CHAPTER THREE: PART-A

Results and discussion of Schiff base metal complexes

 Chapter -III
(Part - A)
RESULTS AND DISCUSSION OF SCHIFF BASES AND THEIR
METAL COMPLEXES
3.1 Introduction
3.2 Characterization of ligands
3.3 Elemental Analysis
3.4 Characterization of Cu(II), Co(II), Ni(II), Cd(II) and Hg(II) complexes:
Contents

3.5 I. R. Spectral analysis of Ligands

3.6 Far I.R. Studies
3.7 Electronic spectral studies of Co(II), Ni(II) and Cu(II) complexes
1
3.8 HNMR Spectral Studies
3.9 LC-Mass Spectral Studies

3.1. Introduction
The following chapter deals with the experimental results and discussion on
analytical data, conductance measurements, magnetic moment value, electronic, IR,
1
HNMR and Mass spectral data.
Coordination compounds containing benzofuran and naphthofuran skeleton are an
important class of compounds which have been studied long back owing to their wide
applications in pharmaceutical, chemical and industrial field. The applications of the
benzofuran and naphthofuran for selective metal complex formation received considerable
attention in the last few years. Based on literature survey it is found that there is a much
scope for the exploration of the field of complex formation ability of various substituted
benzofuran/naphthofuran derivatives. In view of the importance of the Schiff bases and
their metal complexes in biology and chemistry, we decided to synthesize the metal
complexes with Schiff bases derived from condensation of benzofuran-2-
carboxamide/napthofuran-2-carbohydrazide with aldehydes/substituted aldehydes with
some of the transition metal ions like Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II).
Synthesized all the metal complexes have been characterized on the basis of analytical and
spectral data. All the ligands and their metal complexes were screened for their antifungal
and antibacterial activity. Further, some of the ligands and their metal complexes have been

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
tested for their DNA cleaving ability. The following ligands (Figure –3.1 and Figure -3.2)
were synthesized and used for complex preparation.

L-II
L-I

L-III L-IV

Figure – 3.1

L-V
L-VI

L-VIII
L-VII

Figure – 3.2

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
3.2. Characterization of ligands:

The free ligands are characterized by the Elemental analysis and spectroscopic
methods which include I.R. NMR and Mass spectroscopy, etc.

3.3. Elemental analysis:

The elemental analysis data of the ligands [L-I] to [L-VIII] and their metal
complexes are given in the Table-3.1 to 3.8.

3.4. Characterization of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) complexes:

3.4.1. Nature and stoichiometry:

The synthesized metal complexes are characterized by analytical and spectral data
and are given in Table-(3.1 to 3.8.) All the complexes are colored, stable and soluble in
DMF and DMSO and sparingly soluble in common organic solvents at room temperature.

3.4.2. Molar conductance studies:

The conductance measurements were carried out in Dimethyl formamide (DME)
solution at a concentration of 10-3 M and the measured molar conductance values fall in the range
17.80 – 8.18 ohm-1 cm2 mole-1 and are too low to account for any dissociation of the
complexes in DMF solution. These low conductivity values of synthesized complexes,
suggest the non-electrolytic behavior of complexes [1]. The observed molar conductance
values are given in Table-(3.1 to 3.8).

3.4.3. Magnetic susceptibility studies:

A magnetic moment value explains a lot about the stereochemical configuration of
the metal complexes. The magnetic susceptibility measurements help in establishing the
structure of the compounds in combination with electronic spectral data. The
paramagnetism of substance is due to the presence of unpaired electron. Two properties
of an unpaired electron are spin and orbital moment contributes to the magnitude of the
paramagnetic moment. The spin only value of the magnetic moment S is given by the
relation.

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 𝝁𝒔 = [𝒏(𝒏 + 𝟏)]𝟏/𝟐
Where n = number of unpaired electrons.

