Synthesis and characterization of

IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
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Volume: 02 Issue: 12 | Dec-2013, Available @ http://www.ijret.org 583
SYNTHESIS AND CHARACTERIZATION OF
OCTAAZATRICYCLOTETRACOSANE (OCTC) MACROCYCLIC
COMPLEXES OF NI (II), CU (II) TRANSITION METAL IONS DERIVED
FROM 1, 3-DIAMINOPROPANE CONTAINING AZA LIGANDS
Sangeeta Sahu
Department of Applied Chemistry, Bhilai Institute of Technology, Kendri, New Raipur-493661 (Chhattisgarh) India
sangeetasahu76@gmail.com
Abstract
This paper deals with the synthesis and characterization of macrocyclic ligand and its complex compound. Template condensation of
chlorocarbons such as 1,1,2,2-tetrachloroethane with 1,3-diaminopropane in presence of nickel (II) or copper (II) yielded the
corresponding metal complexes such as 3,7,10,14,15,19,20,24- octaazatricyclotetracosane (OCTC). The macrocyclic ligands and
their complexes have been characterized by elemental analysis, molecular weight determination, conductance, IR and NMR spectral
studies. The magnetic moments, along with electronic spectral data suggested hexa coordinated state for Nickel, its geometry is outer
orbit octa hedral and tetra coordinated state for copper, its geometry is square planner .Conductivity data suggests that they behave
as electrolytes. The formulation of the complexes has been established on the basis of chemical composition.
Keywords: Ni (II), Cu (II), Transitional Macrocyclic Complex, Synthesis, Spectroscopy.
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1. INTRODUCTION
Curtis reported the first of a number of pioneering template
reaction for macrocyclic systems which were published in the
period 1960 to 1965 [1].In the Curtis synthesis, a yellow
crystalline product was observed to result from the reaction of
[Ni(1,2-diaminoethane)2]2-
and dry acetone. The yellow
product was shown to be a mixture of the isomeric
macrocyclic complexes. 5,5,7,12,12,14-hexamethyl-1,4,8,11-
tetraazacyclotetradeca-1,14 diene [3]. In this remarkable
cyclization reaction, formation of bridges between the two
1,2-diaminoethane moieties involves condensation of two
acetone molecules per bridge [2]. Here, a hydrogen-bonding
network may act as a template for the reaction and also serve
to stabilize once it is formed. A revised synthesis of the metal-
free ligands has been published [4].
This paper describes synthesis and characterization of
macrocyclic complexes of nickel (II) and copper (II) derived
from1, 3-diaminopropane .The 1, 3-diaminopropane has been
condensed with 1, 1, 2, 2-tetrachloroethane in presence of a
metal-ion in different molar ratios as mentioned in their
synthesis.
2. EXPERIMENTAL
In view of the importance of macro cyclic chemistry the Ni
(II), Cu (II) complexes of new categories of aza macro cyclic
were synthesized. Template condensation of chloro carbon
such as 1,1,2,2-tetrachloroethane with 1,3-diaminopropane in
presence of Cu (II),Ni (II) yield the corresponding metal
complex of the following macro cyclic legend –
3,7,10,14,15,19,20,24-octaazatricuclo[7.5.5.52.8] tetracosane
(OCTC) (Figure 1).
Solvents and reagents used in the synthesis of the nickel (II)
and copper (II) complexes were reagent grade and were used
without further purification.
2.1 Synthesis of the Nickel (II) Complex of 3, 7, 10,
14, 15, 19, 20, 24-Octaazatricuclo [7.5.5.52.8]
Tetracosane (OCTC)
Nickel hydroxide 95.00g, 53.92 (mmole) was added to stir
mixture of 1, 3-diaminopropane (7.99 g, 107.78 mmole) and 1,
1, 2, 2- tetrachloroethane (9.05 g, 53.92 mmole) in 200ml
butanol. The mixture was then refluxed for 4 hrs. After being
refluxed about 5 min. the mixture changed to blue turbid
solution containing a small quantity of the green precipitate.
The whole mixture turned into a blue turbid solution after
being refluxed for 4 h. It was then cooled treated with 150 ml
of water and aqueous bluish-violet solution was separated and
the green precipitate and colourless non-aqueous butanol layer
were rejected. Condensation and refrigeration of the solution
gave crude, sticky violet crystals of [Ni2 (OCTC) (H2O) 4]
Cl4.5H2O. The sticky material was removed by treating the

