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International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190

ICRTIET-2014 Conference Proceeding, 30th -31st August 2014

Synthesis And Characterization Of Cr(III) Complexes With


Thiosemicarbazone And Semicarbazone Based Ligands
Sulekh Chandra 1 ,Smriti Raizada 2*, Sangeeta Sadwal2*
1
Department of Chemistry, Zakir Husain Delhi College, University of Delhi, Jawaharlal Nehru Marg, New Delhi, India
2*
Department of Chemistry, M.M.H.College, Ch.Charan Singh University, Ghaziabad, U.P, India.
Correspondence should be addressed to* Dr Smriti Raizada, Associate professor, Department of Chemistry,
M.M.H.College, Ch.Charan Singh University, Ghaziabad, U.P, India.

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

Schiff base. In view of the above in the present paper we


report the synthesis and characterization of Schiff base
complexes of chromium (III).

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.

3. RESULTS AND DISCUSSION


On the basis of elemental analyses (Table 1) the
complexes were found to have CrL2X3 (X = Cl, NO3
)composition. Molar conductance, measured in DMSO
solution of these complexes indicates that these
complexes are 1:1 electrolytes in nature, therefore,
these complexes may be formulated as [CrL2X2]X.

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115

International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
ICRTIET-2014 Conference Proceeding, 30th -31st August 2014

Table1: Molar Conductance and Elemental Analysis Data of Cr(III) complexes


complexes
colour
Molar
yield
m.p Elemental analysis found/calculated
conducta
C
nce
M
C
H
N
[Cr(L1)2Cl2]Cl
green
74
65
232
9.34
30.54
3.28
25.36
(9.47)
(30.64) (3.31) (25.52)
[Cr(L1)2(NO3)2]NO3

green

86

62

224

[Cr(L2)2Cl2]Cl

green

80

70

232

[Cr(L2)2(NO3)2]NO3

grey

81

64

233

3.1 Infrared Spectra of complexes:IR spectrum of the


ligand L1 shows bands at 3399, 3178 cm1 which may be
assigned to (NH2) and (NH) groups, respectively. The
bands due to [(C=S)] appeared at 801 cm1 ,at 1618
cm1 may be assigned to symmetric or asymmetric
[(C=N)] group and the ligand L2 shows bands at 3400,
3242 cm1 which may be assigned to (NH2) and (NH)
groups, respectively. The bands due to [(C=O)]
appeared at 1684 cm1 and the bands at 1618 cm1 may

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)

be assigned to symmetric or asymmetric [(C=N)] group


. The metal complexes show the shifting of the bands
corresponding to (C=N) and (C=S) for L1 ,(C=O) for
L2 towards the lower side (around ca. 2050 cm1) on
complexation. This suggests that the ligands act as
bidentate chelating agent coordinating through nitrogen
of C=N group and sulphur of C=S group for L1 ,oxygen
of C=O for L2 [18-24][Table 2]

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]
.

3.3 EPR spectra of complexes


The EPR spectra of the complexes were recorded as a
polycrystalline sample Intense EPR line, centered at
about 340 mT (geff 1.972) was observed for all the
analyzed samples in whole temperature range .The
values of indicate that the complexes under study have
a substantial covalent character. g-values were calculated
and found in the range of 1.97-1.99, corresponding to 6coordinated geometry [28-30].Various ligand field
parameters were calculated and their values are listed in
Table 3with the parameters. The values of the ligand
field parameters are consistent with octahedral geometry
for
the
complexes

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

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

17520, 26240, 35550

1.98

LFSE
Kjmol-1
265.8

[ Cr(L1)2 (NO3 )2]NO3

3.89

17620, 24638, 33680

1.96

275.4

[Cr(L2)2Cl2]Cl

3.82

17862, 24572, 33910

1.97

267.2

[ Cr(L2)2 (NO3 )2]NO3

3.88

18100, 25420, 34420

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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International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
ICRTIET-2014 Conference Proceeding, 30th -31st August 2014

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