Polyhedron 89 (2015) 29–38

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Polyhedron
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Synthesis, characterization and corrosion inhibition property of nickel(II)

and copper(II) complexes with some acylhydrazine Schiff bases
Monika Mishra a, Karishma Tiwari a, Punita Mourya b, M.M. Singh b, Vinod P. Singh a,⇑
a
Department of Chemistry, Banaras Hindu University, Varanasi 221 005, India
b
Department of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi 221 005, India

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

Article history: Ni(II) and Cu(II) complexes with 2-amino-benzoic acid (1-phenyl-propylidene)-hydrazide (Habh) and 2-
Received 9 August 2014 hydroxy-benzoic acid (1-phenyl-propylidene)-hydrazide (Hhbh) have been synthesized and character-
Accepted 6 January 2015 ized by different physico-chemical and spectroscopic techniques (UV–Vis, IR & NMR). The molecular
Available online 14 January 2015
structures of the ligands and their complexes [Ni(abh)2(DMSO)2], [Ni(hbh)2(DMSO)2] and [Cu(abh)2] have
also been determined by single crystal X-ray diffraction technique. In all the complexes, each ligand
Keywords: coordinates to metal through azomethine-N and carbonylate-O resulting a 4-coordinate distorted square
Transition metal complexes
planar geometry for Cu(II) complexes and 6-coordinate distorted octahedral geometry for Ni(II) com-
Schiff base
Acylhydrazines
plexes in which two DMSO molecules occupy the axial positions. The structure of [Cu(hbh)2] complex
Single crystal X-ray diffraction study has been satisfactorily modeled by density functional theory (DFT) and time dependent-DFT (TD-DFT)
DFT calculations. The corrosion inhibition study of the synthesized compounds has also been performed for
Corrosion inhibition mild steel in 0.5 M H2SO4 medium. The activity is found in the order: Ni(II) complexes > ligands > Cu(II)
complexes. The DFT study on ligands also supports the experimental observation that Habh is better
corrosion inhibitor than Hhbh.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Schiff base complexes with a variety of metals have been
extensively used as efficient catalysts [1,2], sensors [3] corrosion
inhibitors [4] and model compounds for active centers of metallo-
enzymes [5]. The transition metal complexes of acylhydrazine
Schiff bases exhibit wide range of biological and pharmaceutical
activities that include antimicrobial, antituberculostatic, antibacte-
rial, anticancer and antioxidant behavior [6–8]. These complexes
show good electrical and magnetic properties [9] and are used in
synthetic and analytical chemistry as novel heterogeneous cata-
lysts in various chemical and photochemical reactions [10,11].
The Cu(II) complexes have been reported to be active in DNA
strand scission [12]. Octahedral Ni(II) Schiff base complexes have
been found to possess magnetic interactions covering a broad
range from antiferromagnetism to ferromagnetism [13].
Among the several corrosion protection technologies, the use of
inhibitors is one of the most practical methods especially in acidic
media [14]. The choice of the inhibitor is based on two consider-
ations: first it could be synthesized conveniently from relatively
cheap raw materials, secondly, it should contain an electron cloud
⇑ Corresponding author. Tel.: +91 9450145060.
E-mail address: singvp@yahoo.co.in (V.P. Singh).
on the aromatic ring or, the electronegative atoms such as nitrogen
and oxygen in the relatively long chain compounds [15]. Due to the
presence of C@N group in the Schiff base molecules, they are likely
to be good corrosion inhibitors [16–18]. Schiff bases are adsorbed
on the surface of mild steel and spontaneously form a monolayer
on the surface, therefore, act as effective corrosion inhibitor [19].
The metal complexes of Co(II), Ni(II), Zn(II) and Sn(II) with different
ligands have shown good corrosion inhibition property for steel in
different acidic media at room as well as elevated temperatures
[20]. The transition metal complexes of Schiff base ligands are
expected to provide better efficiency due to their larger size and
compactness, and the synergistic action of metal–organic blends
[21]. It has also been reported that the metal complexes show
greater inhibition efficiency than the free ligands [22].
In persistence of our quest for developing corrosion inhibitors
with high effectiveness and efficiency, we have synthesized and
characterized the Ni(II) and Cu(II) complexes with 2-amino-
benzoic acid (1-phenyl-propylidene)-hydrazide (Habh) and 2-
hydroxy-benzoic acid (1-phenyl-propylidene)-hydrazide (Hhbh)
and studied their anti-corrosion properties on mild steel in 0.5 M
H2SO4 acidic medium. A careful view into the literature shows that
there are only very few reports where transition metal complexes
containing hydrazide Schiff base ligands have been used as
corrosion inhibitor. However, there is no report on the corrosion