The inconsistency between the measured magnetic moment and that calculated
from the above equation is due to the removal of orbital degeneracy of ‘d’ orbitals by
ligands. The magnetic susceptibility of a given material consists of contributions from
paramagnetic and diamagnetic susceptibilities the former being much greater. However,
for molecules containing a large number of diamagnetic atoms per paramagnetic atoms,
the diamagnetic contribution can be appreciable. The effective magnetic moment (eff)
values observed at room temperature (25 C) for the present complexes have been listed in
Table-(3.1 to 3.8.)

3.4.4. Cobalt (II) complex:

The octahedral Co(II) complexes have ground state 4T1g and a large orbital
contribution to the magnetic moment is expected. The mixing of the singlet states lowers
the magnetic moments. The reported magnetic moment values for various Co(II)
complexes are in the range 4.134.70 and 4.70-5.50 B.M. for tetrahedral and octahedral
complexes [1,2]. C. Celik et al. [3] have reported magnetic moment value for the cobalt
complexes in the range of 4.32-4.25. Jha et.al. [4], have reported eff values for Co(II)
complexes in the range 5.005.50 BM for octahedral geometry. Mishra et.al. [5], have
reported some octahedral Co(II) complexes with magnetic moment values in the range 5.00
5.20 B.M and Subbarao [6], have measured magnetic moments of several carboxylates of
Co(II) complexes and values lie between 5.005.22 BM Such complexes have been
assigned high spin octahedral configurations. Patel et.al. [7], have reported the magnetic
moment values in the range 4.50-4.90 BM and suggested an octahedral geometry around
the metal ion Co(II) complexes. The low values of magnetic moments for the complexes
may be due to certain amount of metalmetal interaction arising from polymeric structure
of the complex [8].
In the present investigation the observed magnetic moment values for Co(II)
complexes fall in the range 4.58-4.86 BM which are indicative of octahedral geometry for
the present Co(II) complexes [9]. These values lie in the range expected for s and s+1.

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
3.4.5. Nickel (II) complexes:
From the magnetic point of view, most of the Ni(II) complexes may be divided into
three categories.
1. Six coordinated octahedral paramagnetic complexes with 3A2g ground state.
2. Four coordinated paramagnetic tetrahedral complexes with 3T1g ground state.
3. Four coordinated square planar diamagnetic complexes with spin singlet ground state
of the two magnetic types (1) and (2) the octahedral complexes have a 3A2g ground state
and hence the orbital contribution to the magnetic moment due to orbital degeneracy is
absent.
F. A. Cotton et.al. [10], have reported magnetic moment values in the in the range 2.62
 2.91 BM for Ni(II) octahedral complexes. Charanjit Singh et.al. [11], have reported the
magnetic moment values in the range 3.013.29 B.M. for octahedral Ni(II) complexes.
Carlin [12] have reported the magnetic moment value in the range 3.213.34 BM for spin
free octahedral Ni(II) complexes. Mishra et. al. [13] and others have reported magnetic
moment values in the range 3.213.34 BM for spin free octahedral Ni(II) complexes. A. A.
Osowole et. al. [14] have reported magnetic moment value for nickel complexes in the
range of 3.1-3.5 BM for octahedral geometry. Ray et.al. [15], have reported magnetic
moment values in the range 2.83-3.40 BM for Ni(II) octahedral complexes. Malhotra et.al
[16], have reported some Ni(II) complexes derived from 2,6bis(2
hydroxybenzylidenehydrazone) having magnetic moment value in the range 3.103.20
BM They have reported little spinexchange interaction between the two Ni(II) ions.
In the present investigation the observed magnetic moment values for Ni(II)
complexes fall in the range 2.57 – 2.98 B.M. which are well within the range expected for
octahedral geometry around the central metal ion. The observed magnetic values are
shown in Table-(3.1 to 3.8.).

