International Journal of Medicine and

Pharmaceutical Sciences (IJMPS)

ISSN(P): 2250-0049; ISSN(E): 2321-0095
Vol. 5, Issue 6, Dec 2015, 21-28
TJPRC Pvt. Ltd.

STRUCTURAL STUDIES ON CU (II), FE (III) AND UO2 (II) COMPLEXES WITH

PYRAZINE-2-CARBOXYLIC ACID HYDRAZIDE AND ITS DERIVATIVES
RAVISH KUMAR CHAUHAN
Associate Professor, Department of Chemistry, Indira Gandhi National College,
Ladwa, Kurukshetra, Haryana, India
ABSTRACT
Transition metals and their complexes have evolved great interest due to their biological potential(1,2) unusual
structural aspects, unique stereo and magneto chemistry (3) Azomethine constitute one of the most important class of
biologically active ligands providing potential binding sites through nitrogen and sulphur/oxygen donor atoms. The
different modes of bonding produce appreciable changes in the biochemical properties of the metal derivatives which
are prepared and are of tremendous interest due to the current focus in the study of sulphur nitrogen donor ligands and
their complexes. Our continuing interest in the synthesis of biologically active. Complexes, led us to further synthesise
and characterize a new class of unsymmetrical Cu (II), UO2 (II) and Fe(III) complexes during the course of the present
withdrawing groups at ortho and/ or para positions of the benzene ring may also affect the isomer shift (14, 15). This is
because disubstitution in the benzene ring may affect the nature of (Fe-O) bond to some extent. Similar variations have
been observed in alkyl phosphine and phosphite substituted pentacyano ferrate complexes

(16)

. It is well known that

-values and metal-ligand stretching vibrations are affected 'by the substitution of alkyl or halide group in the ligand.
KEYWORDS: Pyrazine-2-Carboxylic Acid Hydrazide Cu (II), Fe (III) and UO2 (II) Complexes

Original Article

investigation employing pyrazine-2-carboxylic acid hydrazide and its derivatives. Nature of electron donating or

Received: Jul 23, 2015; Accepted: Jul 31, 2015; Published: Nov 21, 2015; Paper Id.: IJMPSDEC20153

INTRODUCTION
Transition metals and their complexes have evolved great interest due to their biological potential(1,2)
unusual structural aspects, unique stereo and magneto chemistry (3) Azomethine constitute one of the most
important class of biologically active ligands providing potential binding sites through nitrogen and
sulphur/oxygen donor atoms. The case of formation of a variety of metal complexes from these ligands like
thiosemicarbazones semicarbazones, dithiocarbazates and benzothiazolines speak for their spectacular progress in
coordination and bioinorganic chemistry.
The different modes of bonding produce appreciable changes in the biochemical properties of the metal
derivatives which are prepared and are of tremendous interest due to the current focus in the studyofsulphur
nitrogen donor ligands and their complexes. Subsequently azomethines and their derivatives are gaining
importance due to their unique structural and stereochemical aspects, and their use as models in industrial,
biological, analytical and antimicrobial systems(4,5) To illustrate a few examples, azomethines and their derivatives
are known to exhibit a wide range of pharmacological properties such as anticancerous and antibacterials(6).
Our continuing interest in the synthesis of biologically active complexes, led us to further synthesise and
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22

Ravish Kumar Chauhan

characterize a new class of unsymmetrical Cu (II), UO2 (II) and Fe(III) complexes during the course of the present
investigation employing pyrazine-2-carboxylic acid hydrazide and its derivatives. Rf-values of complexes along with
different solvent used as eluant are summarized in tabular form. Relative flow of Fe (III), Cu(II) and UO2(II) komplexes
are in the sequence of T2 < T6. < T5 < T4 < T3 < T1, revealing thereby in the progressive increase of Rrvalue, with the
polarity of the solvent.

