Synthesis and Characterization of Cu(II), Co(II) and Ni(II) Complexes

with Schiff Bases Derived from Isatin

ANGELA KRIZA1, IULIANA IGNAT2*, NICOLAE STANICA3, CONSTANTIN DRAGHICI4
1
University of Bucharest, Faculty of Chemistry, Department of Inorganic Chemistry, 23 Dumbrava Roie Str., 020462, Bucharest,
Romania
2
Industrial School Anghel Saligny, Braila, 52 Gl. Eremia Grigorescu Str., Braila, Romania
3
Romanian Academy, Ilie Murgulescu Institute of Physical Chemistry, 202 Splaiul Independentei, 060021, Bucharest, Romania
4
Romanian Academy, Organic Chemistry Center Costin D. Nenitzescu, 202B, Splaiul Independentei, 060023, Bucharest,
Romania

Complexes having formula of type [M(LH)2(H2O)2](ClO4)2 [M=Cu(II), Co(II) and Ni(II)], were synthesized
where LH is formed by the condensation of 2,3-dione 1H-indole with aniline and respectively p-anisidine. We
carried out IR, UV-Vis-NIR, 1H NMR and 13C NMR spectroscopy, magnetic susceptibilities, molar conductivity
measurements and antibacterial activity. The ligands act bidentate and neutral in keto form.
Keywords: aniline, p-anisidine, isatin, Schiff bases, complexes, transitional metal, antibacterial activity

The literature has paid much attention to the study of

transitional metal complexes with Schiff bases derived
from isatin.
The interest for this type of complexes is due to the
versatility of the Schiff bases in the reaction with transitional
metal ions [1, 2]. Mostly, however, a large number of papers
are dedicated to the use of complexes with Schiff bases in
biological, pharmacological and clinical applications [36]. Isatin and its derivatives have activity antifungal,
antibacterial [7, 8] and anti-leukemic [9].
In order to investigate their potential biological activity
and as a part of our continuing goal to study transitional
metal complexes with Schiff bases in a systematic manner
[10-12], we synthesized and characterized six new
transition metal complexes based on perchlorates of Cu(II),
Co(II) and Ni(II). Were also synthesized two derivatives of
Schiff bases with aniline and isatin, whose structure was
confirmed by IR, 1H NMR and 13C NMR spectroscopy.
Experimental part
Materials, methods and instruments
We used: aniline and p-anisidine for synthesis MerckSchuchardt, isatin for synthesis Loba-Chemie
(recrystallized from methanol), metal salts for synthesis
Fluka.
The metal content was determined gravimetrically, as
follows: Co(II) as pyrophosphate, Cu(II) using
salicylaldoxime and Ni(II) with dimethylglyoxime.
The content of C, H, N, was determined by micro
combustion, using a Costech device, model ECS 4010. The
melting points were measured using a Stuart Scientific
SMPJ Melting Point Apparatus.
Molar conductivities of the complexes were measured
in 10-3M DMF solution, at room temperature, using a Consort
C-533 conductivity bridge.
The IR spectra (4000-400 cm-1) were recorded in KBr
tablet, using a BIO-RAD FTS-135 Spectrometer, and the
UV-Vis-NIR electronic spectra (200-1200 nm) were
recorded on a VSU-2P Zeiss Jena Spectrophotometer in
diffuse reflectance. The 1H-NMR and 13C-NMR spectra were
recorded at room temperature with a Gemini 300 BB
device, in DMSO solution, using TMS as internal standard.

