Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Design, spectral characterization, DFT and biological studies of transition

metal complexes of Schiff base derived from 2-aminobenzamide, pyrrole
and furan aldehyde
Prateek Tyagi a, Sulekh Chandra a,, B.S. Saraswat b, Deepansh Sharma c
a
b
c

Department of Chemistry, Zakir Husain Delhi College, University of Delhi, JLN-Marg, New Delhi 110002, India
Department of Chemistry, School of Sciences, IGNOU, Maidan Garhi, New Delhi 110068, India
Dairy Microbiology Division, National Dairy Research Institute, Karnal 132001, Haryana, India

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Synthesis of 2-aminobenzamide

TGA curve of ligand L1 and metal complexes 79.

derived Schiff bases and their metal

complexes.
 Characterization by physical, spectral
and analytical data.
 DFT and TGA study.
1
2
 L , L coordinate in a tridentate
manner around M(II) ions.
 In vitro antimicrobial and cytotoxicity
study of synthesized complexes.

a r t i c l e

i n f o

Article history:
Received 25 October 2014
Received in revised form 19 December 2014
Accepted 4 February 2015
Available online 13 February 2015
Keywords:
Schiff base
Ni(II)
Co(II) and Cu(II) complexes
Spectroscopic studies
Antimicrobial activity
DFT calculations

a b s t r a c t
A series of two biologically active Schiff base ligands L1, L2 have been synthesized in equimolar reaction of
2-aminobenzamide with pyrrol-2-carboxaldehyde and furan-2-carboxaldehyde. The synthesized Schiff
bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar
ratio of ligand: metal as 2:1. The characterization of newly formed complexes was done by 1H NMR, UV
Vis, TGA, IR, mass spectrophotometry, EPR and molar conductivity studies. The thermal studies suggested
that the complexes are more stable as compared to ligand. In DFT studies the geometries of Schiff bases
and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On
the basis of the spectral studies an octahedral geometry has been assigned for Co(II) and Ni(II) complexes
and distorted octahedral geometry for Cu(II) complexes. All the synthesized compounds, were studied for
their in vitro antimicrobial activities, against four bacterial strains and two fungal strains by using serial
dilution method. The data also revealed that the metal complexes showed better activity than the ligands
due to chelation/coordination.
2015 Elsevier B.V. All rights reserved.

Introduction
In medicinal chemistry, benzamides derivatives are widely used
as antimicrobial agents. Benzamides derivatives are well known to
Corresponding author.
http://dx.doi.org/10.1016/j.saa.2015.02.027
1386-1425/ 2015 Elsevier B.V. All rights reserved.

possess diverse pharmacological properties, viz. antimicrobial,

analgesic, anti-inammatory, anticancer, anticonvulsant, and antimalarial to name a few [17]. The ambidentate nature of amide
group leads to the formation of regioisomers when forming a metal
complex, as it is possible to coordinate either through the nitrogen
or the oxygen atoms.

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

Heterocyclic compounds containing nitrogen, oxygen and sulfur

atoms constitute a class of compounds which shows momentous
biological activities [8]. Five membered heterocyclic compounds
in combination with aromatic moieties play a signicant role in
designing a new class of molecules which shows signicant biological behavior and a different mechanism of action. Although a
large number of antibiotics are available, drug resistance against
various pathogens is the major cause of morbidity and mortality
throughout the world. The appearance of antibiotic resistant bacterial strains makes it necessary that new class of antimicrobial
agent with substantial biological activity needs to be developed.
Schiff bases are potential antimicrobial agents and when
administered as their metal complexes, their antimicrobial activity
is further enhanced in comparison to the free ligand [9]. Metal
complexes containing amide functional groups conrm a wide
spectrum of biological activities [1015] and are also used as drugs
in medicinal elds. Very limited research has been carried out on
the synthesis of transition metal complexes with oxygen and nitrogen donor Schiff base derivatives of 2-aminobenzamide. Therefore,
it is worthwhile to carry out the synthesis and study the spectral
properties of the Schiff bases derived from the reaction of
2-aminobenzamide with pyrrol-2-carboxaldehyde and furan2-carboxaldehyde. The goal of the study presented here is to
synthesize the Co(II, Ni(II) and Cu(II) metal complexes of Schiff
base produced from condensation of 2-aminobenzamide with
furan-2-carbaldehyde and pyrrol-2-carbaldehyde and to provide a
baseline of structural data using various spectroscopic techniques,
their thermal behavior, DFT studies and antimicrobial studies.
Experimental
Materials and methods
All the chemicals were used of Anala R grade and received from
SigmaAldrich and Fluka. Metal salts were purchased from
E. Merck and used as received.
General procedure for the synthesis of ligands L1L2
Ligand L1 was synthesized by adding ethanolic solution of pyrrole-2-carbaldehyde (0.01 mol) to a magnetically stirred ethanolic
solution of 2-aminobenzamide (0.01 mol) and the mixture was
reuxed for 4 h through monitoring by TLC (Scheme 1). The reaction mixture was cooled overnight, pale yellow product was precipitated out. It was ltered, washed and recrystallized with
ethanol. The same procedure was used for the synthesis of ligand
L2.
(E)-2-(((1H-pyrrol-2-yl)methylene)amino)benzamide L1
Yield: 82(%). Color (pale-yellow). M.p. 178180 C. IR (KBr,
cm1): 1612 (HC@N), 3240 (NH2), 3112 (NH), 1668 (amide CO).
1
H NMR (DMSO-d6, d, ppm) 6.326.35 (m, 1H, pyrrole AH), 6.80
(d, 1H, J = 4.44 Hz, pyrrole AH), 7.14 (d, 1H, J = 4.48 Hz, pyrrole
AH), 7.307.33 (m, 1H, Ar AH), 7.527.55 (m, 1H, Ar AH), 7.82
(d, 1H, J = 7.2 Hz, Ar AH), 8.01 (s, 2H, D2O exchangeable, ANH2),
8.15 (d, 1H, J = 8.04 Hz, Ar AH), 8.93 (s, 1H, N@CH), 11.91 (s, 1H,
pyrrole ANH). Anal. Calcd. for C12H11N3O (213.24): C: 67.59; H:
5.20; N: 19.71; Found: C: 67.64%; H: 5.19%; N: 19.74%. Mass spectrum (ESI) [M]+ = 213.2.
(E)-2-((furan-2-ylmethylene)amino)benzamides L2
Yield: 88(%). Color (light grey). M.p. 184186 C. IR (KBr, cm1):
1615 (HC@N), 3210 (NH2), 1022 (CAOAC), 1668 (amide CO). 1H
NMR (DMSO-d6, d, ppm) 6.616.64 (m, 1H, furan AH), 6.84 (d,
1H, J = 4.4 Hz, furan AH), 7.447.47 (m, 1H, Ar AH), 7.557.66

