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International Journal of Inorganic and Bioinorganic Chemistry

Universal Research Publications. All rights reserved

ISSN 2249-8540
Original Article
Synthesis, Spectral Characterization and antimicrobial activity of transition metal
complexes of ((R, 2E)-2-(1-(S)-3-oxobutan-2-ylimino) acenaphthylen-2(1H)-
ylideneamino) propanoic acid
S. Magala Sathyasheeli1, S. Theodore David*2, S. Kirubaharan1, R. Biju Bennie2, C.Joel2, S.Daniel Abraham2,
V.Thanga Pandian3.
1
Infant Jesus college of Engineering, Keelavallanadu, Thoothukudi Dist, India
2
P.G.Department of Chemistry, St. John’s College, Tirunelveli-627002, India.
3
Department of Microbiology, Ayya Nadar Janaki Ammal College, Sivakasi-626124, India
*[email protected]
Received 28 June 2015; accepted 08 July 2015
Abstract
Four novel metal complexes of cobalt (II), nickel (II), copper(II) and zinc(II) were prepared with the Schiff base formed by
the condensation of acenaphthene quinone and α-L-alanine. The ligand and its complexes have been characterized by
elemental analysis, molar conductance, 13C NMR, EI-MS, electronic and infrared spectral studies.The low conductance
values reveal the non-electrolytic nature of the complexes. From electronic spectral studies octahedral geometry was
assigned to Co(II), Ni(II) and Zn(II) complexes whereas, the Cu(II) complex shows square planar arrangement. The invitro
antibacterial assay of the complexes against gram positive and gram negative bacterial strains indicate that they are
efficient biocidal agents.

© 2015 Universal Research Publications. All rights reserved

Key words: Schiff base, metal complexes, acenaphthene quinone, biocidal activity
1. INTRODUCTION subtilis, Staphylococcus aureus, E.Coli, Klebsiella
Schiff base metal complexes have been vigorously pneumonia and Pseudomonas aeruginosa.
explored because of their ease of preparation, attractive 2. EXPERIMENTAL
physical and chemical properties and their wide range of All reagents and chemicals were of analytical Grade,
applications. The azomethine(-C=N-) linkage present in purchased from Sigma-Aldrich and Merck and used as
Schiff base ligand and its metal(II) complexes have been such. The solvents employed were of 99% purity. The C13
found to show extensive biocidal activities such as NMR was recorded on a Bruker EXT-40814 spectrometer
antibacterial, antifungal, anticancer, antidiabetic activities using CDCl3 as the solvent. The mass spectral study was
[1,2]. Schiff bases having additional donor group such as carried out using JEOL -300mass spectrometer. The molar
oxygen and nitrogen form stable chelate complexes which conductance values of the complexes were measured using
have been used as drugs[3-5]. The imine group present in Systronic Conductivity bridge type 305 using DMF as
Schiff bases has been shown to be crucial to their biological solvent. Melting points of the samples were determined
activities [6].Reports on the Schiff base complexes of using ‘TECHNICO’ melting point apparatus. The FT-IR
acenaphthene quinone and amino acids are few. Further, spectra of the solid samples were recorded in Perkin Elmer
Schiff base complexes derived from amino acids can be spectrometer in the range 4000cm-1 – 400cm-1 by KBR disc
expected to exhibit still better biological activity. Keeping method. Electronic spectra were recorded using Perkin
the above facts in mind, we have synthesised and Elmer Lambda 35 UV-Visible spectrophotometer in the
characterised a Schiff base named ((R,2E)-2-(1-(S)- range of 190 – 1100 nm using DMF as the solvent.
3-oxobutan-2-ylimino)acenaphthylen-2(1H)-ylideneamino) 2.1. SYNTHESIS OF SCHIFF BASE LIGAND (L)
propanoic acid, derived by the condensation of Schiff base was prepared by condensing 1mmol
acenaphthene quinone andα-L-alanine, and its Co(II), of acenaphthene quinone (0.182g) in 25ml of
Ni(II), Cu(II) and Zn(II) complexes. They were also Dichloromethane (DCM) with 2mmol of α-L-alanine
screened for invitro antibacterial activity against Bacillus (0.178g) (Scheme 1). The mixture was then stirred
International Journal of Inorganic and Bioinorganic Chemistry 2015; 5(3): 56-60
56
overnight on a magnetic stirrer and the resulting yellow powder was obtained by slow evaporation method. It was
Table 1: Analytical and Physical data of the complexes
% of Elements
found(calc) Molar
Yield Magnetic
Complexes Empirical formula Colour conductance
(%) moment (BM)
C H N (S m2 mol−1)