The magnetic susceptibilities were measured at room

temperature, by the Faraday method.
The antibacterial activity was determined in a Petri plate
of 10 cm diameter. The plate, placed on a horizontal
surface, was covered with about 20 mL nutritive gelose
(Mueller-Hinton) with pH = 7.2, melted and cooled at 50C.
Synthesis of the ligand
The ligand L1H was obtained from a mixture of 10-2 mol
isatin in 100 ml ethanol and 10-2 mol aniline in 25 mL ethanol
was refluxed on a water bath for 3 h. The yellow crystallized
compound was filtered off, washed with ethanol and dried
in atmosphere. It was purified by recrystallization from
ethanol.
Elemental analysis for ligand L 1H: C 14 H 10 O 2 N, %
experimental C: 75.67; H: 4.50; N: 12.61 and % calculated
C: 75.85; H: 4.76; N: 12.53.
The determined melting point is 223oC.
The ligand L2H was synthesized in the same way from a
mixture of isatin and p-anisidine, resulting in an orange
crystallized compound.
Elemental analysis for ligand L 2H: C 15 H 12 O 2N 2, %
experimental C: 71.11; H: 4.50; N: 11.33 and % calculated
C: 71.37; H: 4.75; N: 11.10.
The determined melting point is 238oC.
Synthesis of complexes
At the hot solution of the ligand (210-3 moles in 75 mL
absolute ethanol) was added drop-wise under stirring the
solution of the metallic perchlorate (10-3 mol in 15-20 mL
absolute ethanol). The reaction mixture was stirred
continuously, at ~ 60oC. After approx. 1 hour, coloured
precipitates were removed by filtration, washed with
ethanol and diethyl ether and finally dried in vacuum over
anhydrous CaCl2.
Antibacterial studies
The antibacterial activity of ligands and its complexes
was evaluated by the diffusion technique Kirby-Bayer, in a
medium of agar nutrient and using ciprofloxacin,
gentamicin and ampicilin for control.
The samples (10-3M DMF solutions of the ligands and
the metallic complexes) were applied by a micropipette

* email: ignatiuli@yahoo.comTel.: (+40) 0723571708

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REV. CHIM. (Bucharest) 62 No. 7 2011

on paper discs of 3 mm diameter. The discs were left in an

incubator for 48 h, at 37oC, then different bacterial species
grown on blood agar plates were applied on.
A Blood agar medium (from bioMerieux) was used
for the growth of specific Gram positive bacterial species:
Staphylococcus aureus. A Cled agar medium (from
bioMerieux) was used for the growth of specific Gram
negative bacterial species: Escherichia coli and Salmonella
Typhimurium.
The discs with standard antibiotics, the ligands and the
metallic complexes solutions were deposed on the nutrient
layer Mueller-Hinton. After 24 h of incubation at 37oC, the
diameter of the inhibition surfaces was measured (in mm).
Results and discussions
The proposed structural formula of the ligands derived
from 2,3 - dione 1H - indole and aniline respectively
p-anisidine are presented in the figure 1.

Fig. 1. Structural formula of the

ligand (LH)

The 1H-NMR and 13C-NMR spectra for the ligand L1H are
presented in the figures 2 and 3 and those of the ligand L2H
in the figures 4 and 5.
The new obtained complexes are stable in air, partially
soluble in methanol, ethanol or acetone and fairly soluble
in DMF and DMSO.
The table 1 contains the elemental analysis data, the
colour, the melting points and the electrical conductibility
in DMF (10-3M). The values of the molar conductibility
indicate that all complexes are 1:2 electrolytes [13].

Fig. 2. 1H-NMR for the

ligand (L1H)

Fig. 3. 13C-NMR for

the ligand (L1H)

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697

Fig. 4. 1H-NMR for the

ligand (L2H)

Fig. 5. 13C-NMR for the

ligand (L2H)

H-NMR [DMSO-d6, (ppm), J (Hz)] Spectra

In the 1H-NMR spectrum of the ligands L1H respectively
2
L H there is a singlet at 11.00 ppm, corresponding to the
NH group proton of the isatin. The protons (H-11, H-13)
respectively (H-10, H-14) appear as triplets, in the 1H-NMR
spectrum of the ligand L1H, at =7.46 ppm and respectively
=9.96 ppm. They are equivalents two by two and have a
coupling constant J=8.3 Hz.
In the 1H-NMR spectrum of the ligand L2H the protons
(H-11, H-13) respectively (H-10, H-14) are equivalents two
by two and appear as doublets at =7.36 ppm and
respectively =7.33 ppm, with a coupling constant J=8.79
Hz.
The analysis of 1H-NMR spectra of the ligands L 1H
respectively L2H displays that doublets which appear at
=6.89 ppm (J=7.7 Hz) and =6.32 ppm (J=6.6 Hz),
respectively at =7.05 ppm (J=2.74 Hz) and =6.96 ppm
1

