Journal of Molecular Structure 1200 (2020) 127104

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Journal of Molecular Structure

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

Experimental and theoretical studies of the schiff base (Z)-1-

(thiophen-2-yl- methyleneamino) propane-2-ol
Asnake Lealem Berhanu a, Neha Sharma a, Irshad Mohiuddin a, Ashok Kumar Malik a,
Jatinder Singh Aulakh a, *, Jechan Lee b, Ki-Hyun Kim c, **
a
Department of Chemistry, Punjabi University, Patiala, 147002, Punjab, India
b
Department of Environmental and Safety Engineering, Ajou University, Suwon, 16499, Republic of Korea
c
Department of Civil and Environmental Engineering, Hanyang University, Seoul, 04763, Republic of Korea

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

Article history: In this study, a quantum chemical model was developed to better account for the properties of a Schiff
Received 19 June 2019 base, (Z)-1-(thiophen-2-yl-methyleneamino) propane-2-ol, which is derived from thiophene-2-carboxy
Received in revised form aldehyde and 1-amino-2-propanol. To predict its molecular structure, the assignment of the vibra-
24 August 2019
tional wavelength (for FT-IR) and chemical shift (for 1HNMR) of (Z)-1-(thiophen-2-yl-methyleneamino)
Accepted 19 September 2019
Available online 21 September 2019
propane-2-ol was performed experimentally and theoretically. All of the theoretical calculations were
performed using the Gaussian 09 program package. The theoretically and experimentally obtained re-
sults were in good agreement (R2
0.99). The energies of the highest occupied and lowest unoccupied
Keywords:
DFT calculations
molecular orbitals were estimated using B3LYP (Becke three-parameter hybrid functional combined with
HOMO LeeeYangeParr correlation functional)/6-311þþG (d, p). Optimization of the structure of (Z)-1-(thio-
LUMO phen-2-yl-methyleneamino) propane-2-ol provided information concerning the stable form of the ge-
Schiff base ometry of the molecule, stoichiometry of the complexes, and thermodynamic parameters (e.g., energy
and entropy). The results indicate that the Schiff base formed stable complexes with Ni2þ. The energy of
the complex was much lower than that of the free Schiff base. The charge distribution values of each
atom in the Schiff base were in agreement with the Pauling scale for electronegativity and vibrational
wavelength.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction [7]. b-lactam and oxazolidines were also synthesized from phe-
noxyacetic acid and ethanolimines, which are promoted by ben-
Tridentate Schiff bases with nitrogen (borderline), oxygen zenesulfonylchloride [7]. These authors synthesized the Schiff base
(hard), and sulfur (soft) donor atoms show good coordination with from starting materials such as 2-thiophenecarboxyaldehyde and
various metal ions to yield stable complexes with a hard/soft acid/ 1-amino-2-propanol. The product is b-lactam when the amines
base relationship [1e3]. Schiff bases have been applied in different group was protected by tetramethylsilane (TMS) [7].
fields such as efficient degradation of a wide range of unwanted The Schiff bases, N-[2-thinylmethylidene]amino propane and N-
human tissue cells [4], food flavoring [5], production of gold [2-thinylmethylidene]-2-propanol amine, were used for a liquid
nanoparticles with C60 for solar cells [6], and antibacterial, anti- membrane on a graphite rod for the selective identification of Cu2þ
oxidant, and anti-inflammatory materials. The Schiff bases, N- and Ni2þ by direct potentiometer and potentiometric titration [8].
proteo b-lactams, have been synthesized from (N-2- The geometries of complexes formed from the Schiff base, (Z)-1-
hydroxypropyl) imine derivatives and phenoxyacetylchloride in (thiophen-2-yl-methyleneamino)propane-2-ol with Co2þ, Ni2þ,
the presence of trimethylamine to study its antibacterial activity and Cu2þ, were studied [9]. The results show that Ni2þ and Co2þ
formed octahedral geometries while Cu2þ showed a distorted
octahedral geometry.
* Corresponding author.;
If the energy value of the highest occupied molecular orbitals
** Corresponding author. (EHOMO) is high, the molecule can donate its electrons to acceptor
E-mail addresses: [email protected] (J.S. Aulakh), [email protected] molecules [10,11]. The energy of the lowest unoccupied molecular
(K.-H. Kim).