NH2
O

O
+

NH2

Reflux Ethanol
NH2
O
N

L1, L2

N
H2N

N
M

NH2

H2N

O
O

O
O

NH2

X2

7-12

1-6
L1: R=

H
N

, L2: R=

M = Co(II), Ni(II) and Cu(II), X = Cl-1, NO3-1

Scheme 1. Preparation of the ligands L1, L2 and their metal complexes 112.

(m, 1H, Ar AH), 7.68 (d, 1H, J = 7.96 Hz, Ar AH), 7.89 (d, 1H,
J = 4.8 Hz, furan AH), 8.09 (s, 2H, D2O exchangeable, ANH2),
8.19(d, 1H, J = 8 Hz, Ar AH), 8.97 (s, 1H, N@CH). Anal. Calcd. for
C12H10N2O2 (214.22): C: 67.28; H: 4.71; N: 13.08; Found: C:
67.33%; H: 4.75%; N: 13.11%. Mass spectrum (ESI) [M]+ = 214.2.
General procedure for the synthesis of metal complexes 112
Preparation of Co(II) complexes with (E)-2-(((1H-pyrrol-2yl)methylene)amino)benzamide L1 (1).
Hot ethanolic solution (15 mL) of CoCl26H2O (2 mmol) was
added drop wise to a magnetically stirred solution of (E)-2-(((1Hpyrrol-2-yl)methylene)amino)benzamide L1 (4 mmol) in ethanol
(20 mL) (Scheme 1). The resultant mixture was reuxed for 10 h.
On keeping the resulting mixture overnight at 0 C, the product
was separated out, which was ltered off, washed with cold ethanol, ether and dried under vacuum over P4O10. The same method
was used for the preparation of other metal complexes. Physical,
analytical and spectral data of ligand and metal complexes are
given in Table 1.
Analysis
The carbon and hydrogen were analyzed on Carlo-Erba 1106
elemental analyzer. The nitrogen content of the complexes was
determined using Kjeldahls method. Molar conductance was measured on the ELICO (CM82T) conductivity bridge. ESI-MS spectra
were obtained using a VG Biotech Quattrro mass spectrometer
equipped with an elctrospray ionization source in the mass range
of m/z 100 to m/z 1000. IR spectra (CsBr) were recorded on FTIR
spectrum BX-II spectrophotometer. NMR spectra were recorded
with a model Bruker Advance DPX-300 spectrometer operating at
400 MHz using DMSO-d6 as a solvent and TMS as internal standard. The electronic spectra were recorded in DMSO on Shimadzu
UV mini-1240 spectrophotometer. Thermogravimetric analysis
(TGA) was carried out in dynamic nitrogen atmosphere

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111
Table 1
Physical measurements and analytical data of the ligand (L1, L2) and metal complexes (112).
No.

L
L2
1
2
3
4
5
6
7
8
9
10
11
12
a

Molecular mass/molecular formula

C12H11N3O [213.2]
C12H10N2O2 [214.2]
[Co(L1-H)2] [483.2]
C24H20CoN6O2
[Ni(L1-H)2] [483.1]
C24H20N6NiO2
[Cu(L1-H)2] [488.01]
C24H20N6CuO2
[Co(L1-H)2] [483.2]
C24H20CoN6O2
[Ni(L1-H)2] [483.1]
C24H20N6NiO2
[Cu(L1-H)2] [488.01]
C24H20N6CuO2
[Co(L2)2]Cl2 [558.2]
C24H20Cl2CoN4O4
[Ni(L2)2]Cl2.H2O [576.06]
C24H22Cl2N4NiO5
[Cu(L2)2]Cl2 [562.8]
C24H20Cl2CuN4O4
[Co(L2)2](NO3)2 [611.4]
C24H20CoN6O10
[Ni(L2)2](NO3)2 [611.1]
C24H20N6NiO10
[Cu(L2)2](NO3)2 [616]
C24H20CuN6O10

m/z

MP (C)

Yield (%)

Elemental analysis (%) found (calc.)