3.4.6. Copper(II) complex:

The Cu(II) complexes may be broadly classified into two classes. The complexes
with temperature independent magnetic moment values in the range of 1.752.2 BM
agreeable to the spin only value. These complexes are mononuclear having no major spin

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
spin interactions. However, no compromise can be set between the magnitude of the
distortion and other variable factors [17]. The complexes which show subnormal magnetic
moments and diamagnetism. The Cu(II) complexes with this behavior indicate marked
spin exchange and strong coupling interaction between two Cu(II) atoms [18]. Angela
et.al. [19], have reported Cu(II) complexes with magnetic moment values falling in the
range 1.90  2.01 BM for distorted octahedral geometry. S. S. Chavan et. al. [20] have
reported magnetic moment value in the range 1.79-1.89 BM for octahedral and 1.92-1.89
for square planar copper complexes. Hiremath et.al. [21], have reported the magnetic
moment values around 2.01 BM for Cu(II) complexes of distorted octahedral geometry. N.
Raman et. al. [22] have reported magnetic moment value for tetrahedral copper complexes
in the region 1.7-1.8 BM. Sengottavelan et.al. [23], have reported magnetic moment value
of 1.59 BM. for binuclear Cu(II) complex and they have justified this value by measuring
its antiferromagnetic exchange interaction between two Cu(II) centers of binuclear
complexes.
In the present study the observed values of magnetic moments are in the range 1.57-
1.87 B.M. These values suggest the distorted octahedral geometry around Cu(II) ion.
Table-(3.1 to 3.8.).

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Table-3.1. Elemental analysis and physical characteristics of Ligand [L-I] and its metal complexes

Empirical formula
Mol.
Wt.
M.P Yield
(%)
Elemental analysis (%) found(calculated) eff M †
(C) B.M
C H N M Cl
[C16H11BrN2O3](L-I) 359.17 210 65 53.50(53.32) 03.09(3.00) 07.80(7.20) -- --- --- --
[Co(C16H10BrN2O3)2] 775.23 >300 65 48.33(49.58) 2.30(2.60) 6.90(7.23) 7.07(7.60) --- 4.86 14.32
[Ni(C16H10BrN2O3)2] 775.03 289 60 48.88(49.59) 2.49(2.60) 6.55(7.23) 6.89(7.57) --- 2.89 17.80
[Cu(C16H10BrN2O3)2] 492.60 > 300 65 49.10(49.28) 2.52(2.58) 7.07(7.18) 8.01(8.15) --- 1.87 14.60
[Zn(C16H10BrN2O3)Cl] 459.45 280 50 40.98(41.87) 2.13(2.20) 5.89(6.10) 13.88(14.24) 7.66(7.72) --- 15.19
[Cd(C16H10BrN2O3)Cl] 506.03 275 60 37.81(37.98) 1.89(1.99) 5.50(5.54) 22.10(22.21) 6.89(7.01) --- 14.32
[Hg(C16H10BrN2O3)Cl] 594.21 >300 70 32.13(32.34) 1.66(1.70) 4.69(4.71) 33.44(33.76) 5.89(5.97) --- 13.10
† ohm-1 cm2 mole-1

Table-3.2. Elemental analysis and physical characteristics of Ligand [L-II] and its metal complexes

Empirical formula
Mol.
Wt.
M.P Yield
(%)
Elemental analysis (%) found(calculated) eff M †
(C) B.M
C H N M Cl
[C19H21BrN2O2](L-II) 389.2 220 63 53.50(58.62) 03.09(5.44) 07.80(7.20) -- -- -- --
[Co(C19H21BrN2O2)Cl2]n 516.9 >300 72 43.22(43.96) 3.91(4.08) 05.00(5.40) 11.22(11.35) 13.56(13.66) 4.86 14.60
[Ni(C19H21BrN2O2)2Cl2] 908.1 >300 66 49.88(50.26) 4.39(4.66) 06.11(6.17) 06.26(06.46) 07.60(07.81) 2.96 14.08
[Cu(C19H21BrN2O2)2Cl2] 913.0 >300 65 43.44(49.99) 4.35(4.64) 05.11(6.14) 06.81(06.96) 07.21(07.77) 1.87 15.07
[Zn(C19H21BrN2O2)Cl2] 521.9 >300 75 43.38(43.42) 3.94(4.03) 05.21(5.33) 12.19(12.44) 13.36(13.49) __ 15.19
[Cd(C19H21BrN2O2)Cl2] 571.9 >300 68 39.78(39.85) 3.65(3.70) 04.82(4.89) 19.58(19.63) 12.20(12.38) ---- 14.32
[Hg(C19H21BrN2O2)Cl2] 659.9 >300 82 34.10(34.54) 3.11(3.20) 04.11(4.24) 30.12(30.36) 10.58(10.73) 13.10
† ohm-1 cm2 mole-1

