Synthesis, characterisation and structural studies of complexes containing different schiff bases with Mn (lll) and Mn (II) transition metals

Article abstract of DOI:10.13005/ojc/290440

The Schiff bases 5-methyl2-hydroxyacetophenonemorpholine-N-thiohydrazide, 5-methyl2-hydroxyacetophenoneantipyrine 5-chloro2-hydroxyacetophenonemorpholine- N-thiohydrazone has reacted with MnII and MnIII to form co-ordination compounds having general formu

Full text of DOI:10.13005/ojc/290440

ISSN: 0970-020 X
CODEN: OJCHEG
2013, Vol. 29, No. (4):
Pg. 1579-1584
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Synthesis, Characterisation and Structural Studies of
Complexes Containing Different Schiff Bases
with Mn (lll) and Mn (II) Transition Metals
GULREz NIzAMI, POONAM GARG and SHAMIM AHMAD
*Department of Chemistry, Bareilly College, Bareilly, India.
Department of Chemistry, Mohammad Ali Jauhar University, Rampur - 244 901, India.
*Corresponding author E-mail: gulrezkhurramnizami@gmail.com
http://dx.doi.org/10.13005/ojc/290440
(Received: November 03, 2013; Accepted: December 14, 2013)
ABSTRACT
The Schiff bases 5-methyl2-hydroxyacetophenonemorpholine-N-thiohydrazide, 5-methyl2-
hydroxyacetophenoneantipyrine 5-chloro2-hydroxyacetophenonemorpholine-N-thiohydrazone has
reacted with MnII and MnIII to form co-ordination compounds having general formula
[M (C14H19O2N3S) 3H2O] Cl; [M (C14H19O2N3S).3H2O]; [M (C20H20N3O2) 2] Cl; [M (C20H20N3O2)
2];[M(C13H14O2N3SCl).3H2O]Cl and [M(C13H14O2N3SCl].3H2 O] respectively.
Where M=Mn III and Mn II.The adducts have been characterized on the basis of elemental analyses
molar conductance, I.R , visible spectra, magnetic susceptibility measurement andTGA.The ligands
behave in dibasic tridentate manner in 5-methyl2-hydroxyacetophenon emorpholine-N-thiohydrazone
and 5-chloro2-hydroxyacetophenonemorpholine-N-thiohydrazone. While5-methyl2hydroxyacetoph
enoneantipyrine behaves in monobasic tridentate manner. All these compounds are paramagnetic
in nature and have octahedral geometry.
Key words: Coordination compounds, Molar conductance and magnetic susceptibility.
INTRODUCTION
anticancer and herbicidal applications2,3.They serve
as models for biologically important species and
find applications in biomimetic catalytic reaction.
Chelating ligands containing N, O and S donor
atoms show broad biological activity and are of
special interest because of the variety of ways in
which they are bonded to metal ions. It is known
that the existence of metal of metal ions bonded
to biologically active compounds may enhance
their activities4,6.The variety of possible Schiff base
Schiff bases have been used as chelating
ligands in the field of co-ordination chemistry and
their metal complexes are of great interest for many
years It is well known that N and S atoms play a
key role in the co-ordination of metals at the active
sites of numerous metallobiomolecules1. Schiff base
metal complexes have been widely studied because
they have industrial, antiungal, antibacterial,

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The complexes of different Schiff bases
metal complexes with wide choice of ligands and
coordination environments, has prompted us to (5- methyl 2- hydroxy acetophenone morpholine-
undertake research in this area7. The survey of N-thiohydrozone,5-chloro2hydroxy acetophenone-
chemical literature has revealed that Schiff bases morpholine-N-thiohydrazone and 5-methyl 2-hydroxy
possess strong ability to form complexes8. The acetophenone antipyrine) with Mn (III) and Mn (II)
Schiff bases have been investigated because of have been synthesized in the lab. The structures of
easy synthesis & remarkable versatility towards these complexes have been proposed on the basis
coordinating ability with transition metals9-13. The of elemental analyses, electronic and IR spectral
Schiff base compounds have received much data and magnetic properties.
attention owing to their significant biological activities
and medicinal properties such as anti oxidative14, anti
tumor15, antiviral16, antineoplastic17 and antimicrobial
activities18.
EXPERIMENTAL
The carbonyl compounds and the
compounds of amino group used for the preparation
4-Aminoantipyrine MorpholineNthiohydrazone
5-chlorol2-hydroxyacetophenon 5-methyll2-hydroxyacetophenon
of Schiff bases were of AR grade or equivalent were carried out at CDRI (Lucknow). The magnetic
purity.The carbonyl compounds (5-methyl2-hydroxy susceptibility was measured by GOUY method.
acetophenone and 5-chloro2-hydroxy acetophenone) CuSo4 .5H2O was used as calibrant. U.V-visible
and amino compounds (morpholine-N-thiohydrazide spectra were recorded with the help of Beckmans-
and 4-amino antipyrine) were used for the preparation DU at Chemistry Deptt.Bareilly College Bareilly.The
of Schiff base. The metal salts used were MnCl2 conductivity measurement was carried out at room
and MnCl3 (Glaxo). Other chemicals like ethanol, temperature and 10-3M dilution using conductivity
methanol (Glaxo) DMF (Rankem), DMSO (Glaxo) bridge model 910. The thermo gravimetric analysis
etc were of highest purity and used as such.
was carried out at G.N.D. University Amritsar. Anti
bacterial and anti fungal activities were carried out
Infrared spectra and elemental analyses at IVRI Bareilly.
5-methyl2-hydroxyacetophenonemorpholine-N-thiohydrazide
5-methyl2-hydroxyacetophenoneantipyrine
5-Chlorol2-hydroxyacetophenonemorpholine-N-thiohydrazide

