The Clarion

The Clarion Volume 2 Number 2 (2013) PP 6-109-18
The Clarion
E
ISSN : 2277-1697
International Multidisciplinary Journal
Studies on the antimicrobial activity of Co4 (3-O)4 (-O2C.

C6H4-4-Cl)4 (4-Me-Py)4 : tetrakis (3-oxo) tetrakis (-4-chlorobenzoato-O) tetrakis (4-methylpyridine) cobalt (III)
Bapan Saha1, Hrishikesh Upadhyaya2, Soumitra Choudhury3 and Aniruddha Sen4
1. Department of Chemistry, Handique Girls College, Guwahati, India.
2,3,4. Karimganj College, Karimganj, India.
Abstract
Olive-green oxo-bridged Co (III) complex tetrakis[(3-oxo) (-4-chlorobenzoato-O) (4-methylpyridine) cobalt(III)]
having the formula Co4 (3-O)4 (-O2C.C6H4-4-Cl)4 (4-Me-py)4 is synthesized by modification of a reported synthetic
method. The synthetic method involves hydrogen peroxide oxidation of a mixture of Co (II), 4-chlorobenzoic acid and
4-methylpyridine in a 1:2:1 molar ratio in methanol. Spectral studies suggest the presence of a distorted cubane-like
core of [Co3 (3 - O)4]3+ in the complex. The complex is found to exhibit inhibitory effect on Escherichia coli in a dose
dependent manner.
Keyword : Cubane cluster, antibacterial, E. Coli.
1. Introduction
Oxo-bridged carboxylate clusters with ancillary
N- and O-donor ligands are of continued interest
because of their interesting physical properties and
varied structural motifs they display (Winpenny et
al., 2004, Winpenny et al., 2001, Beattie et al.,
1998). Oxo-bridged cluster complexes of cobalt
containing a cubane-like core have recently been the
subject of extensive studies because of their
relevance in various fields viz. materials, catalsis as
well as bioinorganic chemistry (Chakrabarty et al.,
2007). Cobalt (III) cubane-like clusters of the type
Co4O4 (O2CR)4L4, where R is a methyl or an aryl
group and L is either a pyridine or a substituted
pyridine ligand, play active role in the catalyzed
oxidation of organic substrates such as alkylaromatics, alcohols, and -pinene, with air, oxygen, or
TBHP (tetrabutyl hydroperoxide) as the oxidants
(Chakrabarty et al., 2007, Chakrabarty et al., 2007,
Sarmah et al., 2007, Chakrabarty et al., 2004,
Chakrabarty, 2009, Chakrabarty et al., 2009). The
Corresponding author : bapan.chem@gmail.com
[Co4III (3-O)4]4+ core present in these complexes

undergo a reversible one-electron oxidation to the
[Co3IIICoIV(3-O)4]5+ core (Chakrabarty et al., 2007,
Chakrabarty et al., 2009, Chakrabarty et al., 2009,
Chakrabarty et al., 2007)
During the past decades, much attention has
been given to the synthesis of new metal complexes
and the evaluation of these agents for antibacterial
activity (Aliyu et al., 2012, Chang et al., 2010, Saha
et al., 2009). This revival interest was generated by
the discovery of the antibacterial, antifungal and
anticancer activity of several metal complexes. In
the last few years so many studies has been done on
the structure and chemical behaviour of several
metal complexes to find out an alternative against
the drugs. The antimicrobial activity of Cobalt
complex against the multi drug resistant organism is
very scanty; the present study is an attempt to
understand antimicrobial activity of Cobalt complex
(Aliyu et al., 2012). More recently, cobalt (III) based
ligand complexes have been found to possess both
Saha et al., / The Clarion (2013)
antiviral and antibacterial activities (Aliyu et al.,

2012, Chang et al., 2010, Saha et al., 2009 ).
Because of their suitability as redox catalysts for the
oxidation of various organic substrates these
complexes are also expected to show some
antimicrobial property (Beattie et al., 1998). The
present work stems from our interest to study the
antimicrobial activity of redox active cobalt (III)
complex. The interesting finding of the study is the
significant antimicrobial activity displayed by the
complex.
2. Experimental Section
2.1 Materials
All chemicals used were obtained from
commercial sources and without any further
purification. Co (NO3)2.6H2O, hydrogen peroxide
were procured from E. Merck (India), 4methylpyridine E. Merck (Germany). The solvent
methanol used for synthesis was of reagent grade.
Dichloromethane, acetonitrile, DMSO and methanol
used for spectral electrochemical measurements and
antimicrobial study were of HPLC grade. One gram
negative microbial strain viz : Escherichia coli (gram
negative) were obtained from the Institutional
Biotech. Hub, Karimganj College and grown on
nutrient broth (Hi-media) at 370C in an incubator for
18-24 hrs and maintained on respective agar slant at
40C. The standard disc-diffusion method was used to
evaluate the antimicrobial activity.
2.2 Measurements
Infrared spectrum of the complex was recorded
in KBr pellets using a Perkin-Elmer RX1 FT-IR
spectrophotometer in the mid-IR region (4000-450