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product with ether-benzene (1:1) mixture on filter paper. The
product was recrystallized to remove traces of white residue.
Pure product was crystallized from the resulting solution.
Violet crystals were finally washed with ether and dried, yield
10.2 g (Figure 2).
2.2 Synthesis of the Copper (II) Complex of 3, 7, 10,
14, 15, 19, 20, 24-Octaazatricuclo [7.5.5.52.8]
Tetracosane (OCTC)
The cyclization reaction involving 1, 3-diaminopropane (7.60
g, 102.52 mmole) was carried out by refluxing the mixture in
200 ml butanol. The deep blue mixture changed into a
greenish-blue solution after continuous heating for 3 h. The
greenish-blue solution was treated with water and filtered. The
brown residue in small quantity was rejected. The violet
aqueous layer of the filtrate containing the macrocyclic
product was separated from the non-aqueous wine-red layer.
Concentration and refrigeration of the aqueous layer yielded
violet crystals soluble in methanol and water. The crystals
were washed with acetone followed by ether, yield 7.32 g.
(Figure 3)
3. RESULTS AND DISCUSSION
3.1 Synthesis
The nickel (II) complex of 3, 7, 10, 14, 15, 19, 20, 24-
octaazatricuclo [7.5.5.52.8] tetracosane (OCTC) derived from
1:2:1 molar mixture of nickel hydroxide 1, 3-diaminopropane
and 1, 1, 2, 2,-tetrachloroethane contain two nickel ions in the
ligand cavities, where each metal is coordinated to for donars.
The two molecules of 1:2 nickel-ammine complexes formed at
the initial stage condensed with two molecules of 1, 1, 2, 2-
tetrachloroethane yielding the corresponding dinuclear
complex.
In the extension of 1, 3-diaminopropane and 1, 1, 2, 2-
tetrachloroethane condensation to copper (II) ion under the
similar reactant ratio, the macrocyclic OCTC is again
generated. But, the ligand encapsulates four copper ions in its
cavity. Four compared to 1:2 copper-ammine complex where
each copper ion is coordinated to two aza groups of the
ligands.
3.2 Chemical Analysis
Microanalysis for carbon, hydrogen and nitrogen were carried
out at the regional sophisticated instrumentation centre, central
drug research institute (CDRI) Lucknow. The metal content
was determined by EDTA titration.
The ionizable chloride ions
in the compounds were determined by conductanctric titration
using 0.01 M ligand /complex and 0.1 M AgNO3 solution.
(Table 1.1)
3.3 Physical Measurements
Conductivity data of the complex was recorded using their
0.01 M aqueous solution, with the help of a DDR
Conductivity meter type 304. A Jeol D-300 (El/Cl)
spectrometer was used for obtaining the mass spectra of the
ligand hydrochlorides of low molecular weight. Infrared
spectra in the range 4000-250cm-1
were recorded by Perkin
Elmer infrared spectrometer in KBr pellets. FTIR spectra of a
number of compound were recorded by Shimadzu 8201 PC
(4000-350 cm-1
) infrared spectrophotometer. The pmr spectra
were taken in D2O solution and recorded on bruker DRX300
(300 MHz. PT NMR) using tetra methylsilane as an internal
standard. (Table 1.2)
3.4 Infrared Spectra
The infrared spectrum of [Ni2 (OCTC) (H2O) 4] Cl4.5H2 O
includes the absence of bands due to the NH2 group. A very
weak but very sharp band attributed to only a secondary amine
appears at 3150 cm-1
. This suggests the presence of a strong
but sharp band at 1594 cm-1
. A medium but very band at 1065
cm-1
may be assigned in the ν(C-H) vibration. Medium but
sharp scissoring band are seen at 2920, 2870 and 1438 cm-1
,
respectively. The bands at 1470, 1380, 1328, 1278, 1160,
1100, 1008, 900, 878, 364 and 319 cm-1
are associated with
the skeletal vibration of the whole complex. A medium but
sharp band at 478 cm-1
is attributed to the nickel nitrogen
bond. Coordination of water is supported by the presence of a
very strong but very broad band at 3250 cm-1
followed by a
very weak band at 800 cm-1
assigned to stretching and rocking

