P R Shirode

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Chem Sci Trans., 2012, 1(2), 396-400              Chemical Science Transactions 
DOI:10.7598/cst2012.165                  ISSN/E-ISSN: 2278-3458/2278-3318 
Synthesis and Physicochemical Studies of Mixed Ligand 
Complexes of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) with   
Acetophenone Semicarbazone and Acetone Semicarbazone 
P. R. SHIRODE  
Department of Chemistry, Pratap College, Amalner -425401, India 
prshirodepca@gmail.com 
Received 12 May 2012 / Accepted 30 May 2012 
Abstract: The mixed ligand complexes of the type [M(L1)(L2)]Cl2 (where M= Mn (II),Fe(III),Co(II), 
Ni(II) and Cu(II) and L1 =  Acetophenone semicarbazone, L2=Acetone semicarbazone) have been 
synthesized by the reactions of  metal chlorides with two different  semicarbazone  compounds in 1:1:1 
molar ratios. The resulting complexes have been characterized on the basis of elemental analysis, 
magnetic measurement, IR and electronic spectra, conductivity measurement. The metal complexes 
shows ratio 1:1:1 with metal, ligand L1 and ligand L2.The ligands acts as bidentate ligands and are 
bonded through oxygen and nitrogen to metal ion. The two co-ordination positions are occupied by 
two water molecules. The complexes have octahedral structure. 
Keywords:  Sythesis, Physicochemical studies, Semicarbaxone, Ligands 
Introduction 
Mixed ligand complexes play an important role in biological processes like activation of 
enzymes by metals
1,2
. Such complexes are useful in the storage and transport of active 
substances through membranes
3-5
. Mixed ligand complexes have been used in the analysis of 
semiconductor material. Semicarbazones constitute one of the most important class of 
oxygen and nitrogen donar ligands
6-11
. The formation of a variety of metal complexes from 
these ligands indicates the spectacular progress in coordination and bioinorganic chemistry. 
The real efforts used for developing the coordination chemistry of these ligands was 
probably due to remarkable antitumor, antimalarial, antifungal and antibacterial activities. 
They were also found to be useful as potential drugs fungicidal agents. The antibacterial and 
fungicidal activities of transition metal complexes are due to their ability to form chelates 
with the essential metal ions bonding through nitrogen as donar atom of the ligand. 
 The present course of study was initiated to understand the characteristic nature and 
applications of the biologically active metal complexes of nitrogen and oxygen donar 
ligands. By considering all these applications, in this paper we are reporting the synthesis 
and characterization of series of Mn(II), Fe(III),Co(II), Ni(II) and Cu(II) complexes obtained 
from acetophenone semicarbazone and acetone semicarbazone as ligands. 
 RESEARCH ARTICLE 
Chem Sci Trans., 2012, 1(2), 396-400                 397 
Experimental 
All the chemicals used were of Analytical reagent grade and metal salts are also of standard 
quality. All solvents are or of standard spectroscopic grade. All the transition metals were 
determined volumetrically by using EDTA using double burette technique for optimium 
utilization of reagents. Indicator Erichrome Black T is used for Mn(II), ammonium 
thiocynate for Fe(III), Xylenol orange for Co(II) and Mureoxide for Ni(II) and 
Cu(II).carbon, hydrogen and nitrogen analysis were carried out from SAIF, Mumbai. 
Specific conductance were measured at room temp and at 10 
0
C higher than room temp. In 
DMF by a systronics direct reading 304 conductivity meter using glass conductivity cell 
having cell constant 1.0 cm
-1
. Magnetic measurements were carried out at room temp. On a 
Gouy balance using Hg[CO(NCS)4] as a calibrant. IR spectra of the complexes (KBr) were 
recorded in the region 400-4000 cm
-1
. On Perkin Elmer FTIR spectrometer and electronic 
spectra were recorded n a Shimadzu 2450 UV-Visible spectrophotometer in the Department 
of Physics, Pratap College, Amalner. 
Synthesis of ligands 
Ligands L1 and L2 were prepared and the methods of their preparation are given below. 
Ligand L1 
Acetophenone Semicarbazone: To a mixture of hot ethanolic 25 mL (0.1 M) solution of 
acetophenone and 20 mL (0.1 M) sodium acetate solution, 25 mL (01 M) aquous solution of 
semicarbazied hydrochloride were slowly added with constant stirring. This mixture was 
refluxed in water bath at 70-80 
0
C for 20-25 minutes. On cooling white solid product 
separated out. It is filtered, washed with cold ethanol, dried in air and recrystallized from 
ethanol. 
Ligand L2 
Acetone Semicarbazone: To a mixture of hot ethonalic 25 mL (0.1 M) solution of (Acetone 
and (20 mL 0.1 M) solution of sodium acetate 25 mL (0.1 M) aqeuous solution of   
semicarbazide hydrochloride was added slowly with constant stirring. Then the reaction 
mixture was refluxed for 5-10 minutes on a water bath. After cooling thoroughly, white solid 
product was precipitated out from the solution .this solid obtained was filtered, washed with 
cold ethanol and dried in air and recrystallized  from CCl4. 
Synthesis of complexes 
Preparation of M (L1)2 and M( L2)2 complexes 
Hot ethanolic 25 mL (0.01 M) solution of manganese chloride were mixed slowly with hot 
ethanolic 25 mL (0.02 M) solution of the acetophenone semicarbazone with constant 
stirring. The reaction mixture is heated in water bath for one hour. Then the reaction was 
stirred for further one hour after which color solid product was obtained, which was then 
washed with ethanol and dried in air. Similarly, the complexes of other metals Fe(III), 
Co(II), Ni(II) and Cu(II) with acetophenone semicarbazone, acetone semicarbazone were  
prepared by mixing solution of corresponding metal chlorides and semicarbazone ligand in 
1:2 molar ratio respectively. 
Preparation of mixed ligand complexes the type ML1L2 
To a 20 mL (0.02 M) ethanolic solution of manganese chloride, a mixture of 20 mL (0.02 M) 
ethanolic solution of acetophenone  semicarbazone and 20 mL (0.02 M)  ethanolic  solution of  
398       Chem Sci Trans., 2012, 1(2), 396-400 
acetone semicarbazone were added slowly with constant stirring. This reaction mixture is 
heated in water bath for 1 to 1.5 hour and then 10% sodium hydroxide is added to adjust the 
pH to about 7 to 7.5. The pH of the solution is tested by pH
 
