Synthesis and characterization of manganese, copper and zinc complexes derived from Schiff - base ligand

Article abstract of DOI:10.13005/ojc/330563

A Schiff base has been prepared by the condensation of 4- amino -3,5-dimercapto, 1,2,4-triazole with 2,4-diaminobenzaldehyde. The ligand has been used for complexation with Mn(II), Cu(II) and Zn(II) metal ions. The complexes have been characterized by their elemental analysis, molar conductivity, magnetic susceptibility, IR spectra and electronic spectra. The very low value of molar conductivity of complexes shows their non-electrolytic nature. The comparison of IR spectra of complexes with that of free ligand reveals that the ligand is coordinated through azomethine nitrogen and deprotonated thiol sulphur forming five membered heterochelates. The magnetic moment values and electronic spectral bands clearly indicate the octahedral geometry around metal ions in complexes.

Full text of DOI:10.13005/ojc/330563

ISSN: 0970-020 X
CODEN: OJCHEG
2017, Vol. 33, No.(5):
Pg. 2643-2646
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Synthesis and Characterization of Manganese, Copper and
Zinc Complexes Derived from Schiff - Base Ligand
BIRENDRA KUMAR1*, BISHWANATH KUMAR2, SUNNY KUMAR1,
DEEPAK KUMAR3 and SHIVADHAR SHARMA3
1Department of Chemistry, Jagjiwan College, Gaya, India.
Department of Chemistry, S D College, Paraiya, India.
3 Department of Chemistry, Magadh University, Bodh-Gaya, India.
*Corresponding author E-mail: birendra5556@yahoo.in
2
http://dx.doi.org/10.13005/ojc/330563
(Received: August 03, 2017; Accepted: September 02, 2017)
ABSTRACT
A Schiff base has been prepared by the condensation of 4- amino -3,5-dimercapto,
1,2,4-triazole with 2,4-diaminobenzaldehyde. The ligand has been used for complexation with
Mn(II), Cu(II) and Zn(II) metal ions. The complexes have been characterized by their elemental
analysis, molar conductivity, magnetic susceptibility, IR spectra and electronic spectra. The very
low value of molar conductivity of complexes shows their non-electrolytic nature. The comparison
of IR spectra of complexes with that of free ligand reveals that the ligand is coordinated through
azomethine nitrogen and deprotonated thiol sulphur forming five membered heterochelates. The
magnetic moment values and electronic spectral bands clearly indicate the octahedral geometry
around metal ions in complexes
Keywords: Heterochelates, Non- electrolytic, Schiff Base.
INTRODUCTION
been found to get enhanced on complexation with
metal ions14. The literature reveals that schiff base
complexes of 4-(2/,4/-diaminobenzaldimino)-3,5-
dimercapto-1,2,4-triazole has not been taken care
of .Therefore, in continuation of our previous work,15
in the present paper we report the synthesis and
characterization of Mn(II), Cu(II) and Zn(II)
complexes with Schiff base, 4-(2/,4/-diamino
-benzaldimino)-3,5-dimercapto-1,2,4-triazole.
The schiff base transition metal
complexes have invited the attention of Inorganic
Chemists because of vast applications in
pharmaceutical and industrial fields.1-5Due to their
simple synthesis and versatility, Schiff complexes
continue to remain an important and a popular area
of research as such complexes persistently play a
very significant role in understanding the various
aspect of coordination chemistry of transition
metals6-10. The schiff base of triazole derivatives
have been found pharmaceutically active.11-13 The
pharmaceutical activity of these Schiffbase have
MATERIAL AND METHOD
All the reagents used in the present work
were of AnalR grade and were used as received.