NIzAMI, Orient. J. Chem., Vol. 29(4), 1579-1584 (2013)
1581
Preparation of ligands
The Schiff bases were prepared by
the condensation of Carbonyl compounds and
compounds containing amino group. 1.41 gm of
Morpholine N-Thiohydrazide was dissolved in
Ethanol and refluxed on water bath for half an hour.
Then 1.50 gm 5- methyl 2- hydroxy acetophenone
was added to it and refluxed for about five hours.
. 1.41 gm of Morpholine N-Thiohydrazide was
dissolved in Ethanol and refluxed on water bath for
half an hour. Then one mole 5- chloro 2- hydroxy
acetophenone was added to it and refluxed for about
five hours. Similarly 2.06 gm of 4-Amino antipyrine
was dissolved in methanol.Then 1.50 gm 5- methyl
2- hydroxy acetophenone was added to it and
refluxed for about five hours. The crystal of ligand
so obtained was purified by recrystalization. The
purity of crystal was checked by TLC and melting
point. The ligands were characterized by elemental
analysis, electronic and I-R spectra.
Preparation of complexes
All the metal complexes were synthesized
by adding respective metal salts solution drop wise
to the solution of the ligand (5- methyl 2- hydroxy
acetophenone morpholine –N- thiohydrozone,
5chloro 2 hydroxy acetophenone morpholine N
thiohydrozone, 5 methyl 2 hydroxy acetophenone
anti pyrine) prepared. The precipitate obtained was
filtered and washed with suitable solvents (DMSO
and DMF) and dried in vacumm desiccator over
fused P4O10
RESULTS AND DISCUSSION
The analytical data of 5-methyl 2-hydroxy
acetophenone morpholine N thiohydrozone Mn
III chloride complex and 5- methyl 2- hydroxy
acetophenone morpholine N thiohydrozone Mn II
complexes indicated 1/1 metal-ligands stoichiometry
for the complex and hence the molecular formulae
comes out to be [Mn (C14H19O2N3S)3H20]+Cl-
& [Mn(C14H19O2N3S) 3H20] respectively.
Similarly 5-chloro 2- hydroxy acetophenone
morpholine N thiohydrozone Mn III chloride,
5chloro 2 hydroxy acetophenone morpholine N
thiohydrozone Mn II complexes also indicated M/L
ratio 1/1. Hence molecular formulae of complex
comes out to be [Mn(C13H14N3O2SCl) 3H2O]
Cl and [Mn(C13H14N3O2SCl)3H2O] respectively.

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The analytical data indicated 1:2 metal-ligand as [Mn(C20H20N3O2S)2]Cl & [Mn (C20H20N3O2S)2]
ratio for the 5-methyl2-hydroxyacetophenonean respectively. The m.p of the metal complexes was
tipyrineMn(III)chloride complex and 5-methyl2- found to be much higher than that of the ligand which
hydroxyacetophenonean-tipyrineMn(II) complex. indicated the formation of the adduct.
Hence the M.F formula of the adduct may be written
5-methyl2-hydroxyacetophenoneanti pyrineMn(III)
chloride complex
5-methyl2-hydroxyacetophenoneantipyrine Mn(II)
complex
5me2-hydacetophenonemorpholine-N-
thiohydrazideMn(II)Complex
5chl2-hydacetophmorpholine thiohydrazideMn(II)
Complex
5chl2-hydacetophenonemorpholine-N-thiohydrazid
Mn(III)chlorideComplex
5me2-hydacetophenonemorpholine-N-thiohydrazid
eMn(III)chlorideComplex