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vibrations of the water molecule, respectively. A band at 638
cm-1
is attributed to the (Ni-O) vibration of coordinatated
water.
In the complex the N-H stretching mode of the secondary
amine is seen at 3110 cm-1
while the position of the N-H
bending vibration is at 1580 cm-1
. A very weak very sharp
band at 1050 cm-1
is associated with (C-H). Coordination of
the ligand through the nitrogen is evident by a medium but
very band at 488 cm-1
The bands for coordinated water are
seem at 3225,812,670 and 606 cm-1
and are attributed to (O-
H), rocking and wagging vibration of H2O molecule and (Cu-
O) respectively [5].
The OCTC hydrochloride spectrum is different in several
respects from the spectrum of its nickel or copper complex.
The major difference occurs in the 1400-400 cm-1
region
where bands due to water molecules or metal coordinate bond
with nitrogen and oxygen are absent. The ligand hydrochloride
exhibit a series of weak or very weak but generally sharp
bands at 2775,2644,2495,2407,2366 and 2302 cm-1
,and a
prominent band at 2019 cm-1
(medium, sharp) associated with
>NH2Cl groups. Such bands are absent in the OCTC
complexes. The cyclic nature of the metal-free ligand is
demonstrated by the similarly of its amine bands with those of
the nickel or copper complex molecule [6]. A corresponding
(N-H) vibration is seen at 1600 cm-1
strong/medium/weak
bands for C-H asymmetric and symmetric stretching and
scissoring mode appear at 3008,2845 and 1402 cm-1
are also
characteristic of the whole ligand molecule [7]. (Table 1.3)
3.5 Nuclear Magnetic Resonance Spectra
Additional structural evidence for these ligands has been
obtained from the pmr spectra of their hydrochlorides. The
spectrum of OCTC hydrochloride [8] is slight shifting of the
signals. The alpha and bet methylenes resolved into broad
triplets and pentlet, respectively, are centred at 3.16 and 2.01
ppm. Their positions of resonances are in agreement with the
integrated of the signals (proton ratio 16:8). The NH2 protons.
A sharp peak at 3.44 ppm expected for methylene protons is
observed in the pmr spectrum of OCTC hydrochloride. Also, a
broad singlet at 4.95 ppm may be assigned to (CH+NH2)
proton resonance [8].
Nickel Complexes of OCTC
Very complex multiplets in the region 3.09-1.57 ppm in the
spectrum of nickel complex with OCTC are unintepretable.
But, a broad peak observed in the region 5.12-4.38 ppm is
expected for protons of coordinated water and the NH group
[9].
3.6 Mass Spectra OCTC Systems
Determination of molecular weight by mass spectra of the
compounds OCTC.8HCl has been very useful in completing
their characterization. The corresponding peaks in
OCTC.8HCl are very close to their molecular ions. The
slightly low m/z values in these systems may be associated
with the mass lost (H) due to fragmentation of the molecular
ions. The mass loss corresponds to the sum of the masses of
few H atoms and two and seven molecules of HCl attached
with the macrocycles, respectively, through weak coordinate
bonds [10].
3.7 Solubility, Conductivity and Other Data
The nickel complexes [Ni2 (OCTC) (H2O) 4] Cl4.5H2 O have
low decomposition points whereas others are thermally stable
and decompose near their melting points. In addition,
attachment of only one chloride ion through an ionic bond in
the nickel (II)-OCTC complex gives indirect information on
the metal-chloride ion coordinate linkage of the other chloride
ion. Also, the colour of the nickel (II)-OCTC complex is
Violet (bluish-violet). Whereas the complexes of copper (II)
are Violet (brown liquid).All the complexes are highly soluble
in water due to their ionic nature [11].Most of them are
soluble in many other polar solvents, like methanol, ethanol,
DMF, DMSO etc [12]. Similarly, the molar conductance
(ohm-1
cm2
mol-1
) obtained for [Ni2 (OCTC)(H2O)4]Cl4.5H2O
(498) or [Cu4(OCTC)(H2O)8]Cl8.6H2O (886) are consistent
with formation of these complexes[13].
CONCLUSIONS
The present investigation deals with the synthesis and
characterization of macrocyclic ligands and its transition metal
complexes. On the basis of elemental analysis, molecular
weight determination, conductance, IR and NMR spectral
studies, the nature as well as to some extent, structure and
stereochemistry of macrocyclic ligands have been suggested.
The above procedures outlined for the preparation of the
resultant macrocyclic complexes are facile and appear to
proceed smoothly. This is used as electro catalyst in fuel cell,
enhances the electrical conductivity. It should prove useful for
investigation of metal containing-biological molecules such as
metalloenzymes and their catalytic activity for industries. This
catalyst use for major change in Pharmaceutical education
Nahata catalyst which act as an efficient reusable
heterogeneous catalyst, this catalyst use in drug discovery and
drug development
REFERENCES
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[2]. N F Curtis,D A House,Chem. Ind. 1961,1708.
[3]. N F Curtis, Y M Curtis, H K J Powell, J.Chem. Soc. (A)
1966, 1015
[4]. R W Hay, G A Lawrance, N F Curtis, J.Chem. Soc.
Dalton Trans, 1975,591
[5]. R e Shephered, Coord.Chem.Rev, 2003, 247,147.
[6]. Z M Zaki, S S Haggag, A A Soayed , Spectrosc. Lett;
1989, 31,757

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[7]. E C Constable, Coord.Chem. Rev; 1989, 93,205
[8]. M N Patel, N H Patel, P K Panchal, D H Patel, Synth,
React. Inorg. Met.Org. Chem.2004, 34, 873.
[9]. R N Prasad, M Agarwal, R George, Synth. React. Inorg.
Met. Org. Chem.2004, 34, 943.
[10]. B Singh, K K Narang, R Srivastava,
Synth.React.Inorg.Me, Org.Chem.2002, 32, 1561.
[11]. J Rogan, D Poleti , L Karanovic, Bogdanovic, A S De
Bire, Polyhefron,2000, 19,1415.
[12]. H K Shin, K M Chin, J Farkas, M J H Smith, T T Kodas,
E N Duesler, Inorg.Chem, 199231,424.
[13]. G Ambrosi, M Formica, V Fusi, P Rossi, Inorg. Chem,
2007, 46, 309

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