698

(J=2.47 Hz) are attributed to protons H-1 and H-4 from

isatin.
The proton H-3 appears also as a triplet of doublet having
coupling constants J=6.6 Hz and 1.1 Hz for the ligand L1H
and J=4.94 Hz and 2.47 Hz for the ligand L2H, the coupling
being realized with the H-2 and H-4 protons. Similarly, the
H-2 proton appear as a triplet of doublets, having the
coupling constants J=7.7 Hz and 1.1 Hz for the ligand L1H
and J=4.94 Hz and 2.72 Hz for the ligand L2H, due to
screening of the protons H-1 and H-3.
C-NMR [DMSO-d6, (ppm)] Spectra
The structure of the ligands is also confirmed by the
presence, in the 13C-NMR spectrum, of the signals at 163.48
ppm for L1H and 163.55 ppm for L2H, assigned to the C-8
carbon of the azomethine group.
13

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REV. CHIM. (Bucharest) 62 No. 7 2011

Table 1
ANALYTICAL DATA AND PHYSICAL PROPERTIES OF THE COMPLEXES

IR Spectra
The comparative analysis of the IR spectra of the free
ligands and the new obtained complexes offers important
information about the type of the coordination process
between metallic ions and organic ligands.
The most important absorption bands in the IR spectra
of the ligands and its complexes are given in table 2.
In the IR spectra of the ligands, medium intensity bands
are observed in the spectral region 3000-3200 cm-1; these
bands may be assigned to the vibration modes of NH groups
from isatinic ring.
In the double bonds region are presented bands at 1740
and 1650 cm -1 . These bands are specific stretching
frequencies of the carbonyl and azomethine groups [4].
Comparing the bands in the double bonds region, the IR
spectra of the complexes 1-6 and the ligands, important
differences are observed. The characteristic bands for C=O
and C=N groups are shifted to lower values than ligands,
that suggest their involvement in the coordination process
[14]. The bands due to vibration mode NH are practically
unchanged in the spectra of the complexes, suggested
that NH group is not involved in the coordination process
[15]. We also observed a broad band of medium intensity
in the region 3400-3300 cm-1, characteristic for the OH
groups belonging to water molecules in the structure of
the compounds, and at ~800 cm -1 it appears a band

characteristic OH, indicating a coordination of the water

molecules at the central metallic ion [16].
For all the complexes, the presence of the perchlorate
anion in the ionization sphere is indicated by the bands
which correspond to the 3 and 4 frequencies, at 1100
and 625 cm -1, that suggest the Td symmetry of the
perchlorate oxoanion is maintained in the complexes. This
fact allows us to consider that the perchlorate anion is not
involved in the coordination process [17].
The IR spectral data suggest for the two ligands a
bidentate neutral behaviour, by participating in the
coordination with the azomethinic nitrogen atom and the
oxygen atom of the carbonyl group.
Electronic spectra and magnetic properties
The data from the electronic spectra recorded in diffuse
reflectance between 200 1500 nm, correlated with the
magnetic moments values gave us important information
about the geometry of the complexes 1-6 (table 3).
The electronic spectra of the ligands L1H and L2H display
three bands what appear shifted generally to lower values
of the frequencies, reflecting the coordination at the
metallic ions. The band at 41666 cm -1 (240 nm),
respectively 38460 cm-1 (260 nm) and the band at 32258
cm-1 (310 nm), respectively 33333 cm-1 (300 nm) in the
UV-VIS spectrum are assigned to the * and n*

Table 2
INFRARED ABSORPTION FREQUENCIES (CM-1) OF LIGAND AND COMPLEXES

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Table 3
ELECTRONIC SPECTRAL BANDS
(CM-1) AND MAGNETIC DATA OF
THE LIGAND AND COMPLEXES

Table 4
THE ANTIBACTERIAL ACTIVITY
OF THE LIGAND AND
COMPLEXES

transitions, due to benzene rings and to the electronic pair

of the nitrogen atom belonging to azomethine group. The
band at 25000 cm-1 (400 nm) may be assigned to an intraligand transition [7].
In the electronic spectra of the complexes 1 and 2, a
relative broad band appears at 13888 cm -1 (720 nm),
respectively 15037 cm-1 (665 nm), corresponding to the
d xz,yz d x 2-y 2, d z 2d x 2-y 2 transitions specific to an
octahedral surrounding of the Cu(II) ion [18].
700