https://doi.org/10.1016/j.molstruc.2019.127104
0022-2860/© 2019 Elsevier B.V. All rights reserved.
2 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104

orbitals (ELUMO) is an indication of the tendency of a molecule to added with constant stirring and refluxed by using a Dean stark
accept electrons from donor molecules. The lower this energy, the apparatus for 3 h at a temperature of 60  C (Scheme 1). After
better the chance to accept electrons [12]. The energy gap between checking for the completion of the reaction by TLC, the solution was
(HOMO) and (LUMO) was calculated using the Gaussian 09 pro- cooled to room temperature, filtered, vaporized, and recrystallized
gram. Based on this value the stability of the molecules was esti- from hexane to yield white crystals with a melting point of
mated. A larger energy gap between the HOMO and LUMO 68e70  C.
indicates higher stability of a molecule or complex [12]. Hardness
(ƞ) is a measure of resistance to charge transfer, calculated from half 2.3. Synthesis of Ni2þcomplexes
of the energy difference between the HOMO and LUMO. Chemical
softness (S) is the capacity of an atom or group of atoms to receive An ethanolic solution of Nickel nitrate (0.5 mmol, 0.186 g) was
electrons, calculated from half of the hardness (ƞ) [12,13]. mixed to a hot ethanolic solution of the Schiff base (Z)-1-(thiophen-
To the best of the authors’ knowledge, no prior studies have 2-yl-methyleneamino) propan-2-ol (1 mmol, 0.187 g) and refluxed
estimated the theoretical and experimental values of (Z)-1-(thio- for 12 h upon continuous stirring. A white precipitate was formed
phen-2-yl-methyleneamino) propane-2-ol. In this regard, herein, a which was washed with ethanol and water and dried over CaCl2 in
detailed theoretical and experimental investigation of the vibra- dissector.
tional spectra and thermodynamic data of the molecule was carried
out. The agreement between the experimental and theoretical 2.4. Computational details
values was evaluated [14e16]. The binding energy of the metal
cation and ligands was calculated using the following relationship The input files of the L and M-L complexes were prepared with
[3,17]: Gauss view 5.0.8 [10]. All calculations were made using Gaussian 09
[18] by density functional theory (DFT)/B3LYP methods. LANL2DZ
DE ¼ Ecomplex  ðEcation þ nEligand Þ (Loss Alamos National Laboratory 2-Double-Z)/6-311G (d, p) was
used as the standard basis set. This was because 6-311G (d, p) is a
where DE is the change of energy, Ecomplex, Ecation, and Eligand are the popular polarized basis set that adds the p function to hydrogen
total energy of the complex, energy of cation, and energy of the atoms in addition to the d function on heavy atoms, while LANL2DZ
ligand, respectively, and n is the stoichiometric factor. is a basis set for post third row atoms. This basis set uses effective
core potentials in the calculation. The structure of (Z)-1-(thiophen-
2. Experimental 2-yl-methyleneamino) propane-2-ol was first optimized, the metal
ion was optimized separately, and lastly, the complexes were
2.1. Materials and chemicals optimized and the change of energy was calculated.

Reagents were obtained from Avra Synthesis (Hyderabad India) 3. Results and discussion
and TCI Chemicals (Chennai India). They were used without further
purification. Completion of the reaction was checked by using thin 3.1. Thermodynamic parameters
layer chromatography (TLC). 1HNMR and 13CNMR spectra were
obtained by using a BRUKER AVACE II 400 MHz NMR spectrometer Different thermodynamic parameters (e.g., total energy, specific
SAIF. For the Fourier transform infrared (FTIR) analysis, a Perki- heat capacity, zero-point vibrational energy rotational constant,
nElmer 100 FTIR spectrometer was used. A UV-1800 Shimadzu entropy, and dipole moment) of the (Z)-1-(thiophen-2-yl-methyl-
spectrophotometer was used to obtain UVevis spectra. The theo- eneamino)propane-2-ol were calculated using different basis sets.
retical studies were carried out using Gaussian 09 software [18]. From the value obtained, the type of the basis set with a better
stable form was selected. As indicated in Table 1 the B3LYP/6-
2.2. Synthesis of (Z)-1-(thiophen-2-yl-methyleneamino) propane- 311þþG (d, P) provided the results which best match with exper-
2-ol imental value.

The (Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol was 3.2. Mulliken charge distribution

synthesized according to the method reported by Sharma et al. [7].
The steps to synthesize this Schiff are as follows. To a solution of The Mulliken charges are directly related to the vibrational
thiophene-2-carboxyaldehyde (0.1 mol/9.3 mL) in benzene properties of the compound [19], which is a way to quantify elec-
(30 mL), a solution of 1-amino-2-propanol (0.1 mol/8.3 mL) was tronic structure changes under atomic displacement. Mulliken

Scheme 1. Synthesis of (Z)-1-(thiophen-2-yl-methyleneamino) propan-2-ol.

 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104 3

Table 1
Calculated thermodynamic parameters of (Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol using different basis sets.