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KUMAR et al., Orient. J. Chem., Vol. 33(5), 2643-2646 (2017)
Thiocarbohydrazide,carbon disulphide, α-picoline, using Elico direct reading conductivity meter. The
pyridine,ethanol, 2,4-diaminobenzaldehyde were electronic spectra of complexes were recorded on
procured from Merck (India) and metal salts of Mn(ΙΙ), Perkin- Elmer Lamda 950 spectrophotometer. Results
Cu(ΙΙ) and Zn(ΙΙ) procured from Lova Chemic (India are given in Table .1
For the preparation of the ligand at first the
pyridinium salt of 4-amino-3,5-dimercapto-1,2,4-
triazole was prepared by refluxing the mixture of
thiocarbohydrazide and carbon disulphide in
RESULT AND DISCUSSION
The molar conductivity values of
pyridine on oil bath for one hour. There after, the complexes are indicative of their non electrolytic
pyridinium salt was treated with hydrochloric acid nature16-17. On the basis of elemental analysis and
to get 4-amino-3,5-dimercapto-1,2,4-triazole.This molar conductivity values, the complexes are
amine was refluxed with 2.4-diaminobenzaldehyde formulated as[ML2 (α-pico)2], where L is the Schiff
in ethanol in the presence of 2 drops concn sulphuric base ligand. IR spectra of complexes are very
acid for one hour to get yellow crystals of Schiff cumbersome and hence only important bands have
base, i.e.,4- (2/,4/-diaminobenzaldimino)-3,5- been assigned and explained. The IR spectra of
dimercapto-1,2,4-triazole. This ligand was used for free ligand display two bands at 3013 and 2859
complexation with metal chloride in ethanolic cm-1 which are assigned to νasym NH2 and νsym NH2
medium by usual method of reflux by adding 2 ml of stretching vibration18. These two bands do not
α- picoline. On cooling the reaction mixture the solid undergo any appreciable change in their
complex was separated out which was filtered and frequencies in the spectra of complexes. It shows
washed with alcohol. It was dried in desiccator over no coordination of NH2 group to the metal ions. The
anhydrous calcium chloride. The C, H and N band at 3010 cm-1 is assigned to νCH aromatic group
elemental analysis were carried out using Perkin while the band at 2950 cm-1 is fairly assigned toνCHof
Elmer 2400 ΙΙ elemental analyzer. IR spectra of azomethine group19-21. The strong band at 2560
ligand as well as complexes were recorded on cm-1 isassigned to νSH stretching vibration of the
Perkin-ElmerFTIRspectrophotometer(spectrumII)using ligand. In the spectra of complexes this band
KBr pellet. The magnetic moment of complexes were appears at lower frequency with highly decreased
determined by Gouy balance method at room intensity. It shows that out of two SH group one has
temperature. Determination of molar conductivity undergone deprotonation and coordination occur
of complexes with 10-3 M solution in DSMO was done though deprotonated mercapto sulphur.22 The other
Table. 1 : Anlytical data and Conductivity of the Synthesis of Compond
Compound
%Metal
Calc
% C
Calc
% H
Calc
% N
Calc
% S
Calc
µeff(B.M.) Conductivity
mhos cm-1 mole-1
(Found) (Found) (Found)
(Found) (Found)
LH
—
(—)
7.375
42.857
(42.902) (4.051)
48.326 4.564
3.968
27.778
(27.805) (25.401)
22.552 17.183
(22.538) (17.201)
22.295 16.986
(22.307) (16.978)
22.241 16.945
(22.245) (17.013)
25.397
[MnL2
(α-pico)2]
[CuL2
(α-pico)2]
[ZnL2
(α-pico)2]
5.96
2.12
—
16.20
15.48
14.00
(7.405) (48.352) (4.581)
8.432 47.775 4.512
(8.425) (47.485) (4.506)
8.654 47.659 4.501
(8.634) (47.672) (4.488)
LH = 4- (2/,4/-diaminobenzaldimino)-3,5-dimercapto-1,2,4-triazol .α-pico = α- Picoline,
Calc=Calculated

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KUMAR et al., Orient. J. Chem., Vol. 33(5), 2643-2646 (2017)
major change is found in the absorption frequency
of azomethine group of the free ligand which
absorbs at 1630 cm-1 in the spectrum of free ligand
and shifts to lower frequencies by 30-40 cm-1 in the
spectra of the complexes. It is indicative of
coordination through azomethine nitrogen of ligand.
The coordination through deprotonated mercapto
sulphur and azomethine nitrogen is further
confirmed by appearance of new bands at 510 and
370 cm-1 due to νM-N and νM-S stretching vibration
respectively in complexes.The new band appearing
at 755 cm-1 in the spectra of complexes shows the
The magnetic moment of Cu (ΙΙ) complex
is found to be 2.12 B.M. at room temperature which
shows it is magnetically dilute octahedral
complex.35-38 The electronic spectra of Cu (ΙΙ)
complex exhibit a broad band at 20350 cm-1 due to
2Eg→2T2g spin allowed transition. The broadness of
band clearly indicates the further splitting of both
2Eg and 2T2g due to departurate of symmetry from Oh
to D4h symmetry. However, the value is in good
agreement with the reported value of distorted Oh
complexes of Cu (II).5,39-43
presence of coordinated α-picoline in complexes24-28
.
Zn (II) complex is diamagnetic which is in
accordance with its d10 configuration. Hence it
doesn’t display any band in electronic spectra.
However, on the basis of elemental analysis and
molar conductivity Ohstructure is assigned to Zn (II)
complex.
The magnetic moment of Mn (ΙΙ) complex
is determined to be 5.96 B.M. which corresponds to
5 unpaired electrons. It shows that Mn (ΙΙ) complex
is paramagnetic and it is high spin complex29-32
.
Mn(ΙΙ) complex displays three bands in its electronic
spectra which may be assigned to spin forbidden
transition as below:-
The tentative structure of complexes may
be given below:-
19500 cm-1(ν1)=6A1g→4T1g(4G), 23480 cm-1
-1
(ν )=6A g→4T g(4G)and 19500 cm (ν )= 6A g→4E(4D). As the
g
2
1
2
3
1
transitions are spin forbidden and also Laporte
forbidden the intensity is very very poor. Using
Tanabe – Sugano diagram the various crystal field
parameters have been calculated with values
=
1.204, B=844.15 cm-1 Dq= 1063.63 cm-1 So
β=0.879 0.137, as according to Orgel the energy of
6
4G lies above A1gby 17B +5C. So 17B +5C = ν3.
From this the value of C is calculated to be 3029.89
cm.-1 Hence, = 3.589 which is very close to
theoretical value (3.8) for Mn (ΙΙ) complexes. The
values of various crystal field parameters are in
good agreement with the reported value for
octahedral complexes of Mn (ΙΙ).28,33-34
M=Mn, Cu and Zn X=á- picoline
ACKNOWLEDGEMENT
One of the authors Mr. Bishwanath Kumar
is thankful to the Principal, M.G. College, Gaya for
carrying out research work in its P.G. Department
laboratory.
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