The magnetic moment 1.93 BM, respectively 2.01 BM,

corresponding to the spin value for one unpaired electron,
indicates a monomeric complex of the Cu(II).
The electronic spectra of the complexes 3 and 4 show
three bands as follows: the first at 23255 cm-1 (430 nm)
respectively 22727cm-1 (440 nm), corresponding to the 4T1g
4T1g(P) (3) transition; the second at 16128 cm-1 (620
nm) for the both complexes, corresponding to the 4T1g(F)
4A2g (2) transition; the third at 8695 cm-1 (1150 nm)

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REV. CHIM. (Bucharest) 62 No. 7 2011

zone is smaller than the same parameter for the

Ciprofloxacin and Ampicilin antibiotic.
Towards Escherichia coli, the ligand and its complexes
have presented a much intense inhibition zone than the
Gentamicin antibiotic.

Fig. 6. Structural formula of the complexes [M(LH)2(H2O)2](ClO4)2

[M = Cu(II), Co(II), Ni(II)]

respectively 8849 cm-1 (1040 nm), corresponding to the

4
T1g(F) 4T2g (1) transition. These transitions are specific
to an octahedral geometry [19].
Using the Knigs equations [20], the values for the
splitting parameter 10q and Racah B parameter were
calculated; these values support the proposed octahedral
geometry for the Co(II) complex. The nefelauxetic index
(table 3) also indicates a predominant ionic character of
the ML bond for the complexes Co(II).
The magnetic moment 5.04 BM, respectively 4.33 BM,
support the proposed octahedral geometry [21].
In the electronic spectra of the complexes 5 and 6 are
observed three bands: the first band at 22727 cm-1 (440
nm) corresponds to the 3A2g 3T1g(P) (3) transition, the
second band at 13072 cm-1 (765 nm), respectively 12900
cm-1 (775 nm), is assigned to the 3A2g 3T1g (2) transition,
and the third band at 8333 cm-1 (1200 nm), respectively
8771 cm-1 (1140 nm), is attributed to 3A2g(F) 3T2g(F) (1)
transitions, specific to an octahedral geometry of the Ni(II).
The magnetic moment values for the two Ni(II)
complexes, 3.23 BM, respectively 2.98 BM, support the
proposed geometry [22].
Using the same Knigs equations [20], the values for
the splitting parameter 10q and Racah B parameter were
calculated; these values are in accordance with an
octahedral surrounding of the Ni(II) ion.
The nefelauxetic index indicates, in this case, an weak
ionic character of the ML bond for the complexes Ni(II).
Based on the elemental analysis data, magnetic
susceptibilities measurements, molar conductibility
determinations and spectral studies, structural formula of
the new complexes were proposed (fig. 6).
Antibacterial activity
The antibacterial activity of the ligands L1H and L2H and
of the complexes 1-6 was tested on Gram positive and
Gram negative bacteria respectively Staphylococcus
aureus, Escherichia coli and Salmonella Typhinurium. Table
4 summarizes the experimental data on the tested
complexes, indicating the diameter of the inhibition zone
in mm. In order to appreciate correctly the antibacterial
activity of the obtained complexes, standard antibiotics,
usually used in the therapy of the diseases caused by the
respective bacteria, were tested too.
The tests indicate for all the complexes an antibacterial
activity lower than the ligands; only the Ni(II) complexes
present approximately the same values of the inhibition
zone as the ligands. Unfortunately, the value of the inhibition

Conclusions
We have synthesized six new complexes of Cu(II), Co(II)
and Ni(II) perchlorate with Schiff bases obtained by the
condensation of 2,3-dione 1H-indole with aniline and panisidine.
The structure of the ligands was confirmed by 1H-NMR
and 13C-NMR spectra.
The IR spectroscopy showed that the ligand act in keto
form, neutral bidentate, coordinating the metallic ions
through the carbonyl oxygen atom and the azomethine
nitrogen atom.
The electronic spectra and the magnetic moment values
suggest an octahedral geometry, two of the coordination
positions being occupied by water molecules. The
antibacterial activity was tested on gram positive and gram
negative bacteria using appropiated antibiotics as
reference.
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Manuscript received: 23.11.2010

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