Indian Journal of Chemistry

Vol. 47A, August 2008, pp. 1208-1212

Synthesis and physicochemical
characterization of some Schiff base
complexes of chromium(III)
R K Dubey
a,
* U K Dubey
a
& C M Mishra
b
a
Synthetic Inorganic and Metallo-organic Research Laboratory,
University of Allahabad, Allahabad 211002, India
b
Department of Chemistry, RJ College, Ghatkopar,
Mumbai 400 086, India
Email: rajalkoxy@yahoo.com
Received 20 December 2007; revised 22 July 2008
Some chromium(III) complexes of the type, [Cr(L)
2
(H
2
O )
2
]Cl
(1-10)

[where L = Schiff bases (sbH, derived from the
condensation of 2-amino pyridine, 2-aminophenol, o-toluidine,
p-toluidine, 3-nitroaniline and anthranilic acid with
salicylaldehyde/vanillin) and substituted benzimidazole/
benzoxazole or mercaptobenzimidazole] have been prepared by
the reaction of chromium(III) chloride with corresponding ligands
followed by immediate addition of ethanolic solution of
anhydrous sodium acetate in 1:2 molar ratio. The resulting
products have been characterized by elemental analysis, spectral
(IR, UV-visible and FAB-mass) as well as magnetic susceptibility
measurements. Octahedral structure is proposed for the
complexes.
Chromium (III) complexes containing Schiff bases
and substituted benzimidazole/benzoxazole have
attracted many workers
1-3
due to their biological,
pharmacological, clinical and analytical importance.
The biologically important form of chromium is the
trivalent ion, Cr
3+
, which is required for proper
carbohydrate and lipid metabolism in mammals.
Although chromium deficiency is difficult to achieve,
it is excreted after insulin challenge in the form of
oligopeptide. Chromodulin may be the key to
understanding the role of chromium at molecular level
as the molecule has been found to bind the activated
insulin receptor, stimulating its kinase activity.
Chromium picolinate, Cr(pic)
3
has been proposed to
be the biological form of chromium. It has been used
as the supplement in numerous forms including
pills, chewing gums, drinks and nutrition bars
4-8
.
We report herein the synthesis of some mixed
ligand complexes (containing different donor
atoms) and their characterization by means of
spectral and magnetic studies. Structural correlation
of these complexes have also been made and an
octahedral geometry around chromium (III) is
proposed on the basis of electronic and mass
spectrometric studies.

Experimental
Reagent grade (BDH) precursors to ligands and
solvents were purified by the standard procedures
9
.
Chromium chloride was purchased from Loba and
used as received. All other chemicals were
purchased from commercial sources and used as
such. Chromium was determined by atomic
absorption spectroscopy GBC-932 AA and chloride
present in the complexes was estimated by
Volhard's
10
method. Elemental analysis (CHN)
were carried out on Herbaceous Carlo Erba 1108
analyser. IR and electronic spectra were recorded
on Perkin Elmer grating spectrophotometer. FAB-
mass spectra were recorded on JEOLSX 102/DA-
6000 mass spectrometer/data system.

Preparation of ligands and complexes
The Schiff bases were prepared by refluxing a
mixture of equimolar amounts of aldehydes
(such as salicylaldehyde and vanilline) with
corresponding amines (such as 2-aminopyridine,
o-toluidine, aniline, 2-aminophenol, 3-nitrophenol
and anthranilic acid) in methanolic medium
on water bath for 4 h. The ligand,
2-(o-hydroxyphenyl)-benzoxazole (pboxH) and
2-mercaptobenzimidazole (mbzH) were prepared by
literature method
11,12
. The general method of
preparation of complexes along with ligands used
during the course of present investigations are
shown in Scheme l.
To a suspension of Schiff base, sapH (0.95 g,
4.8 mmo1) in ethanol (~40 m1), a solution of
CrC1
3
.6H
2
0 (0.639g, 2.4 mmo1) in ethanol (~30
m1) was added followed by immediate addition of
anhydrous sodium acetate (0.39 g, 4.8 mmo1) in
hot ethanol (~20 m1). The reaction mixture was
refluxed for ~4 h on a water bath and then filtered
while hot to remove the precipitated sodium
chloride and acetic acid. The green filtrate on
concentration and cooling to ~5C overnight
yielded a green crystalline compound. It was
filtered, washed with ethanol and dried over fused
NOTES