cm-1). Perkin-Elmer Lambda 40 spectrophotometer
is used to record the electronic spectra of the
complex. Cobalt analysis was performed gravimetrically by precipitating out cobalt as Hg[Co(NCS)4]
following standard procedure. (Chakrabarty et al.,
2007) Cyclic and differential pulse voltammetric
measurements were performed using an EG&G PAR
model 253 VersaStat potentiostat/galvanostat having
a three-electrode setup consisting of a glassy-carbon
working, platinum-wire auxiliary, and a saturated
calomel reference electrode (SCE). (Chakrabarty
et al., 2009, Chakrabarty et al., 2007)
2.3 Preparation
The complex was synthesized by following a
reported procedure in a modified form (Chakrabarty
et al., 2009). A mixture of Co(NO3)2.6H2O (2.91 g,
10 mM) and sodium-4-chlorobenzoate (3.573 g, 20
mM) in methanol (20 mL) was stirred. 4methylpyridine (0.98 mL, 10 mM) was added to the
reaction mixture and refluxed. 30% (v/v) hydrogen
peroxide solution (5 mL, ~50 mM) was then added
slowly. The reaction mixture was stirred under
refluxing condition for 4 h. Olive green compound
(~0.47 g) precipitated out during the reaction. The
cooled reaction mixture was concentrated in a
rotary-evaporator and the aqueous layer was
separated out by adding dichloromethane to it. An
olive green compound precipitated out on addition
of petroleum ether (40-60 fractions) to the
dichloromethane solution. (Chakrabarty et al.,
2009). The solid was dried in a vacuum desiccator
over fused CaCl2. Yield : 1.97 g (66.7% based on
cobalt).
Co(NO3)2 .6H2O + 4-Cl-C6H4-COONa + 4-CH3-C5H4N

H2O2(30% V/V), Reflux
4hr
CH3OH
Pink Solution
Co4(3-O)4(-O2C.C6H4-4-Cl)4(4-Me-Py)4
Olive Green ppt.
Volume 2 Number 2 (2013) 6-10
2.4 Characterisation
2.4.1 Infrared Spectra
The complex has been characterized by infrared spectroscopy in KBr phase in the mid-IR region (4000
450 cm-1). In the IR spectra, it is possible to identify bands due to bridging carboxylate anions as well
as for the N-donor pyridine ligand. The IR-stretching frequency of the complex in cm-1 is shown below.
asym (COO ) cm-1 sym (COO ) cm-1

1542
1392
pyridyl ring stretches cm-1

1625, 1512, 1494
2.4.2 Electronic Spectra

The UV-visible spectrum for the complexes is
recorded in CH2Cl2 at different concentrations. The
bands in CH2Cl2 (a) 10-3 M occur at 633 nm, and
(b) 10-4 M occur at 362 nm and 246 nm. The spectra
are slightly concentration-dependent. The lowest
energy band corresponds to the d-d transition
involving either 1A11T1 or 1A11T2 for the
approximately octahedral low-spin d6 Co(III) centers
(Chakrabarty et al., 2009, Chakrabarty et al., 2007,
3-oxo-bridge cm-1 -CH stretch cm-1

636
2930, 2826
Aliyu et al., 2012). The other two bands can be

attributed to ligand to metal charge transfer
transitions (LMCT). While the first LMCT band at
362 nm is expected to be due to a transition
involving the 3-O-Co (III) moiety present in the
complex (Chakrabarty et al., 2009), later at 246 nm
most probably involves a transition between a
molecular orbital from the carboxylato ligands and a
vacant cobalt (III) eg* orbital (Chakrabarty et al.,
2007). The uv-visible spectra of the complex in max
(CH2Cl2), nm is given below :
2.4.3 Cyclic Voltammetry

The complex is found to be electrochemically
active. The complex undergoes a one-electron
oxidation. The stoichiometry of the electron transfer
indicates that the process involves one electron
oxidation of the cubane core from [Co4III(3-O)4]4+
to [Co3IIICoIV(3-O)4]5+. (Chakrabarty et al., 2009,
2.5 Antimicrobial study

The chemicals were dissolved in DMSO in
eppendorf tubes at the concentration of 0.01mg/ml,
0.05mg/ml and 0.1mg/ml and sterile paper discs
were made from Whatman No.1 filter paper and
soaked in the respective solutions for an hour and
then left in laminar airflow hood overnight for
drying. Bacteria were cultured over night at 370C in
nutrient agar (NA) media and used as inoculums.
Using the standard disc-diffusion method with
Chakrabarty et al., 2007, Aliyu et al., 2012). The

complex also display well-shaped nearly reversible
redox behaviour. The observed E and EP values
for the complex are found to be 0.83 V and 172 mV
respectively while the DPV peak potentials ranges
from 0.84 V. Cyclic voltammogram for the complex
in CH2Cl2-0.1M TBAP vs. SCE. (scan rate of 20
mVs-1) is shown below.
sterilized glass spreader, the petridishes containing

nutrient agar were seeded. Prepared discs of 6 mm in
diameter (Whatman No-1 filter paper) containing the
compound were placed on seeded nutrient agar
plates. Tetracycline discs were used as positive
control. The organic solvents were used as negative
control. Test plates were incubated at 370C for 18-24
hours. Antimicrobial activity was evaluated by
measuring the zone of inhibition against E. coli
mean value. The experiments were conducted in
triplicates and the data was tabulated.
Figure-1 : Antimicrobial Zone formed by the compound against E. coli. (1) + control. (2)0.1mg/ml.
(3) 0.05mg/ml. (4) 0.01mg/ml. (5) control.
10
2.5.1 Result (Antimicrobial Assay)

