart et al. [26]. Details of the data collection
conditions and the parameters of the refinement process are given in Table 1.

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Table 1 Crystal data and structure refinement details
Empirical formula C21H18O3N2S3
CCDC reference no. 1841892
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Formula weight 442.56

Crystal size (mm) 0.225 × 0.225 × 0.075
Temperature (K) 293(2)
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Crystal system, space group Monoclinic, P21/c

Unit cell dimensions
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a (Å), b (Å), c (Å) 10.618 (3), 13.180 (5), 15.101 (3)

β (°) 97.766 (16)
Wavelength (Å) 0.71073
Volume (Å3) 2093.9(11)
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Z, calculated density (g.cm-3) 4, 1.404

F(000) 920
θ range for data collection 2.06 ‒ 27.50
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Limiting indices −13≤ h ≤ 13 ,−17 ≤ k ≤ 17 , −19 ≤ l ≤ 19

Reflections collected/unique 49016/4801
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Rint 0.0745
Refinement method full-matrix least-squares on F2
Data parameters 265
Goodness of fit, S 1.055
Final R indices[F2 > 2 σ( F2)]
R, wR 0.0405, 0.0836
R indices (all data)
R, wR 0.0671, 0.0945

Quantum chemical calculations

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Density functional theory (DFT) calculations were performed using a hybrid functional
B3LYP (Becke’s three-parameter hybrid model using the Lee-Yang Parr correlation
functional) [27,28] and HSEH1PBE (recommended version of the full Heyd-Scuseria-
Ernzerhof functional) [29,30] at basis set 6-311G(d,p) using Gaussian 09 software [31],
optimized geometries were visualized through GaussView 5.0 program [32].
The atomic coordinates of the title compound were taken from the final X-ray refinement

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cycle, were used as initial coordinates for the theoretical calculations. HOMO and LUMO
energy eigenvalues were exploited to calculate global chemical reactivity parameters, that is,

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chemical potential (ε), electronegativity (χ), electrophilicity index (ω), chemical hardness (η)
and softness (s) [33,34]. The molecular electrostatic potential (MEP) map and the dipole

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moment of the molecule under investigation were studied in order to elucidate the intra and
intermolecular bonding and interaction among bonds. All electronic properties were examined
using results calculated at the HSEH1PBE/6-311G(d,p) level. Hirshfeld surfaces maps and the

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associated 2D fingerprint plots were prepared using CrystalExplorer 3.1 program [35].
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Results and discussion
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Crystal Structure of 2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-methyl -3’N -(2’-methoxyphenyl)

thiazol-2’(3’H)-ylidene] thiazolidin-4-one
A general view of the molecule with atomic labeling is shown in Figure 1. Figure S1 shows a
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perspective view of the crystal packing in the unit cell. Selected bond lengths, bond angles
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and torsion angles for all non-hydrogen atoms obtained by X-ray diffraction are listed in
Tables S1, S2 and S3, together with the calculated parameters, respectively. The full molecule
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has an E configuration about the C11=C12 double bond (Figure 1). The average values of
bond distances and angles in the two benzene rings for both experimental and calculated
results are in good agreement with literature values. From Table 2, the five C–S distances,
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S1–C10, S1–C11, S2–C12, S2–C14 and S3 = C14 in the thiazole ring have values
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intermediate between those reported for C(Sp3)–S single and double bonds [25]. The mean
values of bond angles in thiazole rings are about 108°. Thiazole ring dimensions of the title
molecule are very well comparable with previous studies [36,37]. All bond angles C–C–C, C–
N–C and C–C–N are close to 120°, indicating that the  electrons in the title molecule are
delocalized. On the other hand, the two thiazole rings are coplanar, while, the two phenyl
groups make dihedral angles (C9 – N1 – C1 – C2), (C11 – N1 – C1 – C6), (C13– N2 – C15 –
C20), and (C14 – N2 – C15 – C16) with the plane of the thiazole rings as reported in Table
S3. The obtained dihedral angles reveal that the title compound is not planar.
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Fig. 1. General view of molecule with atomic numbering scheme (thermal ellipsoids drawn at
50% probability). H atoms are omitted for clarity.

