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ABSTRACT
Complexes of chromium(III) metal ion with schiff base
derived from the condensation of pyridine -3carboxamide
with thiosemicarbazone(L1) and
semicarbazone (L2)
have been synthesized and
characterized by elemental analysis, molar conductance,
magnetic susceptibility measurements, electronic and epr
spectral studies. Molar conductance, measured in DMSO
solution of these complexes indicates that the complexes
are 1:1 electrolytes in nature, therefore the complexes
may be formulated as [CrL2X2]X. EPR and electronic
spectral studies reveal that the complexes possess sixcoordinated octahedral geometry.
Keywords- Thiosemicarbazone , chromium complexes,
IR, Magnetic Moment, EPR
1. INTRODUCTION
Semicarbazone and thiosemicarbazone based schiff
bases and their metal complexes present a wide range of
bioactivities often related to the metal ion coordination;
their chemistry and pharmacological applications such as
antibacterial, antifungal, antitumor, antiviral and
anticancer [1-10]. Chromium finds applications in
biological systems wherein Cr(III) ion is required in
trace amounts for sugar and lipid metabolism [11].
Chromium is thought to activate enzymes, maintain
protein stability and enhance carbohydrate metabolism
[12-15]. Chromium compounds are found to lower blood
glucose levels in diabetic patients [16].
In view of above applications it is highly desirable to
synthesize and characterize the Cr(III) complexes with
2. EXPERIMENTAL
2.1. Synthesis of Schiff base ligand L1 (pyridine -3carboxamide thiosemicarbazone) and L2 (pyridine 3-carboxamide semicarbazone): The Schiff base was
prepared by condensing the pyridine -3-carboxamide
with thiosemicarbazone for L1and semicarbazone L2 in
1:1 ,using methods described previously [17]
2.2 Preparation of Cr(III) Complexes with Ligands:
Hot ethanolic solution of metal salts (.005mol) were
mixed with ethanolic solution of the corresponding
ligands (.01mol in 20mL of absolute ethanol) e.g.
pyridine -3-carboxamide thiosemicarbazone (1.9g, 0.01
mol), pyridine -3-carboxamide semicarbazone(1.79g,
0.01 mol),. The mixture was heated under reflux for 810 hours at room temperature. The solid product was
filtered off, washed several times with ethanol and
dried over anhydrous CaCl2.
Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India
115
International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
ICRTIET-2014 Conference Proceeding, 30th -31st August 2014
green
86
62
224
[Cr(L2)2Cl2]Cl
green
80
70
232
[Cr(L2)2(NO3)2]NO3
grey
81
64
233
8.20
(8.27)
10.01
(10.06)
8.56
(8.72)
26.54
(26.75)
32.26
(32.54)
27.98
(28.20)
2.75
(2.89)
3.48
(3.51)
3.01
(3.04)
28.73
(28.97)
27.09
(27.11)
30.42
(30.53)
Table 2: Important IR bands and assignment of ligands and their Cr (III) Complexes
Compound
(C=N )
(C=O )
(NH )
(C-S )
(M-O/M-S )
LIGAND(LI)
1618
3399
801
[Cr(L1)2Cl2]Cl
1574
3269
764
430
[ Cr(L1)2 (NO3 )2]NO3
1580
3307
782
434
LIGAND(L2)
1620
1684
3400
[Cr(L2)2Cl2]Cl
1565
1678
3101
[ Cr(L2)2 (NO3 )2]NO3
1591
1656
3258
3.2. Electronic Spectra of the Complexes
Three spin allowed transitions are observed in high spin
state 4A2g(F) 4T2g(F) (1), 4A2g(F) 4T1g(F) (2) and
4
A2g(F) 4T1g(P) (3). The highest energy band
assignable to the 4A2g 4T2g transition, occurs above
30,000 cm1. The positions of the important bands
indicate that these complexes exhibit 6-coordinate
octahedral geometry, consistent with D4h symmetry
around the metal ion[25] .In all the Cr (III) complex
observed magnetic moment of these complexes, at room
temperature (298 K), lie in the range of 3.71 - 3.84 B.M.
[Table 3] bands at 380 cm1 attributed to charge transfer
while the values 350 cm1 and 295 cm1 are assigned to
the transitions, suggest an octahedral environment.[2627]
.
Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India
116
International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
ICRTIET-2014 Conference Proceeding, 30th -31st August 2014
Table3: Magnetic moment, electronic and EPR spectral data of Cr(III) Complexes:
Complexes
eff (BM)
max(cm-1)
g values
[Cr(L1)2Cl2]Cl
3.75
1.98
LFSE
Kjmol-1
265.8
3.89
1.96
275.4
[Cr(L2)2Cl2]Cl
3.82
1.97
267.2
3.88
1.97
267.8
On the basis of spectral analysis the following structures may be proposed for Cr(III) complexes Fig 1.
(a)
(b)
Fig 1. Cr(III) complexes with ligand (a) L1 where X = Cl-,NO3- (b) L2 where X = Cl-,NO3
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Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India
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International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
ICRTIET-2014 Conference Proceeding, 30th -31st August 2014
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