http://dx.doi.org/10.1016/j.poly.2015.01.003
0277-5387/Ó 2015 Elsevier Ltd. All rights reserved.
30 M. Mishra et al. / Polyhedron 89 (2015) 29–38
inhibition of the synthesized Schiff bases and their complexes in
sulfuric acid media (0.5 M). Although, the structure of most of
the synthesized compounds in this paper have been determined
by X-ray crystallography, the structure of [Cu(hbh)2] has been
established by DFT and TD-DFT calculations by comparing the
experimental electronic and infrared spectral data with theoretical
data.
2. Experimental
2.1. Materials and methods
All analytical grade chemicals were obtained from the commer-
cial sources and used without further purification. Propiophenone,
methyl salicylate, methyl anthranilate and hydrazine hydrate (SD
Fine Chemicals, India) and solvents (Merck Chemicals, India) were
used as such without further purification. The precursors anthra-
nilic acid hydrazide, (NH2)C6H4CONHNH2 and salicylic acid hydra-
zide, (OH)C6H4CONHNH2 were prepared by the literature method
[23].
2.2. Preparation of ligands
The ligands Habh and Hhbh were synthesized by reacting 25 ml
methanolic solution of each of anthranilic acid hydrazide and sal-
icylic acid hydrazide (10 mmol) separately with 25 ml methanolic
solution of propiophenone (10 mmol) in a round bottom flask. The
reaction solutions were refluxed for 3 h. Pale yellow products were
obtained on cooling the above solutions to room temperature. The
products were filtered on a Büchner funnel and washed several
times with methanol. The pure compounds were recrystallised
from hot methanol and dried in a desiccator over anhydrous cal-
cium chloride at room temperature.
2.2.1. 2-Amino-benzoic acid (1-phenyl-propylidene)-hydrazide (Habh)
Yield (80%). M.p. 195 °C. Anal. Calc. for C16H17N3O (267.33): C,
71.89; H, 6.41; N, 15.72. Found: C, 71.62; H, 6.35; N, 15.81%. IR (m
cm1, KBr): m(N–H) 3476, 3236 m, m(C@O) 1650s, m(C@N) 1623s,
m(N–N) 942w. 1H NMR data: 1.06 (3H, CH3); 2.88 (2H, CH2); 6.09
(1H, NH2); 7.77–6.56 (Ar-H); 10.59 (s, 1H, NH). 13C NMR (DMSO-
d6): 11.05 (CH3); 20.01 (CH2); 137.25–115.39 (aromatic carbons);
149.59 (C-NH2); 156.72 (C@N); 161.78 (C@O). The single crystal
structure of the ligand was further confirmed by XRD.
2.2.2. 2-Hydroxy-benzoic acid (1-phenyl-propylidene)-hydrazide
(Hhbh)
Yield (84%). M.p. 183 °C. Anal. Calc. for C16H16N2O2 (268.31): C,
71.62; H, 6.01; N, 10.44. Found: C, 71.45; H, 6.05; N, 10.36%. IR (m
cm1, KBr): m(O–H) 3288b, m(N–H) 3245 m, m(C@O) 1643s, m(C@N)
1605s, m(N–N) 959w. 1H NMR data: 1.16 (3H, CH3); 2.80 (2H, CH2),
8.01–6.80 (Ar-H), 11.02 (s, 1H, NH), 11.49 (s, 1H, OH). 13C NMR
(DMSO-d6): 10.11 (CH3); 20.20 (CH2); 136.75–116.47 (aromatic
carbons); 156.12 (C@N); 161.75 (C@O). The single crystal structure
of the ligand was further confirmed by XRD.
2.3. Synthesis of the metal complexes
Ni(II), and Cu(II) complexes of Habh and Hhbh were synthesized
by reacting 50 ml methanolic solution of the corresponding
metal(II) acetates (5 mmol), separately with a solution of each
ligands (10 mmol) in 25 ml hot methanol in 1:2 (M:L) molar ratio
in a round bottom flask. The Ni(II) complexes were formed as insol-
uble precipitates after refluxing the reaction mixture for 2 h.
Whereas, both the Cu(II) complexes were precipitated immediately
on stirring at room temperature. The metal complexes were filtered
in a glass crucible, washed several times with methanol and finally
with diethyl ether, and dried in a desiccator at room temperature.
The single crystals of Ni(II) and Cu(II) complexes of Habh, and Ni(II)
complex of Hhbh suitable for single crystal X-ray diffraction study
were obtained by slow diffusion of diethyl ether over DMSO solu-
tion of the complexes. However, in spite of all the efforts, single
crystal of Cu(II) complex of Hhbh could not be crystallized.
2.3.1. [Ni(abh)2(DMSO)2]
Green, yield (75%). Decomp. P. 310 °C. leff = 3.13 B.M. Anal. Calc.
for C36H44N6NiO4S2 (747.60): C, 57.84; H, 5.93; N, 11.24; Ni, 7.85.
Found: C, 57.68; H, 5.89; N, 11.20; Ni, 7.80%. IR (m cm1, KBr):
m(N–H), 3463, 3242 m; m(C@N), 1591s; b(NH2), 1540s; m(C–O),
1326s; m(N–N), 975w; m(M–O), 440w; m(M–N), 421w.
2.3.2. [Cu(abh)2]
Brown, yield (74%). Decomp. P. 300 °C. leff = 1.74 B.M. Anal. Calc.
for C32H32N6O2Cu (596.2): C, 64.47; H, 5.41; N, 14.10; Cu, 10.66.
Found: C, 64.33; H, 5.37; N, 14.16; Cu, 10.58%. IR (m cm1, KBr):
m(N–H) 3470, 3271m; m(C@N), 1589s; b(NH2), 1536s; m(C–O),
1328s; m(N–N), 981w; m(M–O), 460w; m(M–N) 418w.
2.3.3. [Ni(hbh)2(DMSO)2]
Red, yield (75%). Decomp. P. 310 °C. leff = 3.15 B.M. Anal. Calc.
for C36H42N4NiO6S2 (749.6): C, 57.68; H, 5.65; N, 7.47; Ni, 7.83.
Found: C, 57.53; H, 5.63; N, 7.41; Ni, 7.76%. IR (m cm1, KBr):
m(O–H), 3292b; m(C@N), 1579s; m(C–O), 1327s; m(N–N), 981w;
m(M–O), 480w; m(M–N), 435w.
2.3.4. [Cu(hbh)2]
Brown, yield (74%). Decomp. P. 290 °C. leff = 1.77 B.M. Anal.
Calc. for C32H30N4O4Cu (598.15): C, 64.26; H, 5.06; N, 9.37; Cu,
10.62. Found: C, 64.10; H, 5.02; N, 9.33; Cu, 10.56%. IR (m cm1,
KBr): m(O–H), 3298b; m(C@N), 1583s; m(C–O), 1332s; m(N–N),
971w; m(M–O), 490w; m(M–N) 449w.
2.4. Physico-chemical measurements
The metal contents were analyzed gravimetrically by the liter-
ature procedure [24]. Carbon, hydrogen and nitrogen contents
were determined on an Exeter Analytical Inc. CHN Analyzer (Model
CE-440). 1H NMR spectra of the Habh and Hhbh were recorded in
DMSO-d6 on a JEOL AL-300 FT-NMR multinuclear spectrometer.
Chemical shifts were reported in parts per million (ppm) using tet-
ramethylsilane (TMS) as an internal standard. Infrared spectra
were recorded in KBr on a Varian 3100 FT-IR spectrophotometer
in the 4000–400 cm1 region. Electronic spectra of the complexes
were recorded on a Shimadzu spectrophotometer, model, Pharma-
spec UV-1700 in DMSO as solvent. Magnetic susceptibility mea-
surements were performed at room temperature on a Faraday
balance using Hg[Co(SCN)4] as the calibrant.
2.5. Crystal structure determination
Single crystal X-ray diffraction data for the ligands and their
complexes [Ni(abh)2(DMSO)2], [Cu(abh)2] and [Ni(hbh)2(DMSO)2]
were obtained at 293(2) K, on a Oxford Diffraction Gemini Diffrac-
tometer equipped with CrysAlis Pro., using a graphite mono-chro-
mated Mo Ka (k = 0.71073 Å) radiation source. The structures were
solved by direct method (SHELXL-97) and refined against all data by
full matrix least-square on F2 using anisotropic displacement
parameters for all non-hydrogen atoms. All hydrogen atoms were
included in the refinement at geometrically ideal position and
refined with a riding model [25,26]. The Mercury and ORTEP-3
software packages for windows program were used for generating
structures [27,28].
 M. Mishra et al. / Polyhedron 89 (2015) 29–38 31