C

Ma

213.21
214.24
483.32

178
184
230

82
77
69

67.45 (67.59)
67.24 (67.28)
59.60 (59.63)

5.17 (5.20)
4.73 (4.71)
4.15 (4.17)

19.76 (19.71)
13.11 (13.08)
17.35 (17.39)

12.17 (12.19)

483.43

232

76

59.62 (59.66)

4.16 (4.17)

17.26 (17.39)

12.13 (12.15)

487.98

237

70

59.04 (59.07)

4.14 (4.13)

17.20 (17.22)

12.98 (13.01)

483.41

228

68

59.58 (59.63)

4.18 (4.17)

17.33 (17.39)

12.13 (12.19)

483.35

225

65

59.60 (59.66)

4.12 (4.17)

17.35 (17.39)

12.10 (12.15)

488.20

242

60

59.01 (59.07)

4.09 (4.13)

17.15 (17.22)

13.01 (13.02)

558.71

220

72

51.60 (51.63)

3.55 (3.61)

9.98 (10.04)

10.53 (10.56)

576.08

231

64

50.12 (50.04)

3.90 (3.85)

9.78 (9.73)

10.21 (10.19)

563.23

236

65

51.17 (51.21)

3.60 (3.58)

9.91 (9.95)

11.25 (11.29)

611.36

231

68

47.12 (47.15)

3.28 (3.30)

13.78 (13.75)

9.61 (9.64)

610.93

219

70

47.16 (47.17)

3.32 (3.30)

13.71 (13.75)

9.55 (9.60)

616.23

227

62

46.72 (46.80)

3.25 (3.27)

13.68 (13.64)

10.28 (10.32)

M = Co(II), Ni(II), Cu(II).

(30 ml/min) with a heating rate of 10 C/min using a Schimadzu

TGA-50H thermal analyzer. EPR spectra of the Cu(II) complexes
were recorded as polycrystalline sample at room temperature on
E4-EPR spectrometer using the DPPH as the g-marker.

suspension. The working inoculums of aforementioned different

microorganisms containing 105 cfu/mL suspension was prepared
by diluting the 108 cfu/mL suspension, 103 times in Brain heart
infusion broth.

DFT calculations

Preparation of antimicrobial suspension (1 mg/ml)

Dissolved 10 mg of each compound in 10 mL of dimethyl sulfoxide to achieve 1 mg/mL concentration.

The DFT calculations were performed using the B3LYP three

parameter density functional, which includes Beckes gradient
exchange correction [16], the Lee, Yang, Parr correlation functional
[17] and the Vosko, Wilk, Nusair correlation functional [18]. The
gas phase geometries of Ligand L1, L2 and metal complexes (13)
were fully optimized with respect to the energy using the 631+g(d,p) basis set using the Gaussian 09W suite [19]. Net atomic
charges had been obtained using natural bond orbital (NBO) analysis of Weinhold and Carpenter [20].
Antimicrobial studies
The newly synthesized Schiff bases L1, L2 and their metal complexes (112) were screened for their antimicrobial activity.
Antimicrobial study was assessed by Minimum Inhibitory Concentration (MIC) by the serial dilution method [21]. For this, Pseudomonas aeruginosa ATCC 15442, Escherichia coli MTCC 143,
Salmonella typhi MTCC 733, Bacillus cereus ATCC 11770, Candida
albicans MTCC 183 and Aspergillus niger MTCC 972 microorganisms
were used to investigate the antimicrobial activity. Standard drugs
used for the antibacterial and antifungal activities were
Ciprooxacin and Fluconazole respectively. Colonies of microorganisms were picked off a fresh isolation plate and inoculated in
corresponding tubes containing 5 mL of brain heart infusion broth.
The broth was incubated for 6 h at 37 C. The MC Farland No. 5
standard was prepared by adding 0.05 mL of 1% w/v BaCl22H2O
in Phosphate Buffered saline (PBS) to 9.95 mL of 1% v/v H2SO4 in
PBS. The growth of all the cultures was adjusted to Mc Farland
No. 5 turbidity standard using sterile PBS to achieve 108 cfu/mL

Preparation of dilutions
In all, for ligands L1, L2, their metal complexes (112) and standard antimicrobial i.e., Ciprooxacin for antibacterial and Fluconazole for antifungal, 28 tubes of 5 mL capacity were arranged in ve
rows with each row containing 6 tubes. 1.9 mL of brain heart infusion broth was added in the rst tube in each row and then 1 mL in
the remaining tubes. Now, 100 lL of antimicrobial suspension dissolved in dimethyl sulfoxide was added to the rst tube in each
row and then after mixing the content, 1 mL was serially transferred from these tubes to the second tube in each of the rows.
The contents of the second tube of each of the rows were mixed
and transferred to the third tube in each of the rows. This serial
dilution was repeated till the last tube in each of the rows. This
provided antimicrobial compounds concentrations of 50, 25, 12.5,
6.25, 3.125, 1.5625 mg/mL in the rst to sixth tube separately in
each row. Finally, 1 mL of 105 cfu/mL of pathogenic strains suspension was added to the rst, second, third, fourth and fth rows of
tubes respectively. Additionally with the test samples and standard
drug (Ciprooxacin/Fluconazole), the inoculum control (without
antimicrobials) and broth control (without antimicrobials and
inoculum) were also prepared. All the test tubes were then incubated for 18 h at 37 C.
In vitro cytotoxicity
In vitro cytotoxic activity of synthesized ligands L1, L2 and their
metal complexes 112 were studied using the protocol of Meyer