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Table 2 Bond distances (Å) for non-hydrogen atoms by X-ray diffraction and theoretical
calculations (e.s.d.’s are given in parenthesis)
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Bond distances X-ray 6-311G(d,p)

HSEH1PBE B3LYP
C11 – C12 1.388(3) 1.387 1.377
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S1 – C10 1.733(2) 1.736 1.758

S1 – C11 1.739(2) 1.739 1.767
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S2 – C14 1.738(2) 1.739 1.765

S2 – C12 1.763(2) 1.762 1.779
S3 – C14 1.648(2) 1.649 1.654
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The optimized bond lengths and bond angles calculated at both HSEH1PBE and B3LYP
levels of theory, using 6-311G (d,p) basis set are listed in Tables S2, S3 and S4 as
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supplementary material. These parameters are in good agreement with the corresponding ones
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determined on the basis of X-ray diffraction.

Hydrogen bonding
The studies of systems including the H–bond have attracted growing interest during the last
decades [38-42]. The formation of intermolecular hydrogen bond has very pronounced effects
on the molecular structure and properties. The crystal structure exhibits C–H⋅⋅⋅O and C–H⋅⋅⋅S
intermolecular interactions in which C atoms (C6, C7, C8 and C17) act as donors and O (O2,
O3 and S3) atoms act as acceptors. In the crystalline state, these intermolecular interactions
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stabilize the crystal structure. The intermolecular hydrogen bonded interactions, responsible
for molecular stability, as obtained from X-ray data are tabulated in Table 3. Figure S4 shows
these hydrogen bonds in the crystal.
Molecules in the crystal are further connected into three-dimensional network by π-π stacking
interactions between the benzene and thiazole rings, with centroid-to-centroid distances of
4.1695(19) Å for Cg1⋅⋅⋅Cg1, 4.3011(19) Å for Cg1⋅⋅⋅Cg2, 5.966(3) Å for Cg3⋅⋅⋅Cg3 and

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5.818(3) Å for Cg4⋅⋅⋅Cg4, where Cg1 and Cg2 are the centroids of the thiazole rings
S1/N1/C9–C11 and S2/N2/C12–C14, respectively, Cg3 and Cg4 are the centroids of the

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benzene rings C1–C6 and C15–C20, respectively. Distances between ring centroids smaller
than 6 Å were selected for analysis. These results are in good agreement with those reported

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in litterature indicating that, for benzene-benzene systems, the most important region is for
Cg⋅⋅⋅Cg within the range of 5.5 Å - 6.0 Å [43].
Hydrogen-bond pattern can be described using graph set analysis. In the title crystal packing

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(Figure S4), pairs of intermolecular C–H⋅⋅⋅O and C–H⋅⋅⋅S hydrogen bonds, namely C6–
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H6⋅⋅⋅O1, C19–H19⋅⋅⋅O3 and C17–H17⋅⋅⋅S3, link the molecules into dimers forming hydrogen
bonded chains C(6),  (18) and  (24) ring motifs [44].
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Table 3 Geometry of the C–H⋅⋅⋅O hydrogen bonds by X-ray diffraction (Å, °)

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D–H…A D–H H…A D…A D–H…A

i
C8–H8C···O3 0.96 2.64 3.318(3) 127.6
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C7–H7B···O2i 0.96 2.58 3.059(3) 111.2

ii
C6–H6···O2 0.93 2.68 3.568(3) 138.4
C17–H17C···S3 0.96 2.91 3.821(3) 167.0
Symmetry codes: (i) -x+2,-y,-z; (ii) -x+2,y-1/2,-z+1/2
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Hirshfeld surface analysis