NIzAMI, Orient. J. Chem., Vol. 29(4), 1579-1584 (2013)
1583
The values of molar conductance in DMF The IR spectrum of the complexes exhibited
and DMSO AT 10-3 dilution and 250C indicated some new bands.The band at 3100 to 3480 cm-1 may
1:1 electrolytic nature of 5-methyl 2- hydroxy be attributed to OH of coordinated water. This is
acetophenone morpholine-N-thiohydrazone Mn further supported by the band at 810 to 880 cm-1 may
(III) chloride and 5-chloro2-hydroxy acetophenone be due to rocking & wagging modes of coordinated
morpholine N-thiohydrozone Mn (III) chloride water molecules23-24
complex. While Mn (II) complexes of respective
.
ligands were found to be non electrolytic in nature.
This inference of IR spectrum regarding the
5-methyl 2-hydroxy acetophenone antipyrine Mn (III), presence of coordinating water molecule is further
chloride complex indicated 1:1 electrolytic nature supported by TGA.The thermogram shows the loss
and Mn (II) complex of respective ligand indicated of three water molecules above 150 to 1700c. In the
non electrolytic nature of the complex.The values of far IR region two bands were observed at the range of
magnetic moment Came out to be about 5.93 B.M 400 to 480 & 500 to 590 cm-1 which may be assigned
for Mn+3 and About 4.70 for Mn+2 complexes18-20
.
to M-N & M-O vibrations respectively22.
The electronic spectra of Mn (III) complexes
The i.r. spectra of the complexes of
recorded in DMF, exhibited four bands in the range 5- methyl2-hydroxyacetophenoneantipyrine on
of 13590 to 14084 cm-1 , 16450 to1695 cm-1 ,18220 comparison with that of ligands indicated co-
to 20202 cm-1 and 25600 to 25641 cm-1 (16) may be ordination through cyclic C=O, phenolic oxygen
assigned respectively to the transitions B1 →5A1 , and azomethine nitrogen.This indicated monobasic
5
5
5
5B1 → B1 , 5B1 → E & LMCT.
tridentate nature of the ligand. The band due to
OH present at 3500 cm-1 which disappeared on
The electronic spectra of Mn (II) complexes complexation and appearance of new band at
were also recorded in DMF, exhibited three bands at 1250 to 1270 cm-1 which indicated the bonding
17000, 24000 and28000 cm-1 corresponding to the of ionized phenolic oxygen to the metal ion26-28
.
4
4
transitions 6A1g → T1g (½1), 6A1g → T1g (ν2) and 6A1g The strong band at 1590 cm-1 characterstics of
4
→ Eg (ν3) respectively17. These are characteristics the azomethine group in the free Schiff base has
of octahedral geometry21.
shifted to lower frequency of 1560-1570 cm-1 in the
complexes indicating that azomethine N is one of
The IR spectra of complexes of 5-methyl the co-coordinating atoms in schiff base. The band
2-hydroxyacetophenonemorpholineNthiohydrozone observed at 1656 cm-1 characterstics of the cyclic
and 2-hydroxy 5-chloro acetophenone morpholine N carbonyl group of the pyrazolone ring of free Schiff
thiohydrozone indicated di-basic tri-dentate nature base has shifted to lower frequency in the i.r range
of the ligand as revealed by the comparison of this of 1610-1620 cm-1 in the complexes, indicated the co
spectrum with that of the ligand shows band due ordination of the above group with metal ion29. This
to phenolic OH and νc=s, which disappeared in is further supported by the formation of new bands
the IR spectra of the complexes and a new band in i.r spectrum of the complex at 460-475 cm-1 and
has appeared at the range of 745 to 760 cm-1. This 410-415 cm-1.Which are due to Å M-O and ÅM-N
suggested the coordination of metal ion with the bands respectively30.
ligand through thiol-sulphur and phenolic oxygen
via deprotonation. In addition to that the lowering of
νc=N in the IR spectrum complexes by 15 to 20 cm-1
indicated the coordination of azomethine N, which
CONCLUSION
On the basis of above mentioned facts the
is further substantiated by the appearance of azine complexes may be tentatively assigned the following
chromophore at 1610 to 1615cm-1 22. This indicated octahedral geometry.
that ligand is behaving in dibasic tridentate manner
coordinating through oxygen, nitrogen and sulphur
atoms.

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