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

et al. Brine shrimp (Artemia salina leach) eggs were hatched in a

shallow rectangular plastic dish (22  32 cm), lled with articial
seawater, which was prepared with commercial salt mixture and
double distilled water [22]. An unequal partition was made in
the plastic dish with the help of a perforated device. Approximately
50 mg of eggs were sprinkled into the large compartment, in dark
while the matter compartment was opened to ordinary light. After
2 days nauplii were collected by a pipette from the side in ordinary
light. A sample of the test compound was prepared by dissolving
20 mg of each compound in 2 mL of DMSO. From this stock solutions 500, 50 and 5 lg/mL were transferred to 9 vials (three for
each dilutions were used for each test sample and Ld50 is the mean
of three values) and one vial was kept as control having 2 mL of
DMSO only for determine its any participating role. The solvent
was allowed to evaporate overnight. After 2 days, when shrimp larvae were ready, sea water (1 mL) and 10 shrimps were added to
each vial (30 shrimps/dilution) and the volume was adjusted with
sea water to 5 mL per vial. After 24 h the number of survivors was
counted. Data were analyzed by Finney computer program to
determine the LD50 values.

Results and discussion

The Schiff base L1 (Scheme 1) was prepared by reuxing in ethanol (2025 mL) an equimolar (0.01 mol) amount of 2-aminobenzamide and pyrrol-2-carboxaldehyde. The same method was used for
the preparation of the ligand L2. The structure of Schiff bases thus
formed was established by IR, 1H NMR, Mass spectrophotometry
and CHN analysis. The synthesized Schiff bases were soluble in
DMF, DMSO and in methanol, ethanol on heating only. The composition of the ligands was consistent with their NMR, IR, mass spectral and CHN data.
The synthesized Schiff bases was further used for the complexation with Co(II), Ni(II) and Cu(II) metal ions, using the following metal salt: CoCl26H2O for complexes 1 and 7, NiCl26H2O for
complexes 2 and 8, CuCl2 for complexes 3 and 9, Co(NO3)26H2O
for complexes 4 and 10, Ni(NO3)26H2O for complexes 5 and 11
and Cu(NO3)23H2O for complexes 6 and 12. The obtained complexes are microcrystalline solids which are stable in air and
decompose above 219 C (Table 1). They are insoluble in common
organic solvents such as acetone and chloroform, sparingly soluble
in ethanol, methanol and completely soluble in DMF and DMSO.
The molar conductance of the soluble complexes in DMF showed
values indicating that complexes 16 (1114) ohm1 cm2 mol1)
are non-electrolytes and complexes 712 (98114) ohm1 cm2
mol1) are electrolytic in nature [23]. Physical measurements
and analytical data of the complexes 112 are given in Table 1.

H NMR spectra

The 1H NMR spectra have been recorded for ligand L1 and L2.
The spectra of ligand L1 (Fig. 2) displayed azomethine (AHC@N)
proton as a singlet at 8.93 ppm. The pyrrole protons appeared as
a set of doublet and multiplet in the region 7.146.32 ppm.
Similarly, aromatic protons appears as a set of doublets and multiplets in the range 8.157.30 ppm. Pyrrole ANH proton appear as a
singlet in 11.91 ppm for the ligand L1. Similarly, in the spectra of
the ligand L2 the azomethine (AHC@N) proton appeared as a singlet at 8.97. The appeared signals of all the protons of the ligand
L1, L2 were found as to be in their expected region.
IR spectra
The characteristic bands of IR spectra of ligands L1, L2 and their
metal(II) complexes are reported in order to conrm the binding
mode of the Schiff base ligands to the corresponding metal ion.
Both ligands possessed potential donor sites like azomethine linkage (AC@N), amide group (ACONH2), furan (O) and pyrrole (ANH)
groups which have tendency to coordinate with metal ions
(Table 2). Peak corresponding to m(C@O) stretching vibrations
was absent in IR spectra of L1 and, instead, a new band assigned
to azomethine m(HC@N) linkage appeared at 1612 cm1 conrming
the formation of Schiff base [24]. Similarly, the peak at 1615 cm1
in L2 corresponds to m(HC@N) linkage. The IR spectrum of the L1, L2
shows peaks in range 32103240 due to the ANH2 vibrations [25].
The peak at 3112 cm1 in ligand L1 is assigned to (ANH) group of
pyrrole ring [26]. Similarly, the band at 1022 cm1 in ligand L2 corresponds m(CAOAC) stretching vibration of the furan ring [27]. The
comparison of the IR spectra of Schiff base ligands with corresponding metal complexes gave clue of binding modes of the Schiff
base ligand to the corresponding metal ion. The IR band due to
azomethine AN shifts to lower frequency (1422 cm1) 1590
1601 cm1, representing the coordination of azomethine AN in
the complex formation [28]. This is also conrmed by the appearance of new band in spectra of metal complexes in the range of
468492 cm1, which has been assigned to the m(MAN) bond
[29]. The m(C@O) stretching vibration of amide group at
16681670 cm1 in free ligands shifts to a lower side (1652
1658 cm1) in all metal complexes, indicating the coordination of

H
N

m/z 92.10

m/z 106.13

Mass spectra
The ESI mass spectrum of ligand showed a molecular ion peak
at m/z = 231.2 amu corresponding to [M]+, which conrms the proposed formula [C12H11N3O]+ and its base peak was observed at m/z
198. Similarly the molecular ion peak of ligand L2 shows a molecular ion peak at 214.1 and its base peak was observed at m/z 199.
Fragmentation pattern of ligand L1 is shown as Fig. 1. The mass
spectrum of the ligand L1 (Fig. 2) shows a series of peaks at
233.2, 214, 186, and 130 corresponding to various fragments. The
intensities of these peaks give the idea of the stability of the fragments. The fragmentation pattern followed the cleavage of C@N,
CAN and CAC bonds. The mass spectrum of the metal complexes
112 showing the fragmentation model beside the m/z peak value
are given in Table 1.