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Hirshfeld surface (HS) analysis [45] provides an indispensable means of studying the solid
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state behavior of molecules, and gives detail information on the different types of
intermolecular interactions. Molecular HS in the crystal structure have been constructed based
on the electron density distribution calculated as the sum of spherical atom electron densities
[46]. For each point on the Hirshfeld isosurface the 2D fingerprint plot represents two
distances  , the distance from the point to the nearest nucleus external to the surface, and  ,
the distance to the nearest nucleus internal to the surface [47].
The normalized contact distance dnorm based on both de, di and van der Waals radii of the atom
( and  ), is given by the equation:
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Before starting the calculations, the bond lengths to hydrogen atoms were set to standardized
neutron values (O–H: 0.983 and C–H: 1.083Å). The three-dimensional HS generated from the
structure of the title compound is presented in Figure 2(a). The value of dnorm can be negative
or positive. dnorm is mapped over the range –0.1124 to +1.2728. The proportion of these

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surfaces show the susceptible areas to strong and weak contacts. A red-blue-white color idea
is used to draw the dnorm surface. For example, the large circulars red region on the surface are

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pinpointing of hydrogen bonding contacts. Weaker C–H⋅⋅⋅O and C–H⋅⋅⋅S type interactions
can be seen on corresponding dnorm plots as pale-red areas. The other color spots are observed

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due to the presence of other close contacts, such as H⋅⋅⋅H, S⋅⋅⋅H, O⋅⋅⋅H and C⋅⋅⋅H. In addition,
the red and blue triangles in shape index and electron density curves in curvedness surface
reveal the    stacking in the title molecule.

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From the two-dimensional fingerprint plot depicted in Figure 2(b), the majority of contact is
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due to H⋅⋅⋅H contact interaction making up to 38.8% of the HS of the title molecule. The
remaining area of the fingerprint plot is occupied by C⋅⋅⋅H ǀ H⋅⋅⋅C (11.3% ǀ 9%), S⋅⋅⋅H ǀ H⋅⋅⋅S
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(13.1% ǀ 8.2%) and O⋅⋅⋅H ǀ H⋅⋅⋅O (7.5% ǀ 6.6%) contact regions.

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(a) (b)
Fig. 2. HS map (a) and full 2D fingerprint plot (b) for the title compound with dnorm selected
intermolecular contacts.
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Electronic molecular properties
Frontier molecular orbitals
The frontier molecular orbitals (FMOs) and their properties such as energy are used to explain
the global chemical behavior and stability of the molecular system. HOMO (highest occupied
molecular orbital) represents the ability to donate an electron and LUMO (lowest unoccupied
molecular orbital) as an electron acceptor represents the ability to obtain an electron. The

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HOMO-LUMO energies of the title compound and their distributions were calculated using
HSEH1PBE/6-311G(d,p) level. In the gas phase calculations, the HOMO and LUMO

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energies for the title compound have been calculated as –4.83 and –1.54 eV, respectively.
As a result, the energy gap is largely responsible for the chemical and spectroscopic

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properties of the molecules [48]. The magnitude of the energy separation between the HOMO
and LUMO is 3.29 eV. This relatively high value indicates that the title structure is quite
stable. Theoretically, calculated frontier molecular orbitals in the ground state are illustrated

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in Figure S5 including HOMO‒LUMO and HOMO-1–LUMO+1 energy differences.
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In this compound, the HOMO and HOMO-1 are delocalized over the Sulphur, Oxygen and
Nitrogen atoms of the two thiazole rings. By contrast, the LUMO and LUMO+1 are located
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over the whole C–C bonds of the two thiazole rings and the terminal phenyl ring. Both
HOMO, HOMO–1, LUMO and LUMO+ 1 are mainly localized on the rings, indicating that
these orbitals are mostly the π –antibonding type orbitals.
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Global reactivity descriptors

Conceptual DFT based descriptors have helped in many ways to understand the structure of
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molecules and their reactivity. The HOMO - LUMO energies can play a crucial role in
finding several new chemical reactivity descriptors, such as the first ionization of molecular
system I and the affinity A, thus I and A can be expressed as I = –EHOMO = 4.83 eV and A = –
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ELUMO = 1.54 eV, Koopmans theorem [49].