paper. In case of complexes of 
cobalt and copper  the pH of the reaction mixture  must not exceed 7.5 unless the color of 
the complexes darken more and more to give a black color. The solution is stirred further for 
one hour, cooled to separate the solid colored complex. It is filtered, washed with ethanol 
and dried in air. In this way the complexes of other metals Fe(III), Co(II), Ni(II) and Cu(II) 
with acetophenone semicarbazone and acetone semicarbazone were prepared by mixing 
solution of corresponding metal chlorides and semicarbazone ligand in 1:1:1 molar ratio 
respectively. 
Results and Discussion 
The reactions of metal chlorides with acetophenone semicarbazone and acetone 
semicarbazone in 1:1:1 molar ratio results in the formation mixed ligand complexes. The 
resulting complexes were having different colors. They are insoluble in chloroform, carban 
tetrachloride, methanol, ethanol but soluble in DMF. The physical properties of ligands are 
indicated in Table 1 and of metal complexes in Table 2. The conductance of the complexes 
are very low (1-42Ω
-1 
cm
2 
mol
-1
) indicating their non-electrolyte nature. 
Table 1. Physical properties of ligands 
Name of the 
ligand 
Colour and 
nature 
Method of 
purification. 
M.P.
 0
C 
(observed) 
reported 
Mol. 
wt 
Moleular 
formula 
Acetophenone 
semicarbazone 
White shining 
crystals 
Recrystallization 
from Ethanol 
(200) 199 177 C9H12N3O 
Acetone 
semicarbazone 
White shining 
crystals 
Recrystallization 
from Ethanol 
167 115 C7H13N3O 
Table 2. Characterization data of the complexes found (Calcd.) % 
Ligand/ 
Complex 
C
o
lo
u
r 
M
o
l.
 w
t 
%
 Y
ie
ld
 