H
N

O
NH2

NH2

H
N

N
m/z 148.16

m/z 213.24

m/z 52.08

N
m/z 198.23

H
N

H
N

m/z 170.22

Fig. 1. Mass fragmentation pattern of ligand L1.

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

Fig. 2. (a) NMR spectra of L1 and (b) mass spectrum of ligand L1.

Table 2
Important infrared spectral bands (cm1) and their assignments.
Compound

m(HC@N)

m(CAOAC)

m(C@O)

m(MAO)

m(MAN)

L1
L2
1
2
3
4
5
6
7
8
9
10
11
12

1612
1615
1594
1597
1592
1590
1601
1597
1594
1599
1595
1593
1590
1598

1022

1668
1670
1656
1654
1652
1658
1652
1654
1655
1658
1653
1655
1658
1652

474
468
482
488
492
476
486
485
487
475
479
480
490

1012
1008
1010
1014
1009
1008

512
516
502
518
522
524
514
517
520
518
522
524

the ligands through the oxygen of amide group. The same is also
supported by the appearance of band in region of 502524 cm1,
which corresponds to m(MAO) bond [30]. A noteworthy point in
the IR spectra of all metal complexes is the position of m(NAH)
stretching vibration of NH2 of amide group. Sharp bands at
32103240 cm1 for all complexes have been found to be unaltered and are in the same position as in ligand L1 and L2 [25], which

indicates the non involvement of amido-N atom in complex

formation.
In complex 8, a broad band at 3430 cm1 and a band at
1632 cm1 corresponds to the stretching (m-OH) and bending
(d(H2O)) vibrations of uncoordinated water molecule. The appearance of sharp band in range 13821388 cm1 in complexes 912,
conrms the uncoordinated behavior of the nitrate ion. The NAH
vibration band at 3112 cm1 in IR spectra of the ligand L1 disappeared in spectra of metal complexes 16 which indicates the
deprotonation of NH moiety during complex formation. Also,
the specic band of m(CAOAC) ring vibration at 1022 cm1 in
ligand shifts to (10081014 cm1) in metal complexes 712 [27].
This is also supported by the appearance of new band in range of
502524 cm1, which has been assigned to m(MAO) bond [30].
Based on these observations it may be appreciated that the ligand
L1 coordinate uninegative tridentately around the Co(II), Ni(II) and
Cu(II) ion. However, ligand L2 coordinates neutral tridentately
around Co(II), Ni(II) and Cu(II) ion.
Conductance and magnetic susceptibility measurements
The molar conductance values of metal complexes 112 were
obtained in DMF as a solvent at room temperature and their results
in (O1 cm2 mol1) are recorded as in Table 3. Generally, higher
molar conductance values are indicative of the electrolytic nature

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

of the metal complexes and lower values shows their non-electrolytic nature. The molar conductance of the metal complexes in
DMF showed values indicating that complexes 16 (1114 ohm1
cm2 mol1) are non-electrolytes and complexes 712 (98
114.4 ohm1 cm2 mol1) are electrolytic in nature. The determined
magnetic moment (BM) values of all the metal complexes, 112 at
room temperature were recorded in Table 3. The magnetic
moment values of Co(II) complexes were found in the range of
4.824.99 BM suggesting the Co(II) complexes as high-spin with
three unpaired electrons in an octahedral environment. The Ni(II)
complexes exhibited magnetic moment values in the range of
2.912.98 BM representative of two unpaired electrons per Ni(II)
ion suggesting these complexes to have octahedral geometry
[31]. The obtained magnetic moment values 1.931.96 BM for
Cu(II) complexes are indicative of one unpaired electron per Cu(II)
ion for d9-system suggesting spin-free distorted octahedral
geometry.
Electronic spectra
The electronic absorption spectra of the Co(II), Ni(II) and Cu(II)
complexes in DMSO were recorded at room temperature and the
band positions of the absorption maxima, band assignments and
the proposed geometry are listed in Table 3. The electronic spectra
of Co(II) complexes generally showed three absorption bands in
the region at 97869892, 17,33417,759 and 29,726
30,150 cm1 which assigned to transitions 4T1g ? 4T2g(F), 4T1g ?
4
A2g(F) and 4T1g ? 4Tg(P), showing an octahedral geometry around
the Co(II) ion. The electronic spectral data of Ni(II) complexes
showed dd bands in the region 10,78511,580, 15,27516,365
and 23,21025,635 cm1 [25] respectively, to assigned the transitions 3A2g(F) ? 3T2g(F), 3A2g(F) ? 3T1g(F) and 3A2g(F) ? 3T2g(F),
which are characteristic of Ni(II) in octahedral geometry. Electronic
spectra of Cu(II) complexes show the dd transition bands in the
range 12,18815,479, 18,62119,132 and 24,40227,322 cm1
[24].These bands correspond to 2B1g ? 2A1g (dx2y2 ? dz2),
2
B1g ? 2B2g (dx2y2 ? dxy) and 2B1g ? 2Eg (dx2y2 ? dxz, dyz) transitions, respectively. On the basis of electronic transitions, a distorted octahedral geometry is suggested for Cu(II) complexes.
Thermal analysis
Thermal behavior of the complexes has been studied using
Thermogravimetric analysis from ambient temperature to 800 C
in nitrogen atmosphere. Based on the thermograms; decomposition stages, temperature ranges, decomposition product as well
as weight loss percentages of the complexes were calculated. The
TG curves were redrawn as% mass loss vs. temperature (TG) curves.
Typical TG curves for Co(II), Ni(II) and Cu(II) complexes (79) in
comparison to ligand L1 are presented in Fig. 3. The temperature