Order Atom B3LYP/3-21G B3LYP/6-31G B3LYP/6-311G B3LYP/6-311þþG(d, P)

1 Energy 1817.2055 1923.446 2016.579 2017

2 Rotational constanThe change was calculated as follows:t
3 A 2.835 2.835 2.835 2.835
4 B 0.364 0.364 0.364 0.364
5 C 0.341 0.341 0.341 0.341
6 CV (Cal mol1k1) 42.169 42.022 42.394 42.372
1 1
7 Entropy (s) Calmol k- ) 106.725 107.802 108.513 108.329
8 Dipole moment (Debye) 2.277 1.306 1.146 0.654

charges affect various properties of molecular systems such as the

dipole moment, polarizability, electronic structure, and non- Hardness ðhÞ ¼ DE ¼ ½ð  0:179Þ ¼ 0:089 a:u:
covalent interactions [19].
To compare the charge distribution on each atom of (Z)-1-(thi- Softness ðSÞ ¼ ½ ðhÞ ¼ 0:045 a:u:
ophen-2-yl-methyleneamino) propane-2-ol, different calculations
The calculations reveal a small energy gap, low resistance to
were conducted using different basis sets such as 3-11G, 6-31G, and
charge transfer, and high affinity for receiving electrons.
6-311G (d, p). The results obtained from the calculations indicate
Data such as the bond length, bond angle, and torsional angle of
that oxygen carries a large negative charge, as expected from the
the optimized structure of the Schiff base (Z)-1-(thiophen-2-yl-
electronegativity point of view. The Mulliken charges with
methyleneamino) propane-2-ol (Fig. 2) are listed in Tables S1 and
hydrogen summed into heavy atoms (carbon, nitrogen, oxygen, and
S2. The bond length calculated using B3LYP/6-311G is comparable
sulfur) [10] are shown in Table 2.
with the reported values for similar position atoms. C1eS in this
calculation 1.801, C4eC9 1.443 and in literature 1.734 and 1.467 A
respectively [20].

3.3. Frontier molecular orbitals

3.4. Natural bond orbital analysis
The frontier molecule orbitals (FMO) theory is useful to predict
The concept of natural orbitals may be used for distributing
relative reactivity based on properties of the reactants [10]. The
electrons into atomic and molecular orbitals, thereby deriving
formulation of this theory is based on the perturbation theory. In
atomic charge and molecular bonds [10]. The idea of the natural
this theory, the energy change at the beginning of the reaction is
atomic orbital occupancies (NAO) and natural bond orbital (NBO)
estimated and inferred for the transition state. This theory con-
was developed to use one electron density matrix to define the
siders a reactant as an unperturbed reference and uses low-order
shape of atomic orbitals in the molecular environment and to drive
perturbation expansion. The assumption of this theory works
molecular bonds from the electron density between atoms. For (Z)-
only for a reaction that follows a shorter path than the different
alternative reaction pathway. The energy difference between the
frontier molecular orbitals of the Schiff base (Z)-1-(thiophen-2-yl-
methyleneamino)propane-2-ol was calculated from Fig. 1 with
EHOMO ¼  0.237 a.u atomic unit (a.u) and ELUMO ¼  0.058 a.u.
The change was calculated as follows:

DE ¼ EHOMO  ELUMO

DE ¼ 0:237a:u:  ð  0:058Þ a:u: ¼ 0:179a:u

and the hardness and softness were calculated based on this value
as follows.

Table 2
Mulliken charges with hydrogen summed into heavy atoms for (Z)-1-(thiophen-2-
yl-methyleneamino)propane-2-ol.

Order No. of 3-11G 6-31G 6-311G(d, p)

atoms

1 1 C 0.3644 0.41836 0.01075

2 2 C 0.0379 0.079739 0.452943
3 3 C 0.0066 0.068374 0.47003
4 4 C 0.4302 0.29537 0.00297
5 9 C 0.2132 0.257618 0.52457
6 11 C 0.1759 0.155214 0.01575
7 12 C 0.2813 0.245853 0.040666
8 13 C 0.2220 0.007683 0.437852
9 14 O 0.1919 0.25938 0.037232
10 5 S 0.5764 0.52286 0.007976
Fig. 1. HOMO-LUMO energy gap of (Z)-1-(thiophen-2-yl-methyleneamino) propane-2-
11 10 N 0.5266 0.36423 0.047402
ol.
4 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104

Table 4
Natural electronic configuration of (Z)-1-(thiophen-2-yl-methyleneamino)propane-
2-ol.