Compounds used
Co-complex
Concentration used
Inhibition zone (mm)
0.1mg/ml
11
0.05mg/ml
0.01mg/ml
Tetracycline
Standard
17
DMSO
Standard
Table-1 : Table showing the concentration of the Co-complexes and the zone of inhibition against
Escherichia coli (microorganism).
3. Discussion
The IR, electronic spectral study and cyclic
voltammetry for the complex indicate that the
complex is found to be identical with the reported
compound (Chakrabarty, 2009) although the single
crystal structure is yet to be obtained. For one Gram
negative bacteria viz. Escherichia coli it was seen
that the compound had significant inhibitory effects
on the microbe. The result obtained from the
experiment with the Co-complex was analysed and
found that the Inhibitory zone of 11.0 mm was
exhibited by the compound at a concentration of

0.1mg/ml followed by a zone of 8.0mm at a
concentration of 0.05mg/ml. It can be inferred that
the compound was not effective at low
concentration. Though in comparison to tetracycline,
the zone formed was smaller, but it can be assumed
that if the concentration of the compound is
increased then, the potency of the antimicrobial
activity can also be increased. The effect of the
complex on gram positive bacteria was found to be
insignificant.
Acknowledgement
The authors acknowledge the assistance provided by the DBT Sponsored Institutional Biotech Hub,
Karimganj College for the experiments and UGC for financial assistance with reference to letter no
F. 5 39/10 11 (MRP/ NERO)/dated 10th March11.
References
Aliyu, A.O., Adamu, H., Maikajes D. B., 2012 : Global J. of Science Frontier Research. 12, 1
Beattie, J. K., Hambley, T. W., Klepetko, J. A., Masters, A. F., Turner, P., 1998 : Polyhedron 17, 1343
Chakrabarty, R., Das, B. K., Clark, J. H., 2007 : Green Chem. 9, 845
Chakrabarty, R., Kalita, D., Das, B. K., 2007 : Polyhedron 26, 12390
Chakrabarty, R., Das, B. K., 2004 : J. Mol. Catal. A : Chem. 223, 39
Chakrabarty, R., 2009 : PhD Thesis, Gauhati University.
Chakrabarty, R., Sarmah, P., Saha, B., Chakravorty, S., Das, B. K., 2009 : Inorg. Chem. 48, 6371
Chakrabarty, R., Bora, S. J., Das, B. K., 2007 : Inorg. Chem. 46, 9450
Chang, E.L., Simmers, C. and Andrew Knight, D., 2010 : Pharmaceuticals. 3, 1711
Saha, S., Dhanasekaran, D., Chandraleka, S., Panneerselvam, 2009 : A. FACTA UNIVERSITATIS Series : Physics,
Chemistry and Technology : 7, 73
Sarmah, P., Chakrabarty, R., Phukan, P., Das, B. K., 2007 : J. Mol. Catal. A: Chem. 268, 36.
Winpenny, R. E. P., McCleverty, J. A., Meyer, T. J., 2004 : Comprehensive Coordination Chemistry; Pergamon Press
: Oxford, Vol. 7, Chapter 7.3, pp. 125-175.
Winpenny, R. E. P., 2001 : Adv. Inorg. Chem. 52, 1-111.

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The Clarion Volume 2 Number 2 (2013) PP 6-109-18

International Multidisciplinary Journal

Studies on the antimicrobial activity of Co4 (3-O)4 (-O2C.

[Co4III (3-O)4]4+ core present in these complexes

Saha et al., / The Clarion (2013)

antiviral and antibacterial activities (Aliyu et al.,

spectrophotometer in the mid-IR region (4000-450

Co(NO3)2 .6H2O + 4-Cl-C6H4-COONa + 4-CH3-C5H4N

Volume 2 Number 2 (2013) 6-10

Saha et al., / The Clarion (2013)

asym (COO ) cm-1 sym (COO ) cm-1

pyridyl ring stretches cm-1

2.4.2 Electronic Spectra

3-oxo-bridge cm-1 -CH stretch cm-1

Aliyu et al., 2012). The other two bands can be

Volume 2 Number 2 (2013) 6-10

Saha et al., / The Clarion (2013)

2.4.3 Cyclic Voltammetry

2.5 Antimicrobial study

Chakrabarty et al., 2007, Aliyu et al., 2012). The

sterilized glass spreader, the petridishes containing

Saha et al., / The Clarion (2013)

2.5.1 Result (Antimicrobial Assay)

Inhibition zone (mm)

exhibited by the compound at a concentration of

Volume 2 Number 2 (2013) 6-10

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