2.6. Computational studies
All the DFT calculations were performed for the ligands and
Cu(II) complex of Hhbh using GAUSSIAN-09 suit of programs. The
compounds were treated as an closed-shell system using spin
restricted DFT wave functions (RB3LYP) for ligands and open-shell
system using spin unrestricted DFT wave functions (UB3LYP) for
complex [29], i.e., the Becke three-parameter exchange functional
in combination with the LYP correlation functional of Lee, Yang
and Parr with 6-31G(d,p) basis set for C, H, N and O atoms [30]
and effective core potentials basis set LANL2DZ (Los Alamos
National Laboratory 2 double zeta) [31] for the metal atoms. The
optimized structures were confirmed to be minima on potential
energy surface (PES) by performing harmonic vibration frequency
analyses (no imaginary frequency found). No symmetry con-
straints were applied and only the default convergence criteria
were used during the geometry optimizations. Based on the opti-
mized geometries, TD-DFT calculations were performed at the
same UB3LYP level to calculate the vertical electronic transition
energies for complex.
2.7. Corrosion inhibition measurements
Coupons of mild steel cut into 3  4  0.05 cm3 dimensions
were used for weight loss measurements whereas specimens of
size 3  1  0.05 cm3 were used as working electrode for electro-
chemical impedance spectroscopy (EIS) measurements. Prior to
the experiments, the specimens were mechanically abraded with
320, 400, 600, 800, 1000, 1500 and 2000 grade of emery papers.
It was then degreased with acetone, washed with double distilled
water and dried in air before immersing in the corrosive medium.
The corrosive solution, 0.5 M of H2SO4 was prepared by dilution
of analytical grade H 2SO4 of predetermined normality with triple
distilled water, respectively. 50 ppm concentration of ligands and
their Ni(II) and Cu(II) complexes were used in 150 ml volume of
electrolyte for each measurement.
Finely polished and dried mild steel specimens of dimension
3  4  0.05 cm3 were weighed on a digital balance with sensitiv-
ity of 0.001 g and immersed for 24 h in each 0.5 M acidic solution
in the absence and presence of 50 ppm of the inhibitor at 308 K.
The corroded/inhibited specimens were washed thoroughly by
liquid soap, rinsed severally with distilled water, cleaned, dried
using acetone and reweighed. The weight loss was calculated as
the difference in weight of the specimen before and after immer-
sion in corrosion media.
In all the above measurements, three close values were consid-
ered, and their average values are reported. The corrosion rate (CR)
in mg cm2 h1 was calculated from the following equation:
DW
CR ¼
st
where, DW is average weight loss, s the total area of the specimen,
and t is the immersion time. From the corrosion rate thus obtained,
the inhibition efficiency (g) was calculated as follows:
CR  CR
g% ¼  100
CR
where, CR° and CR are the corrosion rates of mild steel specimens in
the absence and presence of inhibitor, respectively.
Electrochemical measurements were carried out in a conven-
tional three electrode cell assembly. This assembly consisted of flat
bottom Pyrex glass flask with three openings, each for working
electrode, reference electrode and counter electrode. A rectangular
working electrode of mild steel with an exposed surface area of
1 cm2 was attached through a copper rod fixed with the help of a
screw and the rest being covered with lacquer. A platinum
electrode and a silver–silver chloride electrode with 3 M KCl salt
bridge were used as a counter and reference electrode, respec-
tively. The experiments were measured after 30 min of immersion
in the electrolytic solution in presence and absence of inhibitor.
The working electrode was immersed in the test solution and the
constant steady state (open circuit) potential was recorded when
it became virtually a constant. After attaining the steady state, ano-
dic and cathodic polarization studies were conducted using Elec-
trochemical Analyzer (CHI604A Model).
Electrochemical impedance spectroscopic (EIS) measurements
were carried out using ac signals of 5 mV amplitude for the fre-
quency spectrum from 100 kHz to 0.01 Hz. The Nyquist represen-
tations of the impedance data were analyzed with Zsimpwin
software. The electrode was kept for half an hour in the test solu-
tion before starting the impedance measurements. The charge
transfer resistance (Rct), was obtained from the diameter of the
semicircle of the Nyquist plot. The inhibition efficiency of the
inhibitor has been estimating from Rct values in presence and in
presence of inhibitor by using Eq. (3).
Rct  Rct
g% ¼  100 ð3Þ
Rct
where, Rct and Rct are the charge transfer resistance values without
and with the addition of inhibitor.
In Tafel polarization study, polarization curves were recorded
from 250 to +250 mV with respect to corrosion potential with a
scan rate of 1.0 mV/s. The linear Tafel segments of anodic and
cathodic curves were extrapolated till the point of intersection to
obtain corrosion potential (Ecorr) and corrosion current density
(icorr). Inhibition efficiency has been calculated by using respective
icorr values in place of corrosion rates (CR) in Eq. (2).
The polarization resistance (Rp) values were calculated by per-
forming linear polarization measurements (LPR) in the potential
range Ecorr ±10 mV with the scan rate of 0.1 mVs1. Polarization
resistance (Rp) values were obtained from the resulting current
density versus potential plot. The inhibition efficiency of the inhib-
itor has been determined by replacing Rct and Rct with Rp and Rp ,
respectively, in the Eq. (3).
3. Results and discussion
The analytical data of metal complexes reveal that the reactions
between metal(II) acetates and ligands are performed in 1:2 (M:L)
molar ratio (Scheme 1). The ligands enolize and deprotonate
ð1Þ
ð2Þ
Scheme 1. Formation of metal complexes.
32 M. Mishra et al. / Polyhedron 89 (2015) 29–38
during complexation. The metal complexes are intensely colored
solids and thermally stable up to 250 °C. They are insoluble in
water and common organic solvents viz. ethanol, methanol, chlo-
roform, benzene, cyclohexane, acetone and diethyl ether but are
soluble in DMF and DMSO.
3.1. Electronic spectra and magnetic moments
Electronic spectra of the ligands and their metal complexes are
measured in DMSO solution. The free ligands exhibit strong
absorptions in the range 292–297 nm due to intra-ligand p ? p⁄
transitions. The absorption bands observed in the range 307–
341 nm are attributed to the n ? p⁄ transition of azomethine
group. A bathochromic shift of 15–20 nm in this absorption band
upon complexation is due to the donation of a lone pair of elec-
trons to the metal center indicating the coordination of azome-
thine nitrogen [32,33]. The magnetic moment values 3.13 and
3.15 B.M. observed for the Ni(II) complexes of Habh and Hhbh,
respectively, suggest the presence of two unpaired electrons. The
Ni(II) complexes also show two d–d absorption bands at 775 and
568 nm for Habh complex, and 782 and 573 nm for Hhbh complex,
attributable to the 3A2g ? 3T2g (F) (m1) and 3A2g ? 3T1g (F) (m2) tran-
sitions, respectively. The third transition 3A2g ? 3T1g (P) (m3), could
not be distinguished because it is overlapped with charge transfer
transition. The appearance of m2 band as doublet indicates a distor-
tion in the regular octahedral geometry for the complex [34]. The
Cu(II) complexes of Habh and Hhbh exhibit a leff value of 1.80
and 1.77 B.M., respectively, corresponding to one unpaired elec-
tron. They show a broad d–d transition band centered at 648 and
631 nm for Habh complex and Hhbh complex, respectively, sug-
gesting a distorted square planar geometry [35].
Fig. 1. ORTEP diagram of the ligands (a) Habh and (b) Hhbh showing atomic numbering scheme with 30% probability of thermal ellipsoids.
3.2. 1H and 13
C NMR
1
H NMR spectra of free ligands Habh and Hhbh show weak sig-
nal corresponding to –NH proton at 10.59 and 11.02 ppm, respec-
tively. The signals due to Ar–NH2 proton in Habh and Ar–OH
proton in Hhph appear at 6.09 ppm and 11.49 ppm, respectively.
In addition, the signals due to –CH3 and –CH2 protons are observed
at 1.06 and 2.88 ppm for Habh, and 1.16 and 2.80 ppm for Hhbh,
respectively (Figs. S1 and S2).
In 13C NMR spectra of Habh and Hhbh, a cluster of peaks are
observed in the region 137.25–115.39 ppm and 136.75–
116.47 ppm, respectively, corresponding to aromatic carbons of
phenyl rings. The signals at 156.72 and 161.78 ppm, and 156.12
and 161.75 ppm in Habh and Hhbh are attributed to –C@N and –
C@O carbons, respectively (Figs. S3 and S4).
3.3. IR spectra
The IR spectra of the ligands show characteristic absorption
bands at 1650, 1623 and 942 cm1 for Habh, and 1643, 1605 and
959 cm1 for Hhbh corresponding to m(C@O), m(C@N) and m(N–N),
respectively. In all the metal complexes, m(C@N) band shifts
towards lower wave number by 22–34 cm1 suggesting coordina-
tion of azomethine-N to metal. Moreover, the m(N–H) and m(C@O)
bands are absent in the metal complexes and two new bands
appear in the range 1332–1326 cm1 and 1611–1589 cm1
assigned as m(C–O) and m(C@N), respectively. This indicates the
enolization of C@O group of the ligands during complex formation
and bonding occurs through carbonylate-O. In the complexes, m(N–
N) shifts to higher frequency by 10–39 cm1, suggesting involve-
ment of one of the nitrogen atom of the N–N group in bonding.
 M. Mishra et al. / Polyhedron 89 (2015) 29–38 33