MATERIALS AND METHODS

Synthesis of Cu (II) Complexes
These complexes were synthesised by refluxing the requisite amounts of the pyrazine-2-carboxylic acid hydrazide
and its derivatives as well copper salts in (1:2) molar ratio in ethanol (50 ml). Contents were refluxed for two hours, on
water bath. After complete reaction, the products were filtered off and the excess of the solvent was removed over the ratio
head and the complexes were dried in vacuo. These were purified by repeated washingswith ethanol and finally
recrystallised from methanol
Synthesis of Fe (III) Complexes
Acetonic solution containing iron salt was added to pyrazine-2-carboxylic acid hydrazide and its derivatives
(hydrazones) in a required molar ratio (1:2). The reaction mixture was stirred and refluxed for two hours on water bath to
ensure completion of the reaction. Removal of volatiles in situ under reduced pressure at room temperature, yielded
coloured mass, the analysis of which corresponded to that of the desired product
Thin Layer Chromatographic Screening
Iron (III), Copper (II) and Uranyl(II) complexes of pyrazine-2-carboxylic acid hydrazide and its hydrazones were
screened for thin layer chromatography using different solvent systems. Clear visible spot of the complexes were noticed
and no other spot corresponding to hydrazide and hydrazones were appeared indicating purity of the complexes. Rf-values
of complexes along with different solvent used as eluant are summarized in tabular form. Relative flow of Fe(III), Cu(II)
and UO2(II) komplexes are in the sequence of T2 < T6. < T5 < T4 < T3 < T1, revealing thereby in the progressive increase of
Rrvalue, with the polarity of the solvent.

RESULTS AND DISCUSSIONS

The complexes are highly stable under normal laboratory conditions. They have high melting points and are
slowly attacked by dilute acids and alkalies. The elemental analysis and molar conductance values are given in tables.
The stoichiometries of the complexes were confirmed by their elemental analysis. All these complexes are insoluble in
common organic solvents like ethanol, benzene, chloroform etc, but they are soluble in DMF and DMSO. The molar
conductance measured in DMF at 10-3 M for these complexes fall in the range 2.70-83.4 ohm-1 cm2 mo11 indicating their
electrolytic /non electrolytic behaviour.
Magnetic Susceptibility Studies
Fe (III) complexes exhibit magnetic moment around 5.22-5.88 B.M., which fall in the usual range of 5.0-6.0 B.M.
in octahedral symmetry(7). The room temperature magnetic moment value of Cu(II) complexes lie in the range 1.30-1.70
B.M. as expected for a one electron(8) system. The effective magnetic moment value of dioxouranium(VI) complexes at
room temperature, lie in a narrow range, showing their diamagnetic behaviour.
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Structural Studies on Cu (II), Fe (III) and Uo2 (II) Complxes With

Pyrazine-2-Carboxylic Acid Hydrazide and Its Derivatives

23

Electronic Spectral Studies

The electronic spectral data and their assignments of all the complexes are discussed. For high spin Fe(III) a
pattern of four bands is usually expected for octahedral symmetry, which are assigned to the transitions 6A1g(S) 4T1g (F);
6

A1g (S) 4T2g(F) 6A1g(S) 4Eg(D) and 6A1g(S) 4T2g(D)19. Al.l these four transitions are not observed separately in the

complexes. The Fe(III) complexes reported here reveal two bands in the range ~13000-16000 cm-1 and 16000-22000 cm-1
assignable to 6A1g(S)4T1g (F) and 6A1g(S) 4T2g(F) transitions respectively characteristic of octahedral geometry (19,20).
Table 1: Thin Layer Chromatographic Screening of Fe (III) and UO2(II) Complexes using T1 Methanol : Amnonia
Solution Strong (100:1.5) T2- Glacial Acetic Acid-Benzene (1:9); T3- Ammonia Solution Strong : Ethanol (90%) :
Dioxane (5:60:35), T4- Glacial Acetic Acid : Ethanol (90%) : Water (30:60:10); T5- n Butyl Alcohol : Methanol
(40:60) and T6- Ammonia Solution : Benzene : Dioxane : Ethanol (90%) 5:50:405) as Mobile Phase
S.No.

Compound

Solvent
System I

Solvent
System II

Solvent
System III

1.
[Fe(C12H10N4O)2Cl2]Cl
83.0
3.0
72.60
2.
[Fe(C13H12N4O)2Cl2]Cl
82.6
1.2
66.30
3.
[Fe(C13H12N4O)2Cl2]Cl
59.30
0.65
51.30
4.
[Fe(C16H19N5O)2Cl2]Cl
82.70
2.0
63.75
5.
[Fe(C13H11N4O)2Cl]
77.28
0.0
64.0
6.
[UO2(C13H12N4O2)(CHOO)2]
83.10
0.60
60.36
7.
[UO2(C16H19N5O)(CH3COO)2]
82.6
1.4
60.4
(a)Silica gel-G (incorporating 13% calcium sulphate as binder was used as absortbent,

Solvent
System
IV
61.42
62.20
63.80
59.85
58.2
60.6
56.4

Solvent
System V
58.23
60.0
54.8
63.10
46.40
57.9
64.8

Solvent
System
VI
80.3
10.0
42.5
0.0
40.0

(b)The spot were detected by iodine vapours.

