Synthesis and identification of nickel (ll) , cobalt (ll) and copper (ll) complexes with the organic reagent

Journal of Natural Sciences Research
ISSN 2224-3186 (Paper) ISSN 2225-0921 (Online)
Vol.3, No.10, 2013

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Synthesis and Identification of Nickel (ll) , Cobalt (ll) and Copper
(ll) Complexes with the Organic Reagent ( Sodium – 1 – Amino –
9,10 – Dioxo – 4 – Phenylamin – Anthracene – 2 – Sulphonate )
Jassem Mohamad Abd Al Hassien
University of Babylon , College of science , Department of Chemistry
E-Mail : mjaseem67@yahoo.com*
Abstract
The complexes of Nickel (ll) , Cobalt (ll) and Copper (ll) were synthesized by using Sodium – 1 – Amino – 9,10
– Dioxo – 4 – Phenylamin – Anthracene – 2 – Sulphonate , acid blue – 25 , ( AB25 ) reagent as a ligand . They
were characterized by many techniques such as the element analysis , IR spectroscopy and UV.VIS.
spectroscopy . Their physical properties such as electric conductivity and magnatic properties , were determind .
It was found that Nickel (ll) complex has diamagnetic properties , whereas Cobalt (ll) and Copper (ll) complexes
have paramagnetic properties . Cobalt complex did not have any conductivity , whereas the ligand , Nickel (ll)
complex and Copper (ll) complex have good conductivity . The formula of the complexes under this research
were detected by using the mole ratio method which lead to the formation of ( 1:1 ) metal : ligand formula for
Nickel (ll) and Copper (ll) complexes , whereas Cobalt (ll) complex was ( 1:2) metal : ligand formula . In all the
complexes the coordination was through O and N atoms of the oxo sulfate and amine groups . the suggested
geometrical shapes of the complexes were the squar pyramidal shape for Nickel (ll) and Copper (ll) complexes
and octahedral for Cobalt (ll) complex .
Keywords : Acid Blue – 25 , Ni (ll) complex , Cu (ll) complex , Co (ll) complex , IR spectroscopy , geometrical
shapes
1 – Introduction
The high molecular weight coordination complexes have a wide importance in the field of clinical and analytical
chemistry in recent days that because of their high stability and their useful utilization (Loo & Hu 1994 , Sido &
Brown 1965 , Sony et al. 2004) . There are many antibiotics react with many transition metal ions to form stable
complexes such as ciprofloxacin which reacts with copperic ion to form stable chelate complex ( Wn et al.
2003 ) . From another side , there are many ligands such as 8 – hydroxyl quinolin , oxalate and carbazate used
to form complexes with many heavy metal ions which can be act as antitoumer drugs (Rashan et al. 1990 ) .
Many recrnt studies found that the complexes have antibiotic activity more than the free ligands ( Sadik et al.
2003 ) . In industrial fields , the formation of complexes used in the purification of petroleum ( Salih & Sheriff
1990 ) . Nickel , Cobalt and Copper are within the 25 essential metal ions that are required by most of biological
systems . Many organisms such as Lactobacilli that their ribonucleotide reductase uses cobalt as a cofactor .
nickel appears to be much more extensively utilized by anaerobic bacteria . Copper laccase enzyme catalyses the
oxidation of uroshiol in the production of Japanese Lacquer ( Crichton 2008 ) . Jasem had prepared the
complexes of Pb (IV) , Cd (ll) and Fe (lll) by using the reagent that used in this research and he found that these
complexes had good stability ( Husain 2012 ) . The most stable Co(ll) complexes have the octahedral
coordination and Ni(ll) complexes have the squar planar coordination while Cu(ll) complexes have the
tetrahedral coordination ( Al-Rasaq 1984 ) . In biochemistry , Biuret test , cupric ion has been used to detect and
value the amount of protein in its basic solutions by the coordination via its amino groups to form violet complex
( Yasser 2004 ) . Cytochrome oxidase ( cytochrome a3 + a ) consiste of copper in addition to iron and porphyrin
to establish its biological role of transporting the electrons and oxidative phosphorylation in organisms
( Lehninger 1975 , Kabsh & Asos 1988 ) . Cobalt is an essential element for the functioning of many vital
processes such as the processes of blood formation , stimulation of hemoglobin synthesis , the functioning of
vitamins , the functioning of enzymes , the functioning of hormones , influence on metabolism of vitamins
( ascorbic acid and B12 ) and the synthesis of a number of hormomes , neurotransmitters , bile acids and DNA
( Ahmad 1986 , Grahovav et al. 2006 ) .
2 – Prartical Part
Spectral and Physical Measurments :
IR spectrum were recorded for the ligand and the complexes by using FTIR – 84005 Shimadzu Specroscopy
with KBr discs in the rang ( 400 – 4000 ) cm-1 .
UV.VIS. spectrum were recorded for the aqeous solutions of the ligand and for the ethanolic solutions of the
complexes by using UV – 1650 PC Shimadzu Specroscopy with quartz cells .