Table 1
Selected crystallographic data of Habh, Hhbh, [Ni(abh)2(DMSO)2], [Ni(hbh)2(DMSO)2] and [Cu(abh)2].

Habh Hhbh [Ni(abh)2(DMSO)2] [Ni(hbh)2(DMSO)2] [Cu(abh)2]

Empirical formula C16H17N3O C16H16N2O2 C36H44N6NiO4S2 C36H42N4NiO6S2 C32H32N6O2Cu
Formula weight 267.33 268.31 747.60 749.57 596.18
Temp (K) 293(2) 293(2) 293(2) 293(2) 293(2)
k (Å) 0.71073 0.71073 0.71073 0.71073 0.71073
Crystal system orthorhombic orthorhombic monoclinic monoclinic monoclinic
Space group Pbn21 Pbca P21/c P21/c C2/c
a (Å) 5.9739(9) 13.0563(8) 11.3447(6) 8.5591(6) 28.183(11)
b (Å) 9.3372(12) 11.9877(7) 9.3896(4) 17.4335(12) 6.4473(12)
c (Å) 25.374(3) 18.2531(13) 18.1480(9) 12.6161(7) 18.837(6)
b (°) 90 90 103.421(6) 97.614(6) 121.57(5)
V (Å3) 1415.4(3) 2856.9(3) 1880.37(16) 1865.9(2) 2916.3(16)
Z 4 8 2 2 4
Dcalc (g/cm3) 1.255 1.248 1.320 1.334 1.358
l (mm1) 0.081 0.083 0.673 0.680 0.789
F(0 0 0) 568 1136 788 788 1244
Crystal size (mm) 0.25  0.22  0.20 0.25  0.23  0.21 0.22  0.21  0.20 0.22  0.21  0.20 0.24  0.22  0.21
h range for data collection (°) 3.21–27.47 3.21–26.35 3.17–26.35 3.26–26.35 3.27–26.35
No. of reflections collected 12 547 7711 7635 7698 6614
No. of independent reflections (Rint) 3250 (0.0500) 2905 (0.0280) 3842 (0.0268) 3810(0.0421) 2967 (0.0582)
Number of data/restraints/parameters 3250/1/183 2905/0/184 3842 /0/226 3810/0/228 2967/0/188
Goodness-of-fit (GOF) on F2 1.014 1.013 1.027 1.028 1.042
R1, wR2a,b [(I > 2r(I))] 0.0447, 0.0956 0.0651, 0.1516 0.0546, 0.1373 0.0585, 0.1140 0.0653, 0.1534
R1, wR2a,b (all data) 0.0762, 0.1085 0.1155, 0.1844 0.0793, 0.1547 0.1122, 0.1409 0.1175, 0.2007
Largest difference in peak and hole 0.130, 0.127 0.483, 0.274 0.723, 0.463 0.580, 0.402 0.589, 0.879
a
R1 = R||Fo|  |Fc||R|Fo|.
b
R2 = [Rw(|F2o|  |F2c|)2/Rw|F2o|2]1/2.