o
f 
th
e 
co
m
p
. 
%
 o
f 
m
et
al
 
(C
al
cu
la
te
d
) 
% of C % of H % of N 
Mn[(APS)1(AS)1 
(H2O)2]Cl2 
Faint 
brown 
487.71 63 
(11.70)
10.89 
(44.8) 
41.63 
(4.92) 
4.90 
(17.22) 
17.20 
Fe[(APS)1(AS)1  
(H2O)2] Cl3 
Light 
green 
518.36 69 
(10.77)
10.52 
(41.5) 
41.63 
(4.63) 
4.64 
(16.20) 
16.18 
Co[(APS)1(AS)1  
(H2O)2] Cl2 
Light 
pink 
485.93 71 
(12.07)
11.60 
(44.5) 
44.43 
(4.32) 
4.32 
(17.28) 
17.28 
Ni[(APS)1(AS)1  
(H2O)2] Cl2 
Bluish 
green 
485.71 78 
(12.33)
12.31 
(44.3) 
44.38 
(4.57) 
4.54 
(17.27) 
17.25 
Cu[(APS)1(AS)1  
(H2O)2] Cl2 
Green 429.74 63 
(13.22)
12.70 
(47.49) 
47.45 
(4.61) 
4.57 
(18.47) 
18.44 
Chem Sci Trans., 2012, 1(2), 396-400                 399 
Table 3. IR spectra (cm
-1
) bands of the parent and mixed ligand transition metal complexes 
Ligand/ 
Complex 
ν (OH) 
from H2O 
ν(C=O) ν(C=N) 
Monosubstituted 
benzene ring 
Mn[(APS)1(AS)1 
(H2O)2]Cl2 
3735 1670 1540 692 
Fe[(APS)1(AS)1  
(H2O)2] Cl3 
3529 1668 1539 688 
Co[(APS)1(AS)1  
(H2O)2] Cl2 
3211 1670 1541 692 
Ni[(APS)1(AS)1  
(H2O)2] Cl2  
3229 1659 1548 690 
Cu[(APS)1(AS)1  
(H2O)2] Cl2 
3611 1689 1568 688 
   Table 4. Magnetic moment and molar conductance values of the complexes 
Ligand/ 
Complex 
Magnetic 
moment 
Molar cond.Ω
1
cm
2 
mol
1
 at room temp. 
Molar cond.Ω
-1
cm
2 
mol
1
 at room temp 
Mn[(APS)1(AS)1(H2O)2]Cl2 5.026 17 31 
Fe[(APS)1(AS)1  (H2O)2] Cl3 5.184 16 33 
Co[(APS)1(AS)1  (H2O)2] Cl2  4.7062 10 31 
Ni[(APS)1(AS)1  (H2O)2] Cl2  3.560 09 39 
Cu[(APS)1(AS)1  (H2O)2] Cl2 2.075 21 20 
 Table 3 shows IR spectral data of the complexes and Table 4 shows values of magnetic 
moments and molar conductivities of the complexes. The TLC of the mixed ligand 
complexes exhibit single spots with Rf values being intermediate of the two corresponding 
symmetrical bis-complexes indicating that these are mixed ligand complexes rather than a 
mixture of two corresponding bis-complexes. From the magnetic moments these complexes 
shows octahedral geometry. In the IR spectra of the ligands the bands at 1596-1590cm
-1 
may 
be assigned to the symmetric and asymmetric  υ(C=N) vibrations and a strong band in the 
region 1710-1690 cm
-1 
are due to υ(C=O) groups present in the ligands. On complex 
formation, the position of these bands is shifted towards lower side (1568-1539) and (1689-
1659) as compared to the metal free ligands. This indicates that the coordination takes place 
through the nitrogen and oxygen atom of the(C=N) and (C=O) groups.  
 A broad band appears in the region at 3200-3750 cm
-1 
for -OH group be attributed to the 
coordinated water molecule. Thermogravemetric analysis shows presence of two water 
molecules in the complexes supports the octahedral nature of complexes. The electronic 
spectra obtained for Mn(II) complexes exhibits bands in the range 17534-17568, 23224-
23255 and 28542-28592 cm
-1
 corresponding to 6A1g_4T1g (4G), 6A1g_4E2g (4G), 4A1g 
(4G) and 6A1g_4E2g (4D), transitions, respectively suggesting octahedral environment 
around Mn(II) ion. Fe(III) complexes shows bands in the range 12500-12529,21270-21296 
and 26978-27032 cm
-1
 assignable to 
6
A1g→
4
T1g (G),
 6
A1g→
4
T2g (G) and 
6
A1g→
4
A1g (G) 
transitions, respectively and magnetic moment indicates octahedral geometry. Co(II) 
complexes shows absorption bands in the range 13657-13699, 16947-16978 and 7 744-27781 
cm
-1
, corresponding to 
4
T1g→
4
A2g (F),
 4
T1g(F)→
4
T1g (P) and 
4
T1g(F)→
4
T2g  (F) transitions, 
respectively  for octahedral geometry.  The electronic spectra of Ni(II) complexes exhibits 
three bands in the range 10749-11212, 18524-18595 and 22457-22667 cm
-1
 corresponding 
to 
3
A2g(F)→
3
T2g(F),
 3 
A2g(F)→ 
3
T1g(F)  and  
3
A2g (F)→
3
T1g(P)  transitions,  respectively  
400                  Chem Sci Trans., 2012, 1(2), 396-400  
suggesting octahedral geometry. The six coordinated copper complexes shows bands in the 
range 11151-11521,16216-16671 and 22914-23024 cm
-1
 corresponding to 
2
B1g→
2
A1g,
 2
B1g 
→
2
B2g, 
2
B1g →
2
E2g transitions, respectively.  
Structure of the ligands 
N
H
N
O
H2N
 