ranges and percentage mass losses of the decomposition reaction

are given in Table 4 together with evolved moiety and the theoretical percentage mass losses. The TG curve of ligand L1, refers to
two stages of mass losses at temperature ranges from 150 to
460 C. These stages involved mass losses of 100.0% and mass losses may be due to the successive losses of C12H11N3O at the given
temperature ranges [32]. All metal complexes undergo decomposition in two or three stages. In the rst stage, a peak corresponding
to the loss of uncoordinated anion (chloride), followed with subsequent removal of the ve membered heterocyclic ring in the second stage. In the third stage, there was a loss in mass
corresponding to the decomposition of primary 2-aminobenzamide moiety and as a nal stage; it left air stable metal oxide as
a residue.
EPR spectra
EPR spectra of Cu(II) complexes were recorded at room temperature as polycrystalline sample, on X band at frequency of
9.1 GHz under the magnetic-eld strength of 3000 G. The analysis
of Cu complexes gives gk = 2.1852.297, g\ = 2.0522.098 and
G = 3.033.56 (Table 3). The observed gk values for the complex
are less than 2.3 in agreement with the covalent character of the
metal ligand bond. The trend gk > g\ > 2.0023 observed for the
complex indicates that unpaired electron is localized in dx2y2 orbital of the Cu(II) ion and the spectral features are a characteristic of
axial symmetry. Thus, a tetragonal geometry is conrmed for the
aforesaid complex [33]. G = (gk  2)/(g\  2), which measures the
exchange interaction between the metal centers in a polycrystalline solid, has been calculated. According to Hathaway, if G > 4,
the exchange interaction is negligible, but G < 4 indicates considerable exchange interaction in the solid complexes [34]. The G
value for Cu complexes reported in this paper, is <4 indicating
the exchange interaction in solid complexes.
Geometry optimization and NBO analysis
Geometry optimization was done using B3LYP functional with
6-31+g(d,p) basis sets as incorporated in the Gaussian 09 W programme in gas phase. The fully optimized geometries of the ligand
L1 and complexes 13 are shown in Fig. 4. The numbering scheme
for ligand L1, and complexes 13 are given in Scheme 2. The molecular structure of complex 1 shows octahedral geometry around
the Co(II) center as revealed from the calculated bond lengths
and bond angles (Table 5). The C1AO1, C7AN1, N1AC8 and C9AN2
bond lengths become slightly longer in complexes as ligand L1
coordinates via azomethine nitrogen, oxygen of amide and by the
deprotonated nitrogen of pyrrole ring. The C1@O1 bond distance
in all complexes become longer due to the formation of MAO bond
which make the C1@O1 bond weaker. The pyrrole moiety is bent

Table 3
Conductivity, magnetic, electronic spectra EPR spectra of metal complexes 112.
No.

OM (O1 cm2 mol1)

BM (leff)

kmax (cm1)

gk

g\

1
2
3
4
5
6
7
8
9
10
11
12

11.2
13.8
12.6
14.2
12.8
13.2
99.4
98
112.2
108.6
114.4
110.8

4.78
2.93
1.94
4.72
2.91
1.93
4.89
2.98
1.95
4.83
2.93
1.96

9870, 17,542, 29,918

10,870, 15,275, 25,635
14,792, 18,621, 25,712
9786, 17,559, 29,726
10,785, 15,718, 24,710
15,479, 18,998, 24,402
9892, 17,334, 30,150
11,340, 16,122, 23,210
12,188, 19,054, 25,178
9810, 17,612, 30,012
11,580, 16,365, 24,922
13,970, 19,132, 27,322

2.297

2.232

2.185

2.242

2.098

2.065

2.052

2.075

3.03

3.56

3.55

3.22

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

Fig. 3. TGA curve of (a) ligand L1, (b) complex 7, (c) complex 8, and (d) complex 9.

Table 4
Thermal analysis data the ligand (L1) and metal complexes (79).
Comp. No.

Molecular formula

L1

C12H11N3O

[Co(L )2]Cl2
C24H20Cl2CoN4O4

[Ni(L2)2]Cl2H2O
C24H22Cl2N4NiO5

[Cu(L2)2]Cl2
C24H20Cl2CuN4O4

Stages

1st
2nd
1st
2nd
3rd
1st
2nd
3rd
1st
2nd

Temp (C)

155265
265480
150250
250415
415680
140220
220450
450715
160465
465690

out of the coordination plane and move far from Co(II) ion, which
results in the slight elongation of CoAN bond length. Similarly, the
C@O bond of the amide group moves out of the plane, which
results in increase of Co@O bond length. The CoAN and CoAO bond
lengths in complex 1 lies in the range of 2.0122.014 and 2.122
2.195 , respectively. This elongation in CoAN and CoAO bond
lengths caused a slight distortion from the regular octahedral
geometries. The bond angles in the coordination sphere of Co(II)
complexes are found approximately near to the perpendicular
value.
Similar bonding behavior is observed in case of complex 2 having Ni(II) as metal center. All the bond lengths and bond angles
have very close values as compared to complex 1. However, complex 3 having Cu(II) metal center shows a large degree of distortion
from the regular octahedral geometry. It is because of this

Decomposition species

C4H4N
C8H7N2O
Cl2
C8H8O2
C16H12N4O
HCl, 1/2 O2
C8H9O2
C16H12N4O
C10H8O2N2Cl2
C14H12N2O

Residual species

Mass loss (%)

Found

Calc.