The non ligand bands at 440–490 cm1 and 418–449 cm1 have
been assigned to m(M–O) and m(M–N), respectively. The band
observed in the region 917–920 cm1 in the Ni(II) complexes, is
assigned to m(S@O) of coordinated DMSO molecule [36].
3.3.1. Crystal structure of the ligands Habh and Hhbh
Fig. 1a and b show the ORTEP diagrams of ligands Habh and
Hhbh with atomic numbering scheme. The crystallographic data,
structural refinement details are given in Table 1. Some selected
bond lengths, bond angles and hydrogen bonding parameters of
the ligands are given in Tables 2 and 3. Both the ligand molecules
display a similar Z molecular conformation about the C@N bond.
The bond distances C(7)–O(1), 1.234(2) and C(8)–N(3) 1.292(3) Å
for Habh and C(7)–O(1), 1.226(3) and C(8)–N(2), 1.272(3) Å for
Hhbh, correspond to typical double bonds. N(2)–N(3) and N(1)–
N(2) bond distances are 1.382(2) and 1.378(3) Å for Habh and
Hhbh, respectively, which are slightly shorter than the single bond
distance (1.411(7) Å), indicating a partial double bond character.
The torsion angles C(8)–N(3)–N(2)–C(7), 178.06° and N(3)–
N(2)–C(7)–O(1), 2.65°, in Habh ligand indicate that the C(8) and
C(7) is anti-periplanar to each other while O(1) and N(3) is syn-
periplanar to each other. Similarly, for Hhbh ligand, the torsion
angles C(8)–N(2)–N(1)–C(7), 172.73° and N(2)–N(1)–C(7)–O(1),
2.23°, indicate C(8) and C(7) is anti-periplanar to each other
and O(1) and N(2) is syn-periplanar to each other. Both inter-
and intra-molecular hydrogen bonding interactions are clearly vis-
ible in the crystal structure of Habh and Hhbh, which stabilize the
molecular conformation. The intra-molecular hydrogen bond in
Habh, N(1)–H  O(1) is formed between amine-H and carbonyl-O,
and intermolecular hydrogen bond N(2)–HO(1) is formed
between amido-H and carbonyl-O atoms of two adjacent ligand
molecules (Fig. S5). However, in Hhbh, intramolecular hydrogen
bond N(1)–H  O(2) is formed between amido-H and hydroxyl-O,
and intermolecular O(2)–H  O(1) hydrogen bond is formed
between hydroxyl-H and carbonyl-O atoms of two adjacent ligand
molecules (Fig. S6). In Habh ligand, the intra-molecular C–H  p
interactions occur between the centroid of phenyl rings and
methyl proton of propiophenone with the contact distance of
3.676 Å and inter-molecular C–H  p interaction between the
centroid of phenyl ring and phenyl proton with the contact dis-
tance of 3.771 Å (Fig. S7).
3.3.2. Crystal structures of Ni(abh)2(DMSO)2] and [Ni(hbh)2(DMSO)2]
Figs. 2 and 3 are the ORTEP diagrams of isostructural [Ni(abh)2
(DMSO)2] and [Ni(hbh)2(DMSO)2] complexes, respectively, with
atomic numbering scheme. The crystallographic data along with
the selected bond lengths and angles are presented in Tables 1
and 2, respectively. The crystals are comprised of monoclinic unit
cells in the space group P21/c. In both the complexes, Ni(II) metal
ions have distorted octahedral geometry and are coordinated to
two mono-anionic ligands via a azomethine-N, carbonylate-O at
equatorial position and two DMSO-O on axial positions. The
Ni–N(azomethine), Ni–O(carbonylate) and Ni–O(DMSO) bond lengths are
2.106(3)/2.127(3), 1.997(2)/2.011(2) and 2.139(2)/2.108(2) Å in
[Ni(abh)2(DMSO)2] and [Ni(hbh)2(DMSO)2] complex, respectively.
These bond lengths fall in the normal range of many octahedral
Ni(II) complexes with N,O-donor ligands [37]. The observed bond
angles N(3)–Ni–O(1), 77.40(10)°; O(1)–Ni–O(3), 90.03(11)°, O(3)–
Ni–N(3), 91.42(10)°; and O(3)–Ni–O(3), 180.00(7)° for [Ni(abh)2
(DMSO)2] complex and N(2)–Ni–O(1), 77.77(11)°; O(1)–Ni–O(3),
87.68(11)°, O(3)–Ni–N(2), 88.13(1)°; and O(3)–Ni–O(3), 180.0(3)°
for [Ni(hbh)2(DMSO)2] complex, respectively, indicate that the
octahedral geometry is slightly distorted due to chelation effect.
The torsion angles in [Ni(abh)2(DMSO)2] complex, O(1)–C(7)–
N(2)–N(3), 1.80° and C(8)–N(3)–N(2)–C(7), 165.15°, indicate that
the O(1) and N(3) are syn-periplanar to each other and, C(8) and
C(7) are anti-periplanar to each other. In the complex [Ni(hbh)2
(DMSO)2], the torsion angles N(2)–N(1)–C(7)–O(1), 2.99° and
C(7)–N(1)–N(2)–C(8), 172.22°, indicate that the N(2) and O(1)
are syn-periplanar to each other and, C(7) and C(8) are anti-peri-
planar to each other.
In the [Ni(abh)2(DMSO)2] complex, intra-molecular hydrogen
bond N(1)–H  N(2) is formed between amine-H and amido-N
atom whereas, inter-molecular hydrogen bond N(1)–H  O(3)
between amine-H(1) and DMSO-O atoms (Fig. S8). In [Ni(hbh)2
(DMSO)2] only intra-molecular hydrogen bond O(2)–H  N(1) is
formed between hydroxyl-H and amido-N atom (Fig. S9).
The [Ni(abh)2(DMSO)2] complex is stabilized by intra-molecular
34 M. Mishra et al. / Polyhedron 89 (2015) 29–38

Table 2 Table 3
Selected bond lengths and angles of Habh, Hhbh, [Ni(abh)2(DMSO)2], [Ni(hbh)2 Hydrogen bond parameters [Å and] in Habh, Hhbh, [Ni(abh)2(DMSO)2], [Ni(hbh)2
(DMSO)2] and [Cu(abh)2]. (DMSO)2] and [Cu(abh)2].