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Element analysis was established by using EURO EA ( Element Analyzer ) and Shimadzu – AA – 160 Atomic
Absorption – Flame Emission Spectrosphotometer .
Magnatic susceptibility measurmeants where established by using MSB – MKI Magnatic Susceptibility
Measurment Balance .
The electric conductivity for the solutions were measured by using INOL AB 740 Potentiometer .
Materials :
All the materials which were used in this research were so sensitive to air and moisture that they have been
kept in dry containers .
The water used was double distilled water .
Nickel (ll) , Cobalt (ll) and copper (ll) solutions ( 0.001 M )
were prepared from theres chloride salts .
All the reagent were of high purity , they get from BDH and Fluka companies .
Sodium nitrate used to prepare the background electrolytic solutions .
The used ligand has the commercial name ; acid blue 25
( AB 25 ) . Table ( 1 ) shows some properties of the ligand.
Table ( 1 ) some properties of the ligand :
Sodium – 1 – amino – 9,10 – dioxo – 4 – phenylamin anthracin – 2 - sulphonate
Scientific name
O
NH 2
Chemical structure
SO3 Na

O

Symbol
Commercial name
Molecular formula
Molecular weight
Physical state
apperance

NH

AB25
Acid Blue – 25
C20H13N2O5SNa
416.38
Solid powder
blue

Preparation the Complexes :
Preparation of Ni (ll) Complex :
0.001 moles ( 0.237 g ) of nickel chloride ( NiCl2.6H2O ) , dissolved in 20 ml of distilled water , and 0.001
moles ( 0.417 g ) of the ligand ( AB 25 ) , dissolved in 10 ml of distilled water , mixed together and 2ml of 10%
NaOH added to the mixture . After heating to 70 o c for 30 minutes agreen – blue precipitate was formed ,
separated by filtaration and washed by ethanol then dried at 50o c . The product percentage was 70% .
Preparation of Co (ll) Complex :
0.001 moles ( 0.237 g ) of cobalt chloride ( CoCl2.6H2O ) , dissolved in 20 ml of distilled water , and 0.001
NaOH added to the mixture .
After heating to 70 o c for 30 minutes agreen – blue precipitate was formed ,
separated by filtaration and washed by ethanol then dried at 50o c . The product percentage was 65 % .
Preparation of Cu (ll) Complex :
0.001 moles ( 0.170 g ) of cobalt chloride ( CuCl2.2H2O ) , dissolved in 20 ml of distilled water , and 0.001
NaOH added to the mixture .
After heating to 70 o c for 30 minutes agreen – blue precipitate was formed ,
separated by filtaration and washed by ethanol then dried at 50o c . The product percentage was 67 % .
Determination the Maximum Wavelength ( λmax ) :
10-3 M solutions of the ligand and complexes were prepared , UV.VIS. spectral scanning was obtained , λmax was
recorded for each solution . The figures ( 1-4 ) shows the electronic spectra of ligand and its complexes . Table
( 1 ) shows the λmax values of the ligand and its complexe

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Table ( 2 ) electronic spectra of the ligand and its complexes
compound
nm)(λmax
Assig.
AB25

AB25-Ni

AB25-Co

AB25-Cu

280
390
590
260
380
640
280
380
635
285
380
633

π →π*
π →π*
n →π*
π →π*

π →π*
n →π*
π →π*

π →π*
n →π*
π →π*

π →π*

( Buhlmann & Affolter 2000 ) :
-1
-1
max(L.mol .cm ) ξ
2900
100
330
2200
200
600
2000
150
600
2150
200
350

n →π*

Figure ( 1 ) : electronic spectra of AB25 ligand

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Figure ( 2 ) electronic spectra of Ni – AB25 complex