Atom No. Natural Electron Configuration

C 1 [core]2S(1.05)2p(3.37)3p(0.01)
C 2 [core]2S(0.99)2p(3.28)3p(0.01)
C 3 [core]2S(0.97)2p(3.26)3p(0.01)
C 4 [core]2S(0.98)2p(3.29)3p(0.01)
S 5 [core]3S(1.64)3p(3.92)4S(0.01)4p(0.01)
H 6 1S(0.73)
H 7 1S(0.73)
H 8 1S(0.73)
C 9 [core]2S(0.94)2p(2.94)3p(0.02)
N 10 [core]2S(1.40)2p(4.04)3p(0.01)
C 11 [core]2S(1.03)2p(3.24)3p(0.01)
C 12 [core]2S(0.97)2p(2.92)3p(0.01)
C 13 [core]2S(1.09)2p(3.60)
Fig. 2. Optimized structure of (Z)-1-(thiophen-2-yl-methyleneamino) propane-2-ol. O 14 [core]2S(1.68)2p(5.05)
H 15 1S(0.80)
H 16 1S(0.78)
H 17 1S(0.55)
1-(thiophen-2-yl-methyleneamino)propane-2-ol under study for H 18 1S(0.78)
the 125 natural population, the NAO functions are shown in H 19 1S(0.77)
Table S3. The connectivity of the atom with each other is indicated H 20 1S(0.78)
by number according to the number given for each atom in Fig. 2. H 21 1S(0.76)
H 22 1S(0.78)
For a selected NAO, Table 3 lists the occupancy and energy of the
corresponding orbitals.
The analysis of the natural population indicates that the valence
and core electrons can make contributions for bonding by more approximately assigned [10]. The natural electronic configuration
than 90%. In Table S4, the detailed NBO values of the Schiff base (Z)- of the element in the Schiff base (Z)-1-(thiophen-2-yl-methyl-
1-(thiophen-2-yl-methyleneamino) propane-2-ol are listed. The eneamino)propane-2-ol was calculated using the Gaussian 09
charge distribution showed a different charge between C and H. program. For example, the electronic configuration for C-1 is
The highest negatively charged carbon was C-1 ¼ 0.427. For H, the 1s22s12p33s0. The configurations for S, N, O, and H can be described
slightly more positive charge is H-17 ¼ 0.44693. For S, O, and N, the as 1s22s22p63s23p4; 1s22s12p4, 1s22s22p5, and 1s1, respectively.
values were 0.41342, 0.73659, and 0.44521, respectively. Based on these natural electronic configurations, the transfer of
As shown in Tables S5 and 55 Rydberg orbitals of the non- electrons can be predicted from the valence electrons of each atom
resonant background (NRB) set accounted for only 0.17% of the in the molecules.
electron density, while the 70 natural minimal basis (NMB) func-
tion accounted for 99.8%. For the two types of orbitals, donor (NBO 3.6. Total population density of states
(A)) and acceptor (NBO (B)), the stabilization energy (E(2)) associ-
ated with delocalization was estimated. Entries are included in only The total density of state (TDOS) was studied by using Gauss
when the interaction energy exceeds a default threshold of Sum 2.2 version to evaluate the contribution of each type of bond
0.5 kcal mol1. The strong interaction between nN / p*CH of the N and the converging nature of the energy [10]. The plot of the
lone pair (NBO113) and C3eH antibonding (NBO108) gave the density of state (DOS) indicates the molecular orbital alignments
strongest stabilization energy of 35.31 kcal mol1, as obtained from and their contribution to chemical bonding (Fig. S1). The DOS was
the theoretical calculation. This indicates that the stability of the plotted with a unit height and full width at half maximum (FWHM)
(Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol is likely to be of 3 eV [10]. The bonding, antibonding, and non-bonding in-
due to the formation of an imine or azomethine group. teractions in the molecule are also indicated in this plot. The line is
directed towards zero, which shows that the self-consistent field
(SCF) is converging. To study the optimization step, a graph
3.5. Natural electron configuration showing deviation from the target was plotted, as shown in Fig. S2.
The optimized energy curve (Fig. S4) was obtained by plotting a
The natural electron configuration of the atoms in the Schiff graph of the energy vs. optimization step. From these plots,
base (Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol is shown whether the energy converged or not was evaluated. Raman
in Table 4. spectroscopy analysis of the Schiff base (Z)-1-(thiophen-2-yl-
The occupancies of the atomic orbitals were not integer in a methyleneamino)propane-2-ol was carried out by plotting the
molecule. Even though the calculated number of electrons on the Raman activity vs. frequency, as shown in Fig. S4.
sub-shell is a decimal number, the number of electrons can be The molecular orbital information was extracted from the
output file of the geometry optimization for the Schiff base.
Table 3 Table S6 lists different molecular orbitals relative to HOMO and
Natural populations: natural atomic orbital occupancies of (Z)-1-(thiophen-2-yl- LUMO with different energies. The stability of the molecule can be
methyleneamino)propane-2-ol. approximated based on the magnitude of the difference where a
NAO Atom No. lang Type (AO) Occupancy Energy a. u high magnitude leads to a high stability.