66.66 4.97 8.64

CoL Co(C18H16N2O4). 2H2O Dark brown 62 35.4 5.09
(66.62) (4.95) (8.63)

66.59 4.91 8.47

NiL Ni(C18H16N2O4). 2H2O Light green 64 22.8 3.38
(66.54) (4.87) (8.44)

66.23 4.82 8.64

CuL Cu(C18H16N2O4) green 59 19.5 1.73
(66.19) (4.79) (8.62)

66.31 4.97 8.53

ZnL Zn(C18H16N2O4).2H2O yellow 68 8.9 0.00
(66.28) (4.93) (8.51)

washed with water to remove excess aminoacid and then Klebsiella pneumonia and Pseudomonas aeruginosa by
with diethyl ether to remove excess ketone and dried in Agar well diffusion method. . Mueller-Hinton agar (MHA)
vacuum desiccator over anhydrous calcium chloride. The plates were swabbed with overnight culture of respective
scheme for the synthesis of Schiff base ligand is given as bacteria. Wells were made in each of these plates using
follows: sterile cork borer. Stock solution of each compound was
prepared at a concentration of 1 mg/ml in DMSO. Required
amount of metal complexes were added into the wells and
allowed to diffuse at room temperature for 2hrs. Control
experiments comprising inoculums with cefotaxime disc
were set up. The plates were incubated at 37°C for 18-24 h.
The diameter of the inhibition zone (mm) was measured
and the activity was calculated.
Scheme 1.Synthesis of Schiff base Ligand(L) 3. RESULTS AND DISCUSSION
All the synthesized complexes are stable towards air and
2.2. SYNTHESIS OF SCHIFF BASE METAL are non-hygroscopic in nature. The complexes are insoluble
COMPLEXES (ML) in common organic solvents but are soluble in DMSO and
An equimolar methanolic solution of the Schiff base ligand DMF. The analytical and physical data of the complexes
and metal (II) chloride were mixed and refluxed for 3 are given in Table 1.
hours. The precipitated metal complex was filtered, washed 3.1. Characterization of Schiff base
with ethanol, ether and dried in vacuum over anhydrous 3.1.1 FT-IR Spectra
calciumchloride. The proposed structure for the metal Formation of Schiff base,by the condensation of two keto
complex is given in Scheme 2. groups of acenaphthene quinone with the amino group of α-
L-alanine[7],is confirmed by the presence of imine(C=N)
stretching frequency at 1598 cm-1in the FTIR spectrum.
The peak near 1718 cm-1 is associated with the C=O group
of the carboxylate moiety. The bands around 2850 cm-1 are
related to (C-H) modes of vibration. The FT-IR spectrum is
given in Fig.1

Scheme 2. Synthesis of Schiff base metal complexes (ML)

2.3 BIOCIDAL ACTIVITY
The synthesized Schiff base Co(II), Ni(II), Cu(II) and
Zn(II)metal complexes were screened for antibacterial
activities. The invitro antibacterial activity was tested
against Bacillus subtilis, Staphylococcus aureus, E.Coli, Fig.1. FT-IR Spectrum of Schiff base Ligand (L)
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3.1.2. 13C NMR spectra observed at 188.35 ppm and azomethine carbon is observed
The 13C NMR spectrum of the Schiff base ligand,recorded at 162.11ppm, demonstrating the formation of Schiff base.
in CDCl3, exhibit four signals,confirming the presence of 4 The 13C NMR spectrum of the ligand is given in Fig.2
different types of carbon atoms. Carboxylic carbon is

Fig.2. 13C NMR spectrum of Schiff base Ligand (L)