Figure (3) electronic spectra of Co – AB25 complex

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Figure (4) electronic spectra of Cu – AB25 complex
Determination the Complexes Formula :
By using the continous variation method , the formula of each complex was determined : ( 1:1 ) M:L formula for
Ni- complex and Cu – complex , ( 1:2 ) M:L formula for Co – complex . Table ( 3 ) shows the molecular formula
of these complexes .
Elements Analysis :
Elements analysis had completed for the ligand and the prepared complexes , table ( 3 ) shows the results of the
element analysis .
Table ( 3 ) element analtsis data of the ligand and the complexes :
Com.
AB25
Ni-AB25
Co-AB25
Cu-AB25
M.F.
C H N O SNa NiC H N O S CoC H N O S
CuC H N O S
20

C
H
N
O
S
Na
M

13

57.64
(55.90)
3.12
(3.00)
6.72
(6.64)
19.21
(18.90)
7.68
(6.99)
5.52
(4.98)
---------

2

5

20

17

2

7

40

26

4

10

2

20

49.20
(48.57)
3.48
(3.10)
5.74
(5.21)
22.95
(22.31)
6.56
(6.11)
-------------

56.80
(55.10)
3.08
(2.82)
6.63
(6.01)
18.93
(18.23)
7.57
(6.88)
--------------

48.70
(47.32)
3.45
(3.01)
5.68
(5.12)
22.73
(22.01)
6.49
(5.51)
------------

12.03
(11.72)

6.97
(6.21)

12.89
(12.25)

Com. = compound
M.F. = molecular formula
M = metal
36

17

2

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Molar Conductivity (Ʌm) Measurements :
The molar conductivity for the aqeous solutions of the ligand and the complexes ( 10-3 M ) at 25oc were
measured , the results shown in table ( 4 ) .
Determination the Complexes Magnatic Properties :
Magnatic properties of the complexes were measured due to Gouy Balance Methode . The effective magnatic
momentum

µ eff

at 25o c was calculated and the results are shown in table 4 )(

Table ( 4 ) analytical and physical properties of the ligand and the complexes :
Compound
AB25
Ni-AB25
Co-AB25
416.38
487.80
485.00
M. W.
3.721
4.15
0.182
Ʌm(ms/cm-1)
----------0.23
1.50
)BM( eff

µ

colour
Shape
hypridization

Blue
---------------------

Blue - green
squar planar
Dsp2

=
tetrahedral
d2sp3

Cu-AB25
492.8
4.08
1.52
=
tetrahedral
sp3

IR Specra :
IR specra for the ligand and the complexes , in their solid state , were recorded in the range ( 400 – 4000 ) cm-1
with KBr discs . Figure ( 5 – 8 ) shows these spectra and the absorption bands of important groups of the ligand
and its complexes are shown in table ( 5 ) .
Table ( 5 ) important IR absorption bands for ligand and the complexes :
Assignment
AB25
Ni-AB25
Co – AB25
Cu – AB25
3435(S)
3522(S)
3446(S)
3419(S)
N-H(str.)
3300(W)
3437(W)
3335(W)
2929W)
2924(W)
3215(W)
2950(W)
2854(W)
C-H(str.)
1572(S)
1624(S)
1630(S)
1624(S)
C=O(str.)
1234(S)
1230(S)
1300(S)
1384(S)
C-N(str.)
1363(S)
1533(M)
1530(M)
1530(M)
1506(M)
C=C(str.)
1024(S)
1024(S)
987(S)
1109(S)
S=O(str.)
731(S)
669(S)
848(S)
700(S)
S-O(str.)
950(M)
1815M)
895(M)
835(M)
C-H(ben.)
632(S)
632(S)
630(S)
675(S)
C-S(str.)