 
+ 
 
 
+ 
 
MCl2 
                                                 
++   
N
N
H
O
NH2
M
OH2
2Cl-
2+
N
H
N
O
H2N
OH2
(Acetophenonesemicarbazone)
(Acetone semicarbazone)
(H2O)2 2Cl-M
 
Acknowledgement 
I am grateful to Principal, Pratap College, Amalner and the Head Chemistry Department 
Pratap College, Amalner for laboratory facilities. I am also thankful to the Head Physics 
Department Pratap College, Amalner for Electronic spectra and IR spectra and Head, SAIF, 
IIT  Mumbai for elemental analysis. 
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4. Prasad R N, Kirti Mohan Sharma and Anjali Agrawal, Indian J Chem., 2007, 46A, 600-604.  
5.  Prasad R N, Kirti Mohan Sharma and Anjali Agrawal, J Indian Chem Soc., 2007, 84, 742-745. 
6. Vogel A I, A Text Book of Quantitative Inorganic Analysis, 3
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 Edn., ELBS- 
Longmans, Green & Co. Ltd., London, 1964. 
7. Prasad R N and Jindal M, J Indian Chem Soc., 1989, 66, 188. 
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Synthesis and Physicochemical Studies of Mixed Ligand Complexes of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) with Acetophenone Semicarbazone and Acetone Semicarbazone

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Synthesis and Physicochemical Studies of Mixed Ligand Complexes of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) with Acetophenone Semicarbazone and Acetone Semicarbazone

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