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When I and A are known, we can calculate the global reactivity descriptors, chemical
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potential (ε = – ), electronegativity (χ = ), electrophilicity index (ω =  ), chemical
 
 
hardness (η= 
) and softness (s = ) [50-53].
Using the above equations the global reactivity parameters were calculated in HSEH1PBE/ 6-
311G(d,p) level and the results of ε, χ, ω, η and s were –3.185, 3.185, –3.083, –1.645, –0.607
eV, respectively. According to these quantum chemical parameters, the title compound is a
chemically hard system and can be described as a less reactive compound.
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Molecular electrostatic potential
In the present study, the Molecular electrostatic potential (MEP) map is illustrated in Figure
S6 (see supplementary material), where blue colour represents electron deficient
(electrophile), the red colour for electron rich (nucleophile), yellow indicates moderate
attraction (relatively negative potential) and green indicates neutral electrostatic potential
region. In addition, Figure S6 highlights the charge distributions three dimensionally

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constructed by using HSEH1PBE/6-311G(d,p) level and based on the electron density at
different points of the molecule under investigation. The MEP surface of the title compound

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demonstrated that carbonyl group and sulphur atom linked with thiazolidine group have
relatively negative potential (red and yellow) and are potential sites for electrophilic attack,

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whereas the positive blue regions are concentrated over the hydrogen atom of methyl and
terminal phenyl rings, indicating a possible sites for nucleophilic attack. These sites give
information about the region from where the compound can have intermolecular interactions.

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NLO analysis
Since the nonlinear optical (NLO) materials play a significant role in nonlinear optics such as
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optical communication, optical computing, optical switching and dynamic image processing,
organic molecules, which contain conjugated π electrons, have received great attention due to
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their potential applications in this field of technology [54-56]. In order to understand the
relationship between the molecular structure and NLO properties, it is quite useful to
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determine the total dipole moment (µ), the mean polarizability (α) and the total first
hyperpolarizability (β) [57,58]. The efficiency of the polarizability and the first
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hyperpolarizability properties of molecular systems has determined by electronic

communication between acceptor and donor groups which have a vital role in establishing the
intramolecular charge transfer [59]. To be more NLO active, a molecule should have high
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dipole moment, polarizability and hyperpolarizability values. The dipole moment (µ), mean
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polarizability (α) and first hyperpolarizability (β) for the title molecule are calculated with
HSEH1PBE, B3LYP and CAM-B3LYP functionals using 6-311G(d,p) basis set and the
results are depicted in Table 4. These parameters are computed by using expressions detailed
earlier [60]. Furthermore, LC-B3LYP and CAM-B3LYP functionals are greatly superior to
the conventional methods and are efficient to compute the NLO properties [61,62]. The
highest value for α (4.87× 10-23 esu) is obtained with B3LYP/6-311G(d,p) while, the highest
value for β (5.73 × 10-30 esu) is computed with CAM-B3LYP/6-311G(d,p). According to the
results given in Table 4, the calculated values of β are significantly greater than that of urea
 ACCEPTED MANUSCRIPT
[63] which is one of the prototypical molecules used in the study of the NLO properties of
molecular systems. Furthermore, dipole moment in a molecule is an important property
because it is used as an indicator of the charge movement across the molecule. The calculated
values of dipole moment (µ) were found to be 2.731, 2.697 and 2.672 Debye obtained with
HSEH1PBE, B3LYP and CAM-B3LYP, respectively, using 6-311G(d,p) basis set. The
direction of the dipole moment depends on the positive and negative charge centers. For the

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title molecule, the direction of the computed dipole moment with HSEH1PBE/6-311G(d,p) is
shown in Figure 3.

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Table 4 Total static dipole moment (µ, in Debye), the mean polarizability (α, in 10-23 esu), the
first-order hyperpolarizability (β, in 10-30 esu).