Figure (5) IR spectra of AB25 ligand

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Figure (6) IR spectra of Ni- AB25 complex

Figure (7) IR spectra of Cu- AB25 complex

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Figure (8) IR spectra of Co- AB25 complex
3 - Results and Disscusion
The most important IR absorption bands , in the ligand IR spectrum and the complexes IR specra within the
range ( 4000 – 400 ) cm-1 , are shown in table ( 5 ) . The important stretching bands in the ligand IR spectrum
belongs to N-H , C-H , C=O , C-N , S=O , S-O and C-S bands . The shifting observed in the IR sprctrum bands
of the complexes supports that the coordination between the metals and the ligand via the NH , CO , SO3 groups
and that lead to expect that the electronic environment of the metal atoms had been changed after the
coordination process and complexes formation .
The ligand electronic spectrum shows that there are three principle bands ; 280 nm and 390 nm represent the
position transitions of the aromatic rings while the third , 590 nm , belong to charge transfer band . This
conclution agree with the reference ( Chang 1975 ) . Clear displacement ( 50 nm ) had occurred to these bands
after the formation of the complexes , that refer to that the electronic environment of coordinated atom had been
differed after the coordination process . This result agree with the published research which used like this ligand
( Mohamd et al. 1984 ) .
The results of the molar conductivity measurements indicate that the ligand , Ni – complex and Cu – complex
have good conductivity due to the positive charge on the coordination core and the nrgative charge on the
neighbouring ion , whereas Co – complex has no conductivity due to the neutral coordination core .
The magnetic properties indicate that Ni – complex has diamagnetic properties , whereas Cu – complex and Co –
complex have paramagnetic properties .
The suggested geometrical shapes of the complexes were squar planare for Ni complex and tetrahedral for Cu
complex, whereas Co complex was octahedral . The figures ( 9 – 10 ) shows these shapes .
Acknowledgment : I thank all the teaching staff in chemistry department who help me to established this
research . this work was supported by the University of Babylon ,Hilla , Iraq .

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HN
O
O
O

S
O
NH 2
O
M
H2 O

M = Ni or Cu
Figure ( 9 ) geometrical shapes of Ni and Co complexes

HN
O
O
O

S
O
NH2
O
M

O
H 2N
O
S

O

O
O
HN

M = Co

Figure ( 10 ) geometrical shape of Co complex

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4 – References
Joseph A. Loo and Peifeng Hu , J. Am. Soc. Mass Spectrum , 5 , 959 – 965 ( 1994 ) .
Hideyo Sindo and Theodor L. Brown , Journal of American Chemical Society , 87:9 , May 5 ( 1965 ) .
S. Malathy Sony , K. Saraboji , M.N. Ponnuswamy , J. Manonmani , M. Kandasmy and H.K. Fun , Cryst. Res.
Technol. , 39 , No. 2 , 185 – 192 ( 2004 ) .
G. Wn , G. Wang , X. Fu and L. Zhu , Molecules , 8 , 287 – 296 ( 2003 ) .
L. J. Rashan , T. A. K. AL – Allaf , W. F. Halaseh and R. F. I. Khuzaie , Biologia Bratislava , 35 , 349 (1990 ) .
Sadik , A. Omowunmi and Hangwa , V. S. Patent : 6 , 602 , 989 , Appl. No. : 573993 ( 2003 ) .
H. A. Salih and G. H. Sheriff , Iraqi J. of Chem. , 15 , 68( 1990 ) .
Robert R. Crichton , Biological Inorganic Chemistry An Introduction , Elsevier B. V. (2008 ) .
Jasem M. A. AL – Husain , J. of Babylon University /Pure and Applide Sciences / No. ( 2 ) / Vol. ( 20 ) :
( 2012 ) .
Jaafer A. Al – Rasaq , Coordination Chemistry , Baghdad University , Scinece College ( 1984 ) .
Al – Zamilly O. M. Yasser , Practical Biochemistry , Babylon University , Science College ( 2004 ) .
Lehninger Albert L. , Biochemistry , Worth Publishers Inc. New York ( 1975 ) .
Al – Kabsha T. S. and Asos A. S. , Physical Analytical Chemistry , Mousel University (1988 ) .
Al – Flaih K. Ahmad , An Introduction of Biochemistry , University of Mousel ( 1986 ) .
Zora M. Grahovac , Snezana S. M. , Emilija T. P. and Snezana B. Tosic , J. Serb. Chem. Soc. , 71 , 189 ( 2006 ) .
Pretsch P. Buhlmann and C. Affolter , Structure Determination of Organic Compounds , Sprenger – Verlag
Berlin Heidelberg New York ( 2000 ) .
R. Chang , Physical Chemistry , University Science Books ( 1975 ) .
M. R. Mohamad , A. M. Hammon and S. A. Ibrahim , Z. Phys. Chem. , 265 , 203 ( 1984 ) .

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Synthesis and identification of nickel (ll) , cobalt (ll) and copper (ll) complexes with the organic reagent

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