100

100

CoO

13.46

13.42

NiO

13.04

12.96

CuO

14.22

14.13

distortion that the axial CuAO1 and CuAO10 elongates to 2.456

and 2.584 , respectively. Also the CuAN1 and CuAN10 bond
lengths elongates to 2.364 and 23.93 , respectively. This elongation in bond lengths causes a change in the bond angle values of
coordination sphere. The bond angles N1ACuAN2 and N10 ACuAN20
reduces 69.23 and 72.12 respectively. The bond angle O1ACuAO10
is found to be 164.76. The bond lengths and the bond angles within the pyrrole and benzene ring do not change signicantly on
coordination with metal ion.
Natural Bond Orbital analysis was done on complexes 13 and
the results revealed that the electronic conguration of Co(II) in
complex 1 is: [core]4s0.013d6.584p0.765s0.195p0.01, 18 core electrons,
7.55 valence electrons, and 0.023 Rydberg electrons with 25.573
electrons as a total electrons that is in agreement with the calculated natural charge (+01.421 e) on cobalt atom. Similarly, the elec-

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

Fig. 4. Geometry optimized structures of (a) ligand L1, (b) complex 7, (c) complex 8, and (d) complex 9 (colour code: H = White, C = Grey, N = Blue, O = red, Co = Grey,
Ni = Silver Grey, Cu = Pink). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

C5

C6

C4
C3

C5

C7
C2

C8
N1

C1

C 10
C9
N2

H 2N
C11

C 12

H2 N

C2

C6

C4
C3

C7

O1

(a)

C 10

C8

C9

N1
O1

N2

C 12' N 2'
C 11'

C10'

C 9'

C11

C 12

NH2

O1 '
N 1'

C8 '

C1 '
C 2'

C7 '
C 6'

C3 '
C 4'
C 5'

(b)

Scheme 2. Numbering scheme of the optimized structures (a) ligand L1 and (b) complexes 79.

tronic conguration of Ni(II) in complex 2 is [core]4s0.013d7.85

4p0.725s0.015p0.02: 18 core electrons, 8.61 valence electrons (on
4s, 3d, 4p, 5s and 5p atomic orbitals), and 0.015 Rydberg electrons
with 26.625 as a total electrons and +1.375 e as a natural charge.
The electronic conguration of Cu(II) in complex 3 is [core]4s0.31
3d8.904p0.985p0.01: 18 core electrons, 10.2 valence electrons (on
4s, 3d, 4p and 5p atomic orbitals), and 0.017 Rydberg electrons
with 28.217 as a total electrons and +0.780 e as a natural charge.
We also calculated the energies for Highest occupied molecular
orbital (HOMO) and Lowest occupied molecular orbital (LUMO).
The calculated energies of the HOMO and LUMO for ligand are

0.2278 and 0.0034 hartree, respectively. The HOMO of the ligand

is concentrated on carbonyl oxygen of amide group, while LUMO is
concentrated on C1@O1 amide bond of 2-aminobenzamide.
The 0.020 hartree isovalue contours for the HOMO and LUMO are
displayed in Fig. 5. The lower HOMO energy values shows that
the molecule electron donating ability is weak. On contrary, the
higher HOMO energy implies that the molecule is a good
electron donor. LUMO energy represent the ability of a
molecule receiving electrons. On the basis of the above discussion
following (Fig. 6) structures can be proposed for the synthesized
complexes.

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

Antimicrobial study

Table 5
Optimized geometry of the ligand and metal complexes (bond lengths in Angstroms;
bond angles in degrees).

a
b
c
d

Parametersa

Ligand L1

Complex 1b

Complex 2c

Complex 3d

C1AC2
C1AN3
C1AO1
C2AC7
C7AN1
N1AC8
C8AC9
C9AN2
MAO1
MAN1
MAN2
MAO10
MAN10
MAN20
\N1MO1
\N1MN2
\O1MN20
\N10 MN20
\N2MO10
\N1MO10
\O1MO10

1.510
1.376
1.245
1.419
1.381
1.291
1.434
1.391

1.452
1.360
1.299
1.431
1.397
1.341
1.397
1.412
2.012
2.122
2.195
2.014
2.127
2.193
85.45
82.54
88.87
82.52
84.19
84.64
177.16

1.453
1.364
1.301
1.428
1.399
1.343
1.395
1.420
2.237
2.167
2.210
2.234
2.198
2.234
82.76
83.24
85.43
81.29
85.14
82.23
172.35

1.451
1.368
1.300
1.432
1.403
1.349
1.398
1.422
2.456
2.364
2.243
2.584
2.393
2.297
87.45
69.23
84.32
72.12
78.74
81.34
164.76