3.1.3 Mass spectra CuL and ZnL complexes. This clearly indicates the co-
The mass spectra of Schiff base ligand shown in ordination of free ligand with central metal ion through
Fig.3,exhibits a molecular ion peak at m/z=324 imine nitrogen [8]. It is further confirmed by the
corresponding to its formula weight. Also peaks at appearance of a new absorption band at 517 cm-1, due to
m/z=154, 126, 98 corresponds to various fragments the M – N coordination. Similarly, the frequency due to the
C3H5NO2, C10H8 and C4H5NO2respectively. carboxylic acid in the free ligand (1718cm-1), has been
shifted to 1681 cm-1, 1687 cm-1, 1701 cm-1 and 1698 cm-1,
respectively for CoL, NiL, CuL and ZnL complexes. This
confirms the coordination of the carboxylate group to the
central metal ions. This is also supported by the presence of
M–O stretching frequency at~460 cm-1. Hence we conclude
that the Schiff base (L), binds the metal ion through two
imino nitrogen atoms and two carboxylato oxygen atoms.
The other two position of the octahedral structure of CoL,
NiL and ZnLcomplexes may be occupied with two water
molecules. The CuL complex, however, shows four
Fig.3. EI-Mass spectrum of Schiff base Ligand (L) coordinated square planar geometry.

3.2 CHARACTERIZATION OF METAL

COMPLEXES
3.2.1 FT-IR Spectra
Fourier Transform Infrared spectrum is an effective tool to
elucidate the structure of the compound. The bonding mode
of the metal complexes is confirmed by comparing the IR
spectrum of the free ligand with that of the complexes. The
FTIR spectra of the complexes, shown in Fig.4, S1, S2 and
S3, illustrate that the characteristic absorption of imine
(C=N) group has been shifted from 1598 cm-1,to 1585cm-1,
1579cm-1, 1576 and 1591 cm-1, respectively for CoL, NiL, Fig.4. FT-IR spectrum of CoL complex
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3.2.2 UV-Visible Spectroscopy
UV-Visible spectroscopy is a tool to elucidate the geometry of the complexes. The electronic spectra of CoL
complex, given in Fig.5, exhibits three characteristic absorption bands at 612nm, 414nm and 321nm, corresponding to
transitions respectively, arising due to the octahedral geometry
around Co(II) ion [9,10]. The magnetic moment of Co (II) complex is found to be 5.09 BM which is in the expected range
of 4.3-5.2BM signifying octahedral geometry for the complex CoL. The NiLcomplex shows three absorption bands. The
first band appears at 892 nm corresponding to transition. The second and third absorption bands are found
at 780nm and 472nm, confirming octahedral geometry for the NiLcomlex [11,12]. The observed magnetic moment 3.38
BM, also authenticates octahedral geometry for NiL complex. In CuL complex, the first absorption band at 656nm is due
to and the second at 523 nm corresponds to transition. Hence square planar geometry can
be assigned to CuL complex.The magnetic moments 1.73BM due to one unpaired electron of the Cu (II) complex also
endorse square planar geometry. Zn (II) complexes do not show any d-d transition because of completely filled d10
configuration and are diamagnetic, hence we assume that ZnL complex also show octahedral geometry.

Fig.5 UV Visible spectrum of CoL complex

3.3 BIOCIDAL ACTIVITY complexes have high antibacterial screening potential. The
The synthesized metal complexes have been screened for antimicrobial efficacy of the metal complexes is due to co-
their invitro antibacterial activity using Klebsiellasps, ordination and chelation [13,14]. As a result of chelation,
E.Coli, Bacillus sps, Pseudomonas and staphylococcus sps. the polarity of the central metal atom is reduced, because of
The zone of inhibition against the growth of microbes is the partial sharing of its positive charge with the ligand.
given in Table 2 as well as in Fig.6. Also, the cell process is affected by the formation of
It is inferred that Cu complex has medium inhibition hydrogen bond, through azomethine nitrogen atom with the
potential against all bacteria whereas Co, Ni and Zn active centre of cell constituents [15].
Table 2. Results of Biocidal activity of Schiffbase metal complexes
Compound Bacillus species E.Coli Klebsiella species Pseudomonas species Staphylococcus species
CoL 28 22 21 29 21
NiL 24 18 --- 26 16
CuL 15 --- 17 22 14
ZnL 26 24 21 28 16
Schiff base from acenaphthene quinone and α-L-alanine
and its metal complexes with Co(II), Ni(II), Cu(II) and
Zn(II) salts were prepared. They were characterized by
analytical and spectroscopic studies. The antimicrobial
screening was done with five different bacterial strains. All
the complexes are found to be potent antibacterial agents.
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Conclusion
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Source of support: Nil; Conflict of interest: None declared

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