Table 2: Analytical and Magnetic Data of Iron (III) Complexes with
Pyrazine-2-Carboxylic acid Hydrazide and Its Derivatives

H S O- HIGH Spin Octahedral

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Ravish Kumar Chauhan

Table 3: Analytical and Magnetic Data of Copper (II) Complexes with

Pyrazine-2-Carboxylic Acid Hydrazide and its Derivatives

T.D Tetragonally distorted.

Table 4: Analytical and Magnetic Data of UO2 (II) Complexes with
Pyrazine-2-Carboxylic acid Hydrazide and Its Derivatives

Figure 1: I.R Spectra of Fe (III) Complexes

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Structural Studies on Cu (II), Fe (III) and Uo2 (II) Complxes With

Pyrazine-2-Carboxylic Acid Hydrazide and Its Derivatives

25

Figure 2: I.R Spectra of Cu (II) Complexes

Table 5: Electronic Spectral Data and Relevant Ligand Field Parameters from High Spin Octahedral
Iron (iii) Complexes with Pyrazine-2-Carboxylic acid Hydrazide and its Derivatives

Cu (II) Complexes .Ligand field splitting energy levels diagram for Cu(II) ion for different stereochemical modes
viz octahedral field (Oh) and distorted tetragonal field D4h is given overleaf. The presence of one unpaired electron in the
complex is indicated by ti-effective of 1.30-1.70 B.M. In all complexes of Cu(II) the three (d-d) transitions are observed in
the visible region and have been tentatively assigned as given below 11400-13400 cm-1 2B1g-2A1g; (dx2-y2dzx)(
17200-18400 cm-1 2B1g 2E1g; (dx2-y2 dyz)(

2);

2220023990 cm-1 2B1g 2B29; (dx2-y2 dxy)(

intensity of the first band (vi) was found lower than the other two (d-d) transitions(

2,

3),

3).

1);

The relative

making use of the electronic

spectra of the complexes and effective magnetic moments, tetragonally distorted square planar stereochemistry, may be
assumed around copper(II) complexes(2629). Comparison of the JR-spectra of free ligands pyrizine-2carboxylic acid
hydrazide

(C5H6N4O);

benzylidene

2-pyrazinoyl

hydrazone

(C12H10N4O);

anisalidene-2-pyrazinoyl

hydrazone

(C13H12N4O2); 4-hydroxy-3-methoxy benzylidene-2-pyrazinoyl hydrazone (C16H19N5O); cinnamalidene-2-pyrazinoyl

hydrazone

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Ravish Kumar Chauhan

Figure 3: Energy Level Diagram for the Cu (II) ion in an Octahedral Field (Oh) and the
Distorted Tetragonal Field (D4th) of an Elongated Bipyramid and a Square
(C14H12N4O); 4-methyl salicylidene-2-pyrazinoyl hydrazone (C13H12N4O2); and 2-furfuralidene-2- pyrazinoyl
hydrazone (C11H10N4O2) and their Fe (III), Cu (II) and UO2 (II) complexes show that all ligands are bidentate with
carbonyl oxygen and azomethine nitrogen as coordinating sites except 4-methyl salicylidene-2-pyrazinoyl hydrazone
(C11H10N4O2) which are found to be tridentate, third coordinating site being phenolic-oxygen and furan oxygen respective
l[UO2(C5H6N4O)(CH3COO)2]: The complex was found thermally stable up to 150C and mass loss takes place
rapidly in the temperature range 400-650C. The complex decomposes finally into U3O8, which is most thermally stable
oxide of uranium and fraction decomposed = 0.32 corresponds well to U3O8,. The DTA curve-shows two exothermal
peaks at 425C and 495C, correspond to the corriplete burning of the organic portion of the complex.
[UO2(C13H11N4O2)(CH3COO)]: From the 'TG' curve it was observed that the complex is stable up to 370C and
mass loss takes place rapidly in the temperature range 350-650C, the complex decomposes into oxide at 650C. The
fraction decomposed =0.54 corresponds to the decomposition of the complex into U3O8,. The DTA curve, shows the
endothermal peaks at 155C, 360C and 380C corresponding to the melting of the complex. The endothermal peaks at
360C, 390C 470C and 520C corresponds to the complete burning of the organic portion of the complex.
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Pyrazine-2-Carboxylic Acid Hydrazide and Its Derivatives
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