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Table-3.3. Elemental analysis and physical characteristics of Ligand [L-III] and its metal complexes
eff
M †
Mol. M.P Yield Elemental analysis (%) found(calculated)
Empirical formula Wt. (C) (%) C H N M B.M
[C20H13BrN2O3][LIII] 409.2 220 63 53.50(53.62) 05.09(5.44) 07.80(7.20) -- --- ---
[Co(C20H12BrN2O3)2] 875.4 348 72 54.88(53.96) 2.76(2.08) 6.40(6.01) 6.73(5.88) 4.86 13.60
[Ni(C20H12BrN2O3)2] 875.1 312 66 54.90(53.33) 2.76(2.12) 6.40(6.17) 6.71(6.15) 2.96 09.81
[Cu(C20H12BrN2O3)2] 880.0 310 65 54.59(53.99) 2.75(2.21) 6.37(6.01) 7.22(6.96) 1.67 08.10
[Zn(C20H12BrN2O3)2] 881.8 320 75 54.48(53.42) 2.74(2.00) 6.35(5.89) 7.41(6.96) --- 10.30
[Cd(C20H12BrN2O3)2] 928.9 330 68 51.72(50.85) 2.60(2.55) 6.03(5.55) 12.10(11.63) --- 13.32
[Hg(C20H12BrN2O3)2] 1017.0 340 75 47.24(46.54) 2.38(2.20) 5.51(4.88) 19.72(18.01) --- 12.10

Table-3.4. Elemental analysis and physical characteristics of Ligand [L-IV] and its metal complexes
Mol. M.P Yield Elemental analysis (%) found(calculated)
eff M
B.M †
Empirical formula Wt. (C) (%)
C H N M Cl
[C22H15BrN4O3](L-IV) 463 233 68 56.10(57.04) 03.09(3.26) 12.01(12.09) ---- ---- --- ---
[Co(C22H14BrN4O3)2] 984 >300 65 53.20(53.73) 02.30(2.87) 11.10(11.39) 05.78(05.99) ---- 4.77 13.14
[Ni(C22H14BrN4O3)2] 983 >300 68 53.01(53.75) 02.20(2.87) 11.00(11.40) 05.97(05.97) ---- 2.82 15.01
[Cu(C22H14BrN4O3)2] 988 >300 73 53.01(53.48) 02.70(2.86) 11.30(11.34) 06.20(06.43) ---- 1.65 11.85
[Zn(C22H14BrN4O3)Cl] 598 >300 76 44.01(44.15) 02.03(2.36) 08.99(09.36) 10.88(10.92) 11.52(11.85) __ 16.16
[Cd(C22H14BrN4O3)Cl] 646 >300 69 40.88(40.93) 01.89(2.19) 08.56(08.68) 17.22(17.41) 10.82(10.98) ---- 14.58
[Hg(C22H14BrN4O3)Cl] 734 >300 85 35.83(36.01) 01.75(1.92) 07.22(07.64) 27.01(27.34) 09.42(09.66) ---- 11.09
† ohm-1 cm2 mole-1

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Table-3.5. Elemental analysis and physical characteristics of Ligand [L-V] and its metal complexes

Empirical formula
Mol.
Wt.
M.P Yield
(%)
Elemental analysis (%) found(calculated) eff M †
(C) B.M
C H N M