42 S 5 px Val(3p) 1.03184 0.14362

72 N 10 pz Val(2p) 1.15582 0.16381 3.7. Vibrational analysis
90 C 12 pz Val(2p) 0.85348 0.00406
108 O 14 pz Val(2p) 1.59457 0.35371 To identify the geometric arrangement of nuclei corresponding
110 H 15 S Val(1S) 0.79622 0.14387
to a stable molecule, Schiff base (Z)-1-(thiophen-2-yl-
 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104 5

methyleneamino)propane-2-ol was optimized based on the mini- correlation coefficient (R2) was calculated from the slope and
mum of the potential energy surface by B3LYP/6-311þþG (d, p). intercept (Fig. S7). From the equation of a straight line:
For the vibrational analysis, the Gaussian 09 program was used
to generate theoretical values of vibrations of the atoms and Y ¼ am þ b
functional groups to compare with the experimental values. The IR
spectra of Schiff base (Z)-1-(thiophen-2-yl-methyleneamino) pro- ncal ðcm1 Þ ¼ 1:0163nexp  7:5844ðR2 ¼ 0:9979Þ
pane-2-ol obtained from the theoretical calculations and experi-
ments are shown in Figs. S5 and S6, respectively. The spectrum was where ncal is the theoretical value, nexp is the experimental value,
theoretically obtained by using B3LYP/6-311þþG (d, p). By plotting and R2 is the correlation factor. The value of R2 (0.9979) demon-
the experimental IR value versus the theoretical IR value (Table 5) a strates that there is good agreement between the theoretical and
experimental values of different vibrations.