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6-311G(d,p)
C21H18O3N2S3 HSEH1PBE B3LYP CAM-B3LYP
µxx −1.958 −2.621 −2.599
µyy −0.173

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0.519 0.506
µzz −1.897 0.364 0.355
µ (Debye)
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2.731 2.697 2.672
αxx 347.641 411.809 391.147
αxy 29.611 −25.912 −22.979
αyy 300.583 322.916 312.457
αxz 76.914 −18.918 −17.829
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αyz −12.591 −6.304 −6.239

αzz 324.914 250.291 244.063
α (u.a) 324.379 328.339 315.889
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α × 10-23 (esu) 4.81 4.87 4.68

βxxx 322.927 769.376 873.373
βxxy −55.290 −198.282 −143.149
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βxyy −203.758 −244.323 −278.026

βyyy −41.062 164.609 160.947
βxxz 244.496 −123.317 −138.301
βxyz 18.247 27.043 24.719
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βyyz −144.308 45.088 46.999

βxzz 309.291 63.240 60.528
βyzz 151.884 −77.517 −72.414
βzzz 274.243 13.169 9.097
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β (u.a) 571.716 602.233 663.259

β × 10-30 (esu) 4.94 5.20 5.73
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Fig. 3. Direction of the computed dipole moment of the title compound with HSEH1PBE/6-
311G(d,p) level.

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Conclusion
In this paper, we have reported synthesis of the 2-thioxo- 3N-(2-methoxyphenyl) -5 [4’-

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methyl -3’N -(2’-methoxyphenyl) thiazol-2’(3’H)-ylidene] thiazolidin-4-one that has been
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characterized by means IR, 1H and 13C NMR spectroscopy. Its structure was determined using
single crystal X-ray diffraction and DFT (B3LYP and HSEH1PBE levels using 6-311G(d,p)
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basis set) methods. The title compound crystallized in the monoclinic P21/c space group. X-
ray diffraction and the selected DFT model results generally agree. The crystal structure
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exhibits intermolecular interactions. Weaker C–H⋅⋅⋅O and C–H⋅⋅⋅S H-bonds type along with
π-π stacking interactions are observed using Hirshfeld surface analysis. These intermolecular
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interactions link the molecules into dimers with C(6), R (18) and R (24) graph sets. The two-
dimensional fingerprint plot shows that the majority of contact is due to H⋅⋅⋅H contact
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interaction with 38.8% of the HS of the title molecule. The other molecular properties such as
energy gap, hardness, softness, chemical potential, electronegativity and electrophilicity index
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were described. The energy gap is 3.29 eV indicating that the title structure is quite stable and
HOMO, HOMO–1, LUMO and LUMO+ 1 energy levels are mainly localized on the rings,
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indicating that these orbitals are mostly the π –antibonding type orbitals. The calculated
global reactivity parameters indicate that the title compound is a chemically hard system and
can be described as a less reactive compound. Furthermore, information regarding the size,
shape, charge sites of the molecule are identified from the MEP mapped surface. The MEP
surface of the title compound demonstrated that carbonyl group and sulphur atom linked with
thiazolidine group have relatively negative potential (red and yellow) and are potential sites
for electrophilic attack, whereas the positive blue regions are concentrated over the hydrogen
atom of methyl and terminal phenyl rings, indicating a possible sites for nucleophilic attack.
 ACCEPTED MANUSCRIPT
Finally, nonlinear optical behavior of the title compound was investigated via determination
of the electric dipole moment, the polarizability and the hyperpolarizability using
HSEH1PBE, B3LYP and CAM-B3LYP functionals with 6-311G(d,p) basis set. NLO analysis
shows that the title molecule can be a candidate to promising NLO materials.

Supplementary Materials

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CCDC 1841892 contains supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic Data Centre via

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www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by
contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2

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1EZ, UK; Fax: +44 1223 336033.

Acknowledgments

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The authors thank Dr. Francesco Baldassarre (Institute of Crystallography CNR, Bari, Italy)
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for his technical support.
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HIGHLIGHTS

Synthesis and characterization of the title compound have been reported.

X-ray single crystal and molecular structures were determined.

Hydrogen bonds were examined using Hirshfeld surface analysis.

HOMO, LUMO and MEP were investigated.

Molecular NLO properties were calculated.

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