After incubation, the tubes showing no visible growth were

measured to be demonstrating the minimum inhibitory concentration(MIC). Inoculum control showed growth, whereas the broth
control observed no growth. Among all the screened samples for
antimicrobial activity, 1, 6, 7, and 12 observed as signicant
antimicrobial agents at quiet low concentration and could be considered as broad spectrum antimicrobial compounds (Table 6).
Whereas metal complexes 25 and 811 showed moderate activity
against all the tested pathogens. Whereas the standard drug was
effective against all the pathogens at the concentration of
1.56253.1250 mg/mL. The biological activity results showed that
majority of the Schiff base ligands possessed increased activity
upon coordination with different metal ions.
Cytotoxic bioassay
The synthesized ligands L1, L2 and their metal complexes 112
were screened for their cytotoxicity (Brine Shrimp bioassay) using
the protocol of Meyer et al. [35]. The cytotoxic data recorded in
Table 7 revealed that all compounds were considered as almost
inactive in this assay. It was interesting to note that the metal complexes showed potent cytotoxicity as compared to the ligands. This
activity relationship may serve as a basis for future development of
certain cytotoxic agents in clinical practices.

Scheme 1 for numbering.

M@Co.
M@Ni.
M@Cu.

Fig. 5. Plot of HOMO (a) and LUMO (b) of ligand L1.

C5

C6

C4

C7

C3

C2
C1

H 2N

C 10

C8

C9

N1

N2

C10'

C6

C4

C7

C3

C 12

C2
C1

O1

C 12' N 2'
C 11'

C5
C11

C 9'

O1 '
N 1'

C8 '

NH2

C7 '
C 6'

1-6

H 2N

C1 '
C 2'

C 10

C8

C9

N1
O1

N2

C 12' N 2'
C3 '

C 11'

C 4'
C 5'

C10'

C 9'

C 12

NH2

O1 '
N 1'

C8 '

C11

X2.nH2O

C1 '
C 2'

C7 '
C 6'

C3 '
C 4'
C 5'

7: X=Cl-1, n=1, 8-9; X=Cl-1, 10-12: X=NO3-1

M = Co, Ni, Cu

Fig. 6. Proposed structure of the newly obtained metal complexes.

10

P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 143 (2015) 111

Table 6
MIC (minimum inhibitory concentration) values of L1, L2 and metal complexes 112 (mg/mL).
Compounds

L
L2
1
2
3
4
5
6
7
8
9
10
11
12
a
b

Pathogenic strains
P. aeruginosa

E. coli

S. typhi

B. cereus

C. albicans

A. niger

Ciprooxacina

Fluconazoleb

12.500
12.500
3.1250
6.2500
12.500
6.2500
6.2500
1.5625
3.1250
6.2500
3.1250
6.2500
12.500
3.1250

12.500
6.2500
1.5625
3.1250
6.2500
6.2500
0.1250
3.1250
3.1250
12.500
6.2500
1.5625
6.2500
1.5625

6.2500
6.2500
3.1250
6.2500
3.1250
3.1250
6.2500
3.1250
3.1250
6.2500
6.2500
3.1250
6.2500
3.1250

6.250
12.500
3.1250
1.5625
6.2500
3.1250
6.2500
3.1250
12.500
3.1250
1.5625
3.1250
6.2500
1.5625

12.250
12.250
12.500
12.500
6.2550
3.1250
6.2550
12.500
6.2550
6.2550
12.500
6.2550
12.500
6.2500

12.250
12.250
3.1250
6.2500
12.250
6.2500
3.1250
6.2500
6.2500
3.1250
12.250
6.2500
6.2500
3.1250

1.5625
3.1250
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625
1.5625

6.2550
6.2550
6.2550
3.1250
3.1250
6.2550
6.2550
3.1250
3.1250
6.2550
3.1250
3.1250
6.2550
3.1250

Standard antibacterial drug.

Standard antifungal drug.

Table 7
Brine shrimp bioassay data of the ligands L1, L2 and their metal complexes 112.
Compounds
1

L
L2
1
2
3
4
5

LD50 (M/mL)
3

>2.16  10
>1.98  103
>2.94  104
>3.16  103
>2.99  104
>4.35  104
>3.23  104

Compounds
6
7
8
9
10
11
12

LD50 (M/mL)
3

>4.65  10
>4.12  104
>3.76  104
>2.78  104
>3.11  104
>3.23  104
>3.87  104

Conclusion
The newly synthesized Schiff bases ligands L1, L2 act as tridentate ligands, and all these are coordinated through the azomethineN, oxygen of amide and through nitrogen of pyrrole/oxygen of
furan to the metal ion. All the synthesized metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which
showed a distorted octahedral geometry. The reasonable agreement between the theoretical and experimental data reects to
the great extent the suitability of the applied basis set, 631+g(d,p) for this type of work and conrms the suggested structure. The ndings of antimicrobial studies indicated that the Schiff
base ligands possessed mostly moderate activity and metal(II)
complexes mostly possessed moderate to signicant activities
against different bacterial and fungal strains which might be due
to azomethine (AHC@NA) linkage and/or heteroatoms present in
these compounds. The biological activity results showed that
majority of the Schiff base ligands possessed increased activity
upon coordination with different metal ions. The improvement in
biological activity upon coordination may be explained on the
basis of Overtones concept and chelation theory. The cytotoxicities
values indicates that metal complexes displayed signicant cytotoxic activities, that might help in the development of potent
antimicrobial drugs. Further structural optimization studies might
thus represent a rationale for further investigation.
Acknowledgements
We thank the Principal, Zakir Husain Delhi College for providing
lab facilities, National Dairy Research Institute, Karnal for Antimicrobial activities. Authors are thankful to Defence Research &
Development Organisation, New Delhi, India, for nancial
assistance.

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