Bond lengths (Å) Bond angles (°) D–H  A D–A H. . .A D. . .A D–H. . .A

Habh Habh
N(3)–C(8) 1.292(3) C(8)–N(3)–N(2) 118.56(16) N(2)–H(2)  O(1)#1 0.86 2.16 2.997(2) 165
N(3)–N(2) 1.382(2) O(1)–C(7)–N(2) 120.72(19) N(1)–H(1B)  O(1) 0.86 2.10 2.705(3) 126
C(7)–O(1) 1.234(2) O(1)–C(7)–C(1) 121.09(19) C(6)–H(6)  O(1)#1 0.93 2.50 3.078(3) 120
C(7)–N(2) 1.358(3) N(2)–C(7)–C(1) 118.19(17) C(15)–H(15A)  O(1)#1 0.97 2.28 3.116(3) 144
C(2)–N(1) 1.365(3) N(1)–C(2)–C(3) 119.7(2) #1 = 1/2  x, 1/2 + y,z
N(1)–C(2)–C(1) 122.6(2)
Hhbh
C(7)–N(2)–N(3) 116.83(15)
N(1)–H(1)  O(2) 0.86 1.95 2.622(3) 134
Hhbh O(2)–H(2)  O(1)#1 0.82 1.76 2.580(3) 169
O(1)–C(7) 1.226(3) C(8)–N(2)–N(1) 117.5(2) C(3)–H(3)  O(1)#1 0.93 2.48 3.152(3) 129
N(2)–C(8) 1.272(3) O(1)–C(7)–N(1) 120.7(2) C(6)–H(6)  O(1) 0.93 2.42 2.751(4) 101
N(2)–N(1) 1.378(3) O(1)–C(7)–C(1) 121.0(2) #1 = 1/2 + x, 1/2  y, 1 – z
C(7)–N(1) 1.340(3) N(1)–C(7)–C(1) 118.3(2)
[Ni(abh)2(DMSO)2]
O(2)–C(2) 1.357(3) N(2)–C(8)–C(9) 115.6(3)
N(1)–H(00A)  O(3)#1 0.86 2.21 3.051(3) 165
C(7)–N(1)–N(2) 119.2(2)
N(1)–H(00B)  N(2) 0.86 2.06 2.698(4) 130
[Ni(abh)2(DMSO)2] C(6)–H(008)  O(1) 0.93 2.37 2.717(4) 102
Ni–O(1) 1.997(2) O(1)–Ni–O(1)#1 180.00(13) C(15)–H(01A)  O(1)#2 0.97 2.28 3.089(7) 141
Ni–O(1)#1 1.997(2) O(1)#1–Ni–N(3) 77.40(10) #1 = x, 1 + y, z; #2 = 1  x, 1  y, 1  z
Ni–N(3) 2.106(3) O(1)–Ni–N(3)#1 102.60(10)
[Ni(hbh)2(DMSO)2]
Ni–O(3) 2.139(2) N(3)–Ni–N(3)#1 180.00(14)
O(2)–H(2)  N(1) 0.82 1.80 2.527(4) 147
S(1)–O(3) 1.509(2) O(1)–Ni–O(3)#1 89.97(11)
C(6)–H(6)  O(1) 0.93 2.47 2.790(5) 100
O(1)–C(7) 1.274(4) O(1)–Ni–O(3) 90.03(11)
C(13)–H(13)  O(2)#1 0.93 2.56 3.384(7) 148
N(2)–C(7) 1.306(4) N(3)–Ni–O(3)#1 88.58(10)
C(15)–H(15A)  O(1)#2 0.97 2.21 3.072(4) 147
N(2)–N(3) 1.412(4) N(3)–Ni–O(3) 91.42(10)
C(17)–H(17A)  O(3)#3 0.96 2.60 3.525(6) 163
N(3)–C(8) 1.276(5) O(3)–Ni–O(3)#1 180.00(7)
#1 = 1  x, 1  y, z; #2 = 2  x, 1  y, 1  z; #3 = 1  x, 1  y, 1  z
#1 = x + 1, y + 2, z
[Cu(abh)2]
[Ni(hbh)2(DMSO)2]
N(1)–H(3B)  N(2) 0.86 1.90 2.560(6) 132
Ni–O(1) 2.011(2) O(1)–Ni–O(1)#1 180.00(13)
C(6)–H(3)  O(1) 0.93 2.47 2.784(5) 100
Ni–O(1)#1 2.011(2) O(1)–Ni–O(3) 87.68(11)
C(15)–H(15B)  O(1)#1 0.97 2.15 2.965(7) 140
Ni–O(3) 2.108(2) O(1)–Ni–O(3)#1 92.32(11)
#1 = 1/2  x, 1/2  y, 1  z
Ni–N(2) 2.127(3) O(3)–Ni–O(3)#1 180.00
O(1)–C(7) 1.277(4) O(1)–Ni–N(2) 77.76(11)
N(1)–C(7) 1.315(4) O(1)–Ni–N(2)#1 102.24(11)
N(1)–N(2) 1.402(4) O(3)–Ni–N(2)#1 91.87(11)
N(2)–C(8) 1.287(4) O(3)–Ni–N(2) 88.13(11)
O(2)–C(2) 1.342(4) O(1)–Ni–N(2)#1 102.24(11)
N(2)–NiN(2)#1 180.00(1)
#1 = x, y + 1, z + 1
[Cu(abh)2]
Cu–O(1) 1.904(3) O(1)–Cu–O(1)#1 180.0(2)
Cu–N(3) 2.048(4) O(1)–Cu–N(3) 81.62(13)
O(1)–C(7) 1.279(5) O(1)–Cu–N(3)#1 98.38(13)
N(1)–C(2) 1.324(5) N(3)–Cu–N(3)#1 180.00
N(3)–C(8) 1.281(6)
N(3)–N(2) 1.424(5)
N(2)–C(7) 1.307(5)
#1 = x + 1/2, y + 1/2, z + 1

C–H  p interactions between the centroid of phenyl ring and

methyl proton (3.662 Å) of propiophenone and inter-molecular
C–H  p interactions between the centroid of phenyl ring and phe-
nyl proton (2.788 Å) (Fig. S10). However, only inter molecular
C–H  p interactions are observed in [Ni(hbh)2(DMSO)2] between
the centroid of phenyl rings and methyl proton of DMSO (2.854
and 3.418 Å) (Fig. S11).
3.3.3. Crystal structures of [Cu(abh)2]
An ORTEP diagram of [Cu(abh)2] complex with atomic number-
ing scheme is shown in Fig. 4 and its selected bond lengths and
bond angles are presented in Tables 1 and 2. The Cu(II) complex
crystallizes in the monoclinic unit cell with C2/c space group. The
molecule posses a two-fold symmetry in which symmetrical atoms
are generated by symmetry operation = x + 1/2, y + 1/2, z + 1.
The metal center coordinates with two molecule of a ligand
through azomethine-N, and carbonylate-O forming a distorted
square planar geometry shared by two fused five-membered che-
late rings {CuN3N2C7O1}. The C(8)–N(3) bond length (1.280(5) Å)
Fig. 2. ORTEP diagram of [Ni(abh)2(DMSO)2] showing atomic numbering scheme
with 30% probability of thermal ellipsoids (symmetric atoms are generated by
symmetry operation = x + 1, y + 2, z).
in the complex is longer than the ligand (1.290(2) Å) due to coor-
dination of azomethine-N to the metal ion. The N(2)–C(7) distance
(1.306(5) Å) in the complex is significantly shorter than the free
ligand (1.358(3) Å) because of deprotonation of imine group. The
O(1)–C(7) bond length (1.279(5) Å) is significantly longer than
the free ligand (1.234(2) Å) due to enolization of >C@O group dur-
ing complexation. The bond distances for Cu–N(3) and Cu–O(1) are
2.048(4) and 1.904(3) Å, respectively, which are comparable to the
bond lengths reported for similar Cu(II) complexes with N,O-donor
ligands [1,38]. The bond angles O(1)–Cu–N(3), 81.62(13)°; O(1)–
Cu–N(3)#, 98.38(13)° and O(1)–Cu(1)–O(1)#, 180.0(2)° indicate a
distorted square planar geometry for the complex. The torsion
angles N(3)–N(2)–C(7)–O(1), 1.28°, and C(8)–N(3)–N(2)–C(7),
179.97° indicate that N(3) and O(1) are syn-periplanar but C(8)
 M. Mishra et al. / Polyhedron 89 (2015) 29–38
Fig. 3. ORTEP diagram of [Ni(hbh)2(DMSO)2] showing atomic numbering scheme
with 30% probability of thermal ellipsoids (symmetric atoms are generated by
symmetry operation = x, y + 1, z + 1).
Fig. 4. ORTEP diagram of [Cu(abh)2] showing atomic numbering scheme with 30%
probability of thermal ellipsoids (symmetric atoms are generated by symmetry
operation = x + 1/2, y + 1/2, z + 1).
and C(7) are anti-periplanar to each other. N(1)–H(1B)  N(2)
intra-molecular hydrogen bond is formed between amine N(1)–
H(1B) and amido-N atom (Fig. S12). The complex is well stabilized
due to presence of inter-molecular p  p interactions between the
centroid of phenyl ring and five membered chelate ring (3.686 Å)
and intra-molecular C–H  p interactions between the centroid of
phenyl ring and methyl proton of propiophenone (3.646 Å)
(Fig. S13).
3.4. DFT optimized structure of [Cu(hbh)2]
The density functional theory calculations were carried out in
gas phase to optimize the structure of [Cu(hbh)2] complex, using
coordinates from the CIF file of [Cu(abh)2] complex. The DFT opti-
mized structure is shown in Fig. 5. The selected bond lengths and
bond angles of the complex are given in Table S1. The bond dis-
tances Cu–O(2), Cu–O(4), Cu–N(2) and Cu–N(4) are 1.916, 1.916,
2.110 and 2.110 Å, which are comparable to the bond lengths
reported for similar Cu(II) complexes in literature [38]. The
observed bond angles around the metal center agree reasonably
well with other reported Cu(II) complexes of N,O donor ligands
in distorted square planar system [38]. The bond lengths
35
Fig. 5. ORTEP diagram of optimized geometry of [Cu(hbh)2] showing atomic
numbering scheme.
N(1)–C(7), N(3)–C(17), C(8)–N(2) and C(24)–N(4) are 1.321,
1.321, 1.301 and 1.301 Å, respectively, which correspond to typical
double bond characteristic.
The experimental IR spectral data for the complex [Cu(hbh)2]
have been correlated with the DFT calculated data based on peak
intensities and peak frequencies (cm1) (Table S2). Apart from
some minor deviations in theoretical group frequencies from the
experimental (5–30 cm1), the theoretical–experimental agree-
ment is satisfactory. Little deviations are due to the negligence of
anharmonicity in B3LYP method [39]. The average error in fre-
quencies calculated with B3LYP method is reported to be of the
order of 40–50 cm1 [40].
In order to get a deeper understanding of the electronic transi-
tions, TD-DFT calculations have also been performed. The assign-
ments of the calculated transitions to the experimental bands are
based on the criteria of energy and oscillator strength of the calcu-
lated transitions. In the description of the electronic transitions,
only the main components of the molecular orbitals are taken into
consideration. The calculated absorption bands for the complex are
shown by the vertical lines together with experimental UV–Vis
spectrum in Figs. S14 and S15 and the band assignments are given
in Table S3 with their oscillator strengths and energies. The results
of time-dependent density functional theory (TD-DFT) calculations
at the UB3LYP level reveal that the band calculated in the region
285–378 nm is due to mixed ligand ? metal (LMCT) and intra-
ligand (ILCT) charge transfer transitions. The other low energy
absorption band at 698 nm is due to d–d transition with smaller
oscillator strength. The orbital analysis of above d–d transition sug-
gests that it originates from dz2 ; dx2 y2 to dxy, dyx, and dxz orbitals, as
expected for a distorted square planar Cu(II) complex (Fig. S16).
3.5. Corrosion inhibition efficiency
3.5.1. Weight loss measurement
Corrosion inhibition study of Habh, Hhbh and their Ni(II) and
Cu(II) complexes were performed by using weight loss measure-
ment. The concentration of both the ligands and their complexes
was chosen to be 50 ppm. From Table 4, it is observed that Habh
exhibits better inhibition efficiency than Hhbh. This difference in
inhibition efficiency is because of the presence of –NH2 group in
Habh which increases p electron density to greater extent and as
compared to –OH group in Hhbh. This results in better adsorption
of Habh on the corroding surface. Hence, all the metal complexes of
36 M. Mishra et al. / Polyhedron 89 (2015) 29–38