Table 5
Experimental and theoretical values of the IR spectrum of (Z)-1-(thiophen-2-yl- 3.7.1. OeH mode
methyleneamino)propane-2-ol. In compounds containing this group, the OH stretching modes
Experimental IR Calculated IR Assignment are assigned in the 3752-3430 cm-1 region [21,22]. The signal
appeared at 3828 cm1 experimentally and at 3827 cm1 was
3822.9w 3827.4 ʋO14-H16
3245.9w 3241.39 ʋC1-H6
assigned to OeH stretching. DFT calculation predicted the in plane
3211.77 ʋC2-H7 deformation or rocking mode at 1143 cm1.
3196.12 ʋC3-H8
3119.3 ʋasCH2
3095.8w 3099.8 ʋasCH3 3.7.2. CeH mode
3064.12 ʋsC9-H15 A stretching vibration appeared from 3245 cm1 to 2902 cm1
3032.91 ʋsCH3 was assigned to CeH stretching. Experimentally, the thiophene
3010.31 ʋsCH2 moiety(ring hydrogen) eH stretching vibration appeared at
2965.5w 2989.55 ʋa C12H19
2902.9w 2958.56 ʋs C12H19
3245 cm1, azomithene hydrogen (C9eH15) appeared at
1636s 1687.51 ʋsN14-C9 3095 cm1 and C12eH19 appeared at 2965.5 cm1 [22].The out of
1570w 1498.25 ʋC3-C4 plane deformation or wagging at 539 cm1 was assigned for
1491.42 bC1H6bC2-H7bC3-H8 C9eH15 and in plane deformation rocking mode at 1111 cm1 was
1464.94 daCH3 assigned for C12eH19.
1457.04 daCH2
1431.31 ʋsC1C2C3 Aliphatic hydrogens of CH2 and CH3 appeared at 3066 and
1430w 1430.31 scN10C9H15 2902 cm1, respectively. Based on the B3LYP/6-311þþG (d, p)
1395.6 dsCH3 computation, they appear at 3,248, 3,101, 3,063, and 3041 cm1,
1389.01 dsCH2 respectively. The band due to CH2 scissoring is usually occurred at
1369.5w 1362.16 ʋC2-C3
1465 cm1 and for CH3 is near 1375 cm1 [23]. The calculated value
1349.6w 1333.24 ʋC1-C2
1295.9w 1285.13 ʋaC-O 1464 cm1 and 1457 cm1 was assigned to in plane deformation of
1249.2w 1245.86 ʋaC-O CH3 and CH2 respectively.
1242.76 bC1-H6
1209.07 bC2-H7
1138.1w 1143.3 dO-H 3.7.3. C]C mode
1115.3w 1111.1 bC12-H19 The ring C]C stretching vibration appears in the range from
1103.76 bʋC2-C3 1475 to 1600 cm1 [23]. The bands of C]C stretching vibrations
1080.58 bʋC1-C2
1069.9 m 1072.56 ʋsC-O
experimentally appeared at 1,520, 1,430, 1,365, 1,222, and 937 cm1.
989.56 sN10-C11 Based on the B3LYP/6-311þþG (d, p) level method, the vibrations
964.73 rC9-H15 were observed at 1,549, 1,431, 1,362, 1,242, and 956 cm1, respec-
937.3 m 956.8 rCH3 tively. The calculated value at 1489 cm1 was assigned to vibration
925.01 tC2-H7tC3-H8 of C3eC4 and for C2eC3at 1362.16 cm1. Out of plane vibration of
902.94 tC3-H
870.96 rC1-H6rC2-H7 C1eC2 was assigned at 1080 cm1
859.8 rC8-H8
844.9 m 834.47 rC1-S-C4
764.71 bC-O
3.7.4. C]N mode
737.6w 717.75 scC4C9N10 The Schiff base contained eC]Ne bonds. The eC]Ne band
715.56 tRing appeared at 1635 cm1 experimentally. It was theoretically calcu-
647.56 twCH2 lated to appear at 1688 cm1 using the B3LYP/6-311þþG (d, p) level
578.2w 539.21 wC9-H15
method. The results obtained in the experiment and theoretical
530.48 scN10C11C12,scS5C1C4
476.3w 480.53 sc C11C12C13 studies were in good agreement. The in plane bending or scissoring
432.4w 434.4 tS5C4C1 of C4C9N10 was assigned at 715 cm1. The wave number for each
406.46 bO14C12C13 group was consistent with the results reported previously [23e25].
398.47 scC11C12C13
298.18 tO14-H16
239.65 b CeO 3.7.5. CeO mode
195.23 wC11C12C13 Stretching vibration of OeC usually occurs in the range
190.33 tN10C11C12
1260e1000 cm1 [23]. Such stretching vibration was assigned
117.71 wC11N10C9
85.55 tC11C9 1020 cm1 by S.Kumar et al., [26]. Asymmetrical stretching of CeO
52.11 rO14C12C13 was assigned at 1285 cm1 and the medium band at 1069.9 cm1
32.55 twC11C12C13 obtained experimentally and 1072.56 cm1 obtained by calculation
Abbreviations: a, antisymmetric; s, symmetric, ʋ, stretching, w, wagging; t, torsion; was assigned to CeO symmetrical stretching vibration and at
b, deformation in the plane, tw, twisting; d, deformation out of plane; r, rocking. 764 cm1 was assigned to deformation mode.
6 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104

Table 6 to TMS. For theoretical studies, a gauge including atomic orbitals

Theoretical and experimental values of the chemical shift for (Z)-1-(thiophen-2-yl- (GIAO) using the B3LYP/6-311þþG (d, p) method was applied to
methyleneamino)propane-2-ol.
calculate the 1HNMR and 13CNMR chemical shifts [15]. The exper-
Order Group Chemical shift (ppm) imental 1HNMR results are given in Fig. S9.
Theoretical Experimental The 1HNMR results (400 MHz instrument frequency, Dimethyl
sulfoxide (DMSO) as the solvent, chemical shift (d) in ppm) were
1 CH3 1.30 1.25
2 OeH 2.80 2.53 1.25 d with DJ ¼ 6.32 Hz (d,3H of CH3), 2.53 d (s, 1H, of OeH), 3.43
3 CH2 3.26 3.43 d (m, 2H, of CH2), 4.08 d (m, 1H of CH), 7.19 d (m, 3H of thiophene)
4 CH 3.95 4.08 this was reported as 6.61e7.88 ppm [27], and the most downfield at
5 N¼CeH 8.80 8.39
8.39 d (m, 1H of HeC]N) which is consistence for azomethine
6 Azomithen hydrogens 7.20 7.19
Hydrogen reported as 8.34 d [12]. The formation of azomethine is
confirmed by the absence of spectrum in the range of 9.0e10.0
d which is for the spectrum of aldehyde hydrogen [21].
Table 7
Experimental and theoretical13CNMR spectrum data of (Z)-1-(thiophen-2-yl-
This information was plotted vs. the experimental values to
methyleneamino)propane-2-ol. study the linearity among the two values. The experimental and
theoretical 1HNMR values are shown in Table 6. Fig. S10 shows
Order C No. Experimental Theoretical
Correlation graph of the experimental and theoretical 1HNMR
1 C13 21.6 14.44 values. A linear relationship was obtained between the two values
2 C11 65.63 60.45
with R2 ¼ 0.9946:
3 C12 68.14 65.26
4 C4 127.64 110.95
5 C3 129.16 112.89 dcal ðppmÞ ¼ 0:9649dexp þ 0:0865ðR2 ¼ 0:9946Þ
6 C2 131.05 115.87
7 C1 142.44 125.23 where dcal is the calculated chemical shift and dexp is the experi-
8 C9 155.2 146.12
mental chemical shift.
The theoretical 13CNMR chemical shift values are compared to
3.7.6. CeS mode the experimental data in Table 7 and Fig. 3 shows the correlation
The medium band at 844 cm1 was assigned to vibration of graph. A strong signal appearing at 155.ppm can be assigned to
(CeSeC) and similar assignment for such vibration (850 cm1) was azomethine and 127e142 ppm was assigned to thiophene moiety.
reported by M. Shakira [27] and bending vibration was also This is consistent with the report for thiophene [27]. All the carbon
assigned at 239.9 cm1. appeared in the region expected [23]. Carbon numbering was ac-
The complex of Ni2þ of the Schiff base was characterized by its cording to Fig. 2. The experimental and theoretical results can be
melting point which is much above the free Schiff base (above correlated as follows.
250  C) and FT-IR. The formation of Ni2þcomplex was confirmed by
existing of new band which is not in the ligand at 420 cm1 which dcal ðppmÞ ¼ 0:9123 dexp
is common for M-N and M-O stretching which was consistent with  2:0349 ðR2 ¼ 0:9911ðP ¼ 9:2  104 ÞÞ
the reported value [13]. This indicates there is a bond formation
between metal and oxygen and nitrogen. The broad band at around
3247 cm1 in the ligand is not appeared which is another indication
of removal of proton from OH. and the eC]N which at 1635 cm1
3.9. Ni complex of (Z)-1-(thiophen-2-yl-methyleneamino)propane-
also shifts to 1414 cm1 which is supported by the result reported
2-ol
by Ref. [13] indication of bond formation between metal and azo-
methine nitrogen. FT-IR of the complex is indicated by (Fig. S8).
The optimized structure of the Ni2þ complex of (Z)-1-(thiophen-
2-yl-methyleneamino) propane-2-ol is shown in Fig. 4, which was
3.8. NMR spectra optimized by using a basis set of the GEN/B3LYP.This structure was
proposed (1:2) metal to ligand was based on the optimization of
Chemical shifts are reported in parts per million (ppm) relative structures since this type of connectivity gives the lowest energy

13
Fig. 3. Correlation of the experimental and theoretical values of CNMR of (Z)-1-(thiophen-2-ylmethyleneamino) propane-2-ol.
 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104 7

Fig. 4. Optimized structure of the Ni2þ complex of (Z)-1-(thiophen-2-yl- methyleneamino)propane-2-ol.