1209
CaC1
2
to obtain the desired product,
[Cr(sap)
2
(H
2
0)
2
]C1 (0.81g, 68% yield). Similar
procedure was adopted for the preparation of other
chromium (III) complexes. The synthetic and
analytical details are collected in Table 1.
Results and discussion
The complexes of chromium (III) have been
prepared by the addition of ethanolic solution of
chromium (III) chloride (hydrated) with the
corresponding ligands followed by immediate

Synthesis of chromium (III) metal complexes with Schiff bases

Scheme 1

Table 1Synthetic, analytical and melting point data of various mixed ligand complexes of chromium (III)

Found (Calc.) (%) Complexes
yield (g, %)
Colour
Melting pt (C)
Cr Cl C H N
[Cr(sap)
2
(H
2
O)
2
]Cl (1)
(0.81g, 68)
[Cr(o-smab)
2
(H
2
O)
2
]Cl (2)
(0.68g, 60)
[Cr(p-smab)
2
(H
2
O)
2
]Cl (3)
(0.66g, 64)
[Cr(sab)
2
(H
2
O)
2
]Cl (4)
(0.81g, 67)
[Cr(saph)
2
(H
2
O)
2
]Cl (5)
(0.77g, 72)
[Cr(snab)
2
(H
2
O)
2
]Cl (6)
(0.84g, 69)
[Cr(saa)
2
(H
2
O)
2
]Cl (7)
(0.99g, 75)
[Cr(vaa)
2
(H
2
O)
2
]Cl (8)
(1.11g, 71)
[Cr(pbox)
2
(H
2
O)
2
]Cl (9)
(0.70g, 70)
[Cr(mbz)
2
(H
2
O)
2
]Cl
c
(10)
(1.15g, 78)
Yellowish green
(320)
b

Green
(325)
b

Green
(295)
a

Light green
(310)
b

Reddish brown
(315)
b

Yellowish brown
(298)
a

Whitish brown
(310)
b

Dark green
(325)
b

Brown
(320)
Ash green
(300)
b

9.92
(10.03)
9.41
(9.55)
9.36
(9.55)
9.95
(10.07)
9.29
(9.48)
8.26
(8.58)
8.29
(8.61)
7.69
(7.83)
9.33
(9.56)
12.09
(12.32)
6.72
(6.85)
6.39
(6.51)
6.43
(6.51)
6.72
(6.87)
6.23
(6.47)
5.46
(5.85)
5.65
(5.87)
5.15
(5.34)
6.29
(6.52)
8.21
(8.40)
55.20
(55.59)
61.52
(61.76)
60.89
(61.76)
60.20
(60.47)
56.45
(56.94)
51.40
(51.49)
55.40
(55.63)
54.10
(54.21)
57.20
(57.41)
39.50
(39.86)
4.20
(4.25)
5.00
(5.15)
5.10
(5.15)
4.45
(4.65)
4.25
(4.38)
3.50
(3.63)
3.58
(3.97)
4.20
(4.22)
3.60
(3.68)
3.40
(3.32)
10.41
(10.81)
5.0
(5.15)
5.00
(5.15)
5.31
(5.43)
5.00
(5.11)
9.0
(9.24)
4.51
(4.64)
4.20
(4.22)
5.00
(5.15)
13.20
(13.29)
a
decomposed;
b
neither melted nor decomposed;
c
analysis for sulphur: Found = 15.0%; Calc. 15.18%
INDIAN J CHEM, SEC A, AUGUST 2008


1210
addition of hot ethanolic solution of anhydrous
sodium acetate in 1:2:2 molar ratio. The reaction
mixture was refluxed on water bath and then
filtered while hot to remove the precipitated sodium
chloride. The filtrate on concentration and cooling
to 5C overnight gave complexes of the type
[Cr(L)(H
2
0)
2
]Cl, which can be represented as
follows:

(i) CH
3
COOHa
CrCl
3
.6H
2
O + 2sbH
(ii) ~4h
[Cr(sb)
2
(H
2
O)]Cl + 2NaCl + 4H
2
O + 2CH
3
COOH
1-8
(sb=sapH, o-smabH, p-smabH, sabH, saphH, snabH,
saaH and vaaH)

(i) CH
3
COOHa
CrCl
3
.6H
2
O + 2pboxH
(ii) ~4h
[Cr(pbox)
2
(H
2
O)
2
]Cl + 2NaCl + 4H
2
O
9

(i) CH
3
COOHa
CrCl
3
.6H
2
O + 2mbzH
(ii) ~4h
[Cr(mbz)
2
(H
2
O)
2
]Cl + 2NaCl + 4H
2
O
10

The complexes are coloured solids, soluble in
DMSO and DMF, but insoluble in ether, benzene
and chloroform.
Similar reactions of CrC1
3
.6H
2
0 with the above
ligands in hot pyridine yielded different reaction
products and can be represented as follows:

(i) hot pyridine
CrCl
3
.6H
2
O + 2LH
(ii) ~1g zinc dust
[Cr(L)
2
(Py)Cl].2H
2
O + ZnCl
2
+ 4H
2
O

where LH = salicylidene-2-aminopyridine(sapH),
salicylidene-2-methyl-1-aminobenzene (o-smabH),
salicylidene-4-methyl-l-aminobenzene (p-smabH),
salicylidene-l-aminobenzene (sabH), salicylidene-
2-aminophenol (saphH), salicylidene-2-
nitroaniline (snabH), salicylidene-anthranilic acid
(saaH), 2-(o-hydroxyphenyl)benzoxazole (pboxH)
and 2-mercaptobenzimidazole (mbzH). These
complexes are non-hygroscopic, air stable and
green coloured solids. The purity of the complexes
was checked by TLC. They are soluble in hot
pyridine, DMSO and DMF, but insoluble in ether,
benzene and chloroform. The complexes are
thermally stable and do not melt or decompose up
to 250C. Molar conductance of the complexes (in
DMSO) reveals their non-electrolytic nature. The
synthesis and structures of the representative
complexes are given in Scheme 1.

IR spectral studies
The IR spectra of the ligand showed bands in
range 1650-1630 cm
-1
which are attributed to
C=N

band. The band is shifted to lower frequency region
1618-1595 cm
1
in all the chromium (III) complexes
indicating that bonding is taking place through the
azomethine nitrogen
11
. The
C-O
(phenolic) stretching
frequencies of the ligands were observed at 1728-
1259 cm
1
in the free ligands which get shifted to
higher region 1265-1290 cm
-1
in the complexes. It is
indicative of bonding through phenolic oxygen
12
.The
broad band appearing at ~1030 cm
-1
in the spectrum
of the ligand has been assigned to -OCH
3
group. A
broad band observed at ~3300 cm
1
is indicative of
NH group present in imidazole rings. This peak is
almost unchanged in complex 10. However,
C=N

mode occurring at ~1610 cm
-1
in the complex
indicates the coordination of ligand to chromium via
their imidazole tertiary nitrogen
13
. A broad band is
observed in all the complexes in the range
~3450 cm
1
due to
OH
of the coordinated H
2
O. This
is supported by the appearance of an additional band
in the range 840-800 cm
1
for (O-H) rocking
deformation. The new bands also appear in the range
750-710 cm
1
which is not observed in the ligand
spectrum. This band can be assigned to the wagging
mode of the coordinated water. The complexes also
showed medium to strong intensity bands in the
region 570-535 cm
-1
, 461-440 cm
-1
and 402 cm
1

which can be attributed to
(Cr-N)
,
(Cr-O)
and
(Cr-S)
bands respectively
14


Electronic and magnetic studies
The electronic absorptive spectra of all the
chromium(III) complexes were measured in DMSO.
These spectra are quite similar to one another and
may be interpreted on the basis of an octrahedral
environment around chromium(III) in these
complexes. All these spectra exhibits three bands
(Table 2) in the regions ~16200 cm
-1
, ~22500 cm
-1
and ~32,400 cm
-1
assigned to ) (
2
4
2
4
1
F T A
g
v
g

and ) ( and
1
4
2
4
2
F T A
g
v
g
) (
1
4
2
4
3
P T A
g
v
g

NOTES


1211
transitions respectively in order of increasing energy.
The various ligand field parameters have been
evaluated for Cr(III) complexes. The value of the first
spin allowed transition (
1
) at ~16200cm
-1
is directly
taken as 10Dq. The value of Racah parameters (B)
has been calculated by the Underhill and Billing
equation
15
= v
3
+ v
2
= 30Dq/5.
The covalency factor,
35
for spin allowed transition
for these derivatives, i. e., ratio of value of Racah
interelectronic repulsion parameter (B) for the
complexes against that for the free Cr
3+
ion
(1030 cm
-1
) is also given in Table 2.
The room temperature magnetic moment values
16

(Table 2) observed, for chromium (III) complexes
synthesized during the present course of
investigations, are in the range 3.61-3.90 BM, and are
close to theoretical spin only values (
eff
= 3.87BM)
for Cr
3+
(3d
3
system).

FAB-mass studies
The FAB-mass
11,17
spectrum of the chromium (III)
complex [Cr(pbox)
2
(H
2
O)
2
]Cl 9 shows a characteristic
molecular ion (M
+
) peak at m/z = 543, which
corresponds to the molecular weight of the complex
for a monomeric structure. The mass spectrum shows
multiple peaks representing successive degradation of
the complex molecule by the formation of radical
C
6
H
4
O

. The fragmentation pattern showing the

structure of the complex is given in Scheme 2. On the
other hand, complex [Cr(mbz)
2
(H
2
O)
2
C1] 10 shows a
molecular ion peak at m/z = 386 suggesting the
monomeric form of the complex. Successive
fragmentation gives many more important peaks, due
to the formation of C1

, C
6
H
4
N

and CHN

radicals


Fragmentation pattern [Cr(pbox)2(H2O)2]Cl (9) using FAB-mass spectrum

Scheme 2
Table 2Electronic and magnetic data of the chromium (III)
complexes
Electronic
transitions (cm
-1
)
No.
4
A
2g

4
T
2g
(F)
4
A
2g

4
T
2g
(P)
10Dq
(cm
-1
)
B
(cm
-1
)

35

eff

(BM)

1 22817 35037 15995 670 0.65 3.84
2 23533 35482 16949 625 0.60 3.85
3 23436 36200 16856 620 0.60 3.85
4 22886 35441 16215 660 0.64 3.88
5 22425 34270 15537 720 0.69 3.78
6 23451 36965 16960 645 0.62 3.78
7 22426 34894 15897 667 0.64 3.78
8 23094 37230 17193 610 0.59 3.90
9 23591 35722 16290 712 0.68 3.80
10 23771 36729 16786 690 0.66 3.85
INDIAN J CHEM, SEC A, AUGUST 2008


1212
which confirms the structure (Scheme 3) of the
complex 10. These complexes show molecular ion
peaks in good agreement with the structure suggested
by elemental analysis, spectral and magnetic studies.
On the basis of the above elemental analysis and
spectral studies, confirmed by FAB-mass spectra
(9 and 10) showing characteristic molecular ion peak
at their expected m/z value for their monomeric form,
octahedral structure is proposed for these complexes.
Definite structures of these fascinating Schiff base
complexes in solid state would be possible only after
X-ray crystallographic studies, which have not been
successful so far.

Acknowledgement
Authors are grateful to IIT, Mumbai and CDRI,
Lucknow for providing spectral and analytical data.

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FAB-mass fragmentation pattern of [Cr(mbz)2(H2O)2]Cl (10)
confirming composition and structure of the complex.

Scheme 3