Table 4
Weight loss and electrochemical parameters for mild steel in 0.5 M H2SO4 in absence and presence of 50 ppm concentration of Habh and Hhbh and their metal complexes at
308 K.

Inhibitor Weight loss EIS

CR (mg cm2 h1) g (%) Rct (X cm2) CPE g (%)
Y0 (l X sn cm2) n
Blank 4.920 – 7 1952 0.965 –
Habh 1.878 61.8 19 796 0.944 63.2
[Ni(abh)2(DMSO)2] 1.225 75.1 29 494 0.946 76.0
[Cu(abh)2] 3.626 26.3 10 1355 0.916 30.0
Hhbh 1.783 63.7 18 718 0.999 61.1
[Ni(hbh)2(DMSO)2] 1.333 73.0 26 566 0.943 73.1
[Cu(hbh)2] 3.847 21.8 9 1372 0.926 22.2

Fig. 6. Nyquist diagrams for mild steel in 0.5 M H 2SO4 at 308 K in the absence and presence of (a) Habh and its metal complexes, (b) Hhbh and its metal complexes.

Habh also show better inhibition than the corresponding metal
complexes of Hhbh. It has also been observed that the Ni(II) com-
plexes exhibit better efficiency than the parent ligands, but the
Cu(II) complexes show much lower efficiencies than the ligands.
3.5.2. Electrochemical impedance spectroscopy (EIS)
The corrosion behavior of mild steel in 0.5 M H2SO4 solution in
the presence of 50 ppm of all the additives was investigated using
EIS measurement. Nyquist plots for Habh and Hhbh ligands, and
their metal complexes in 0.5 M sulfuric acid are given in Fig. 6(a)
and (b). It is clear from the plots that the impedance response of
the blank solution changes with the addition of the ligands and
their metal complexes. The impedance response exhibits charac-
teristic semicircles with a little bit of distortion. The impedance
spectrum is composed of a large capacitive loop at high frequencies
followed by a small inductive loop at low frequency values. The
high frequency capacitive loop is usually related to the charge
transfer of the corrosion process and double layer behavior. On
the other hand, the low frequency inductive loop may be attributed
to the relaxation process obtained by the adsorbed species like
FeSO4 [41] or inhibitor species [42] on the electrode surface. In acid
solution, comparing with blank solution, the shape is maintained
throughout all tested complexes, indicating that the corrosion
mechanism remains unaltered on addition of any of the inhibitor
to the blank solution [43].
The Nyquist plots are analyzed by fitting the experimental data
to a simple equivalent circuit model, that includes the solution
resistance Rs and the constant phase element (CPE) placed in par-
allel to charge transfer resistance element, Rct. The value of Rct is
a measure of electron transfer across the surface and is inversely
proportional to corrosion rate. To compensate for non-homogene-
ity in the system, the capacitance is implemented as a constant
phase element (CPE) defined by two values, viz., Y0 and n. The
impedance, Z, of CPE is presented by Eq. (4).
Z CPE ¼ Y 1
n
0 ðixÞ ð4Þ
where, Y0 is a proportionality factor and ‘n’ has the meaning of
phase shift. The value of ‘n’ represents the deviation from the ideal
behavior and it lies between 0 and 1 [15]. The values of Rs, Rct and
CPE are obtained from the above mentioned equivalent circuit and
are presented in Table 4. The value of Rct increases while the double
layer capacitance decreases with the change of inhibitor. The
increase in Rct values is attributed to the formation of an insulating
protective film at the metal/electrolyte interface. The decrease in
CPE values can be attributed to a decrease in local dielectric con-
stant and/or to an increase in the thickness of the electrical double
layer, suggesting that the inhibitor molecules are adsorbed at the
interface [44,45].
3.5.3. Potentiodynamic polarization measurements
The polarization curves of mild steel in 0.5 M H2SO4 in the
absence and presence of Habh, Hhbh and their metal complexes
at 308 K are presented in Fig. 7(a) and (b). The collected parame-
ters deduced from the polarization curves such as the corrosion
 M. Mishra et al. / Polyhedron 89 (2015) 29–38 37

(a) (b)

Fig. 7. Potentiodynamic polarization behavior of mild steel in 0.5 M H2SO4 at 308 K in absence and presence of (a) Habh and its metal complexes, (b) Hhbh and its metal
complexes.