for the complexes and further confirmed with UV.VIS titration. A formed more stable complexes with Ni2þ than the other metal
series of different mole ratio of metal to ligand was prepared and ions studied. To study the energy of the complexes formed, both of
maximum absorbance was obtained when 6.67 volume of ligand the structures must be optimized separately. This optimization
was added to 0.33 volume of metal salt solution of equal concen- should be carried out using a similar base set. The metal ions, Schiff
tration which gives a 0.67 mol ratio of ligand to metal by keeping base, and metal complexes of Schiff base (Z)-1-(thiophen-2-yl-
wave length at 289 cm1. This establishes a 1:2 binding stoichi- methyleneamino)propane-2-ol were optimized using a similar
ometry. Based on this value Fig. 4 was proposed for the complex. basis set. Using the above equation, the change of energy for each
The energy gap between the HOMO and LUMO of the Ni complex complex was calculated and the values are listed in Table 8. The
with Schiff base (Z)-1-(thiophen-2-yl-methyleneamino)propane-2- Schiff base selected in this study was found to form a more stable
ol was 0.10076 hartree and the dipole moment is 6.3302. complex with Ni2þ.
When the Schiff base (Z)-1-(thiophen-2-yl-methyleneamino)
propane-2-ol was complexed with Ni2þ, the energy of the complex 4. Conclusions
decreased by 2033 Hartree. The energy for free (Z)-1-(thiophen-2-
yl-methyleneamino)propane-2-ol was found to be 2017 Hartree DFT calculations were conducted for the structures and vibra-
while that of the complex with Ni decreased to 4050 Hartree. The tional spectra of (Z)-1-(thiophen-2-yl-methyleneamino)propane-
calculated change of energy for Ni2þ was 13 Hartree using the 2-ol and its metal complexes. By comparing the experimental and
following equation. theoretical results, the thermodynamic parameters indicate that
the experimental results obtained using 1HNMR, 13CNMR, and FT-IR
DE ¼ Ecomplex  ðEcation þ nEligand Þ are in good agreement with the calculated values. This study
demonstrates that the scaled DFT/B3LYP calculations can offer a
¼ 4050  ð3 þ ð2 ð2017ÞÞÞ ¼ 13 Hartree useful approach to understand the vibrational spectra of medium-
sized organic compounds and their stability based on the energy
By using the same basis set, the energies of the different metal gap between the HOMO and LUMO, softness, and hardness of the
complexes of (Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol molecules. The information of the bond length and contribution of
were studied and compared to determine the relative stability. each type of bond can also be calculated by using the Gaussian 09
The smallest energy obtained was for the Ni-(Z)-1-(thiophen-2-yl- program. These theoretical approaches are useful when designing,
methyleneamino)propane-2-ol complex. This result indicates that synthesizing, and predicting the stable form of molecular ar-
Schiff base (Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol rangements of complexes and their dipole moments. The theoret-
ical evaluation can play an important role in correcting the
assignment of the vibrational wavelength and chemical shifts that
Table 8 can be applied for the identification of metal ions with which a
Binding energy (DE) of (Z)-1-(thiophen-2-yl-methyleneamino)propane-2-ol with Schiff base forms a more stable complex. This theoretical study
different metal ions.
could also help investigate the molecular properties that are un-
Mnþ Emnþ EL-Mnþ DE(Hartree) DE(KJ/mol) stable under certain conditions by designing optimized conditions
Ni2þ
3 4050 13 34,138 under which a molecule becomes stabilized.
Pb2þ 35 4060 12 31,500
Cu2þ 101 3945 192 504,096
Zn2þ 154 4200 10 26,255 Acknowledgements
Hg2þ 160 4125 71 186,410.5
Fe3þ 200 3900 336 882,168 The authors thank the Department of Chemistry, Punjabi Uni-
Fe2þ 241 4055 222 582,861 versity, Patiala, India and the Federal Democratic Republic of
Cd2þ 250 4100 186 488,343
Ethiopia for their support. KHK also acknowledges the support
8 A.L. Berhanu et al. / Journal of Molecular Structure 1200 (2020) 127104

made by the R&D Center for Green Patrol Technologies through the [13] Sheida Esmaielzadeh, Leila Azimian, Khadijeh Shekoohi, Khosro Mohammadi,
Coordination chemistry, thermodynamics and DFT calculations of copper (II)
R&D for Global Top Environmental Technologies funded by the
NNOS Schiff base complexes, Spectrochim. Acta A Mol. Biomol. Spectrosc. 133
Ministry of Environment (Grant No: 2018001850001) as well as by (2014) 579e590.
a grant from the National Research Foundation of Korea (NRF) [14] Neha Sharma, Jaspreet S. Dhau, Avtar Singh, Amritpal Singh, K. Ashok, Malik,
funded by the Ministry of Science, ICT & Future Planning (Grant No: FT-IR, NMR, molecular structure, and HOMO-LUMO studies of 3, 5-dimethyl-
2-pyridylselenium compounds by density functional theory." Phosphorus,
2016R1E1A1A01940995). This work was also supported by the Sulfur Silicon Relat, Elements 192 (2017) 368e375.
“Cooperative Research Program for Agriculture Science & Tech- [15] M. Govindarajan, M. Karabacak, Spectroscopic properties, NLO, HOMOeLUMO
nology Development (Project No. PJ014297)” Rural Development and NBO analysis of 2, 5-Lutidine, Spectrochim. Acta A Mol. Biomol. Spectrosc.
96 (2012) 421e435.
Administration, Republic of Korea. [16] Ram N. Patel, Yogendra Singh, Yogendra Pratap Singh, Raymond J. Butcher,
Arti Kamal, I.P. Tripathi, Copper (II) and nickel (II) complexes with N0 -[(Z)-
Appendix A. Supplementary data phenyl (pyridin-2-yl) methylidene] acetohydrazide: Synthesis, crystal struc-
tures, DFT calculations and antioxidant effects, Polyhedron 117 (2016) 20e34.
[17] V.K. Gupta, A.K. Jain, Pankaj Kumar, PVC-based membranes of N, N0 -dibenzyl-
Supplementary data to this article can be found online at 1, 4, 10, 13-tetraoxa-7, 16-diazacyclooctadecane as Pb (II)-selective sensor,
https://doi.org/10.1016/j.molstruc.2019.127104. Sens. Actuators B Chem. 120 (2006) 259e265.
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