Table 5 be attributed to their larger size and more active sites for adsorp-
Linear polarization and potentiodynamic polarization parameters for corrosion of tion because of coordinated DMSO molecules at axial position.
mild steel in 0.5 M H2SO4 in the absence and presence of 50 ppm concentration of Such an increased activity of the metal chelates can be explained
Habh and Hhbh and their metal complexes at 308 K.
on the basis of the chelation theory [47]. On chelation, the polarity
Inhibitor LPR Potentiodynamic polarization of the metal ion will be reduced to a greater extent due to the over-
Rp (X cm2) g (%) Ecorr (mV) icorr g (%) lap of the ligand orbitals and partial sharing of the positive charge
(lA cm2) of the metal ion with donor groups. Further, because of this the
Blank 9.0 – 484 4228 – delocalization of p electrons increases over the whole chelate ring.
Habh 25.3 64.4 459 1529 63.8 While the Ni(II) complexes behave exactly as expected from the
[Ni(abh)2(DMSO)2] 37.8 76.2 460 977 76.8 above discussion, Cu(II) complexes exhibit very poor inhibition
[Cu(abh)2] 12.2 26.2 508 3253 23.0
efficiency, even lower than the ligands. The lower efficiency of
Hhbh 23.5 61.7 504 1626 61.5
[Ni(hbh)2(DMSO)2] 34.6 74.0 495 1086 74.3 Cu(II) complexes as compared to those of the ligands may be due
[Cu(hbh)2] 12.2 26.2 488 3356 20.6 to Jahn–Teller distortion in these complexes. The order of inhibi-
tion efficiency for the tested inhibitors in the two series is:

potential (Ecorr), corrosion current (icorr) and percentage inhibition
efficiency (g%) are shown in Table 5. From the results shown in
Tables and Figures, no systematic variation in Ecorr is seen with
the addition of inhibitor. The maximum displacement is observed
to be 25 mV with respect to OCP in either direction. The observed
variation in Ecorr is much less than ±85 mV and hence these cannot
be classified as anodic or cathodic inhibitors [46]. Further, the
decrease in anodic and cathodic current densities at a given
applied potential indicates that these compounds inhibit both
the reduction of hydrogen ion as well as the dissolution of metal.
This suggests that ligands and the metal complexes are mixed
inhibitors. From the linear polarization studies, it has been
observed that the polarization resistance Rp increases on addition
of inhibitor to the blank solution (Table 5).
The increase in polarization resistance in the presence of the
inhibitor suggests that a poorly conducting physical barrier is
formed at the metal electrolyte interface. This barrier is formed
due to the adsorption of ligands and their metal complexes on mild
steel surface. Inhibition efficiencies observed from LPR study are
almost equal to those obtained earlier from other measurements.
As expected, [Ni(abh)2(DMSO)2] and [Ni(hbh)2(DMSO)2] give the
highest inhibition efficiency of 75.1% and 73.0% at 50 ppm because
of high polarization resistance (37.8 and 34.6 X cm2).
Both Ni(II) complexes of Habh and Hhbh, used in the present
investigation are found to possess distorted octahedral structure
while Cu(II) complexes have four-coordinated distorted square
planar geometry. From the data of Tables 4 and 5, the increased
efficiency of Ni(II) complexes compared to Habh and Hhbh may
NiðIIÞ complex > ligand > CuðIIÞ complex
The above order of inhibition efficiency can also be explained in
terms of the size of the central metal Ni(II) > Cu(II) metal ion.
3.6. Theoretical investigation on corrosion inhibition of ligands
To compare the corrosion inhibition efficiency of ligands Habh
and Hhbh, their geometries were optimized by DFT method
(Fig. S17). The quantum chemical parameters listed in Table S4, such
as the energy gap DE (ELUMO  EHOMO) and dipole moment (l) were
obtained for molecules to predict their activity in corrosion inhibi-
tion. Frontier orbital density distribution is useful in predicting
adsorption centers of the molecules responsible for the interaction
with metal surface. It can be seen from Fig. S17 that the ligands have
slightly different distribution of HOMO and LUMO energy levels.
The HOMO of Habh shows greater electron density at NH2 group
attached to the benzene ring than OH group in Hhbh. It is well doc-
umented that the higher values of EHOMO are likely to indicate a ten-
dency of the molecule to donate electrons to appropriate acceptor
state of molecule with low energy. A molecule with lower DE is
more polarisable and is generally associated with a high chemical
reactivity [48]. Quantum chemical parameters reveal that Habh
has higher EHOMO and lower DE value, which is obvious from its
higher inhibition efficiency than Hhbh. It has been reported that
low values of dipole moment favor the accumulation of inhibitor
molecules on the metal surface [49]. From DFT study, it is concluded
that Habh may exhibits better inhibition efficiency than Hhbh.
38 M. Mishra et al. / Polyhedron 89 (2015) 29–38
4. Conclusion
This paper describes the synthesis and characterization of two
Schiff bases, Habh and Hhbh and their Ni(II) and Cu(II) complexes.
The single crystal structure of the ligands and three of the metal
complexes reveals that Ni(II) form a distorted octahedral geometry
while Cu(II) adopts a distorted square planar structure. The molec-
ular structures of the complexes are well stabilized by H-bonding
and other weak interactions. The ligands bind through azome-
thine-N, carbonylate-O to metal ions. The geometry of [Cu(hbh)2]
complex has also been optimized by DFT and TD-DFT calculations.
The corrosion inhibition behavior of the synthesized compounds
has also been studied for mild steel in 0.5 M H2SO4 medium.
Acknowledgements
The authors thank the Head, Department of Chemistry, Banaras
Hindu University, for providing laboratory and instrumental facil-
ities. One of the authors (V.P.S.) is grateful to UGC, New Delhi for
financial assistance and two of the authors (M.M. and K.T.) are
thankful to CSIR, New Delhi for awarding Senior Research
Fellowship.
Appendix A. Supplementary data
The Figs. S1–S17 and Tables S1–S4 are available in supplemen-
tary materials. CCDC 1012767, 1012768, 1012770, 1012771 and
1012772 contain the supplementary crystallographic data for
Habh, Hhbh, [Ni(abh)2(DMSO)2], [Ni(hbh)2(DMSO)2] and
[Cu(abh)2], respectively. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/10.
1016/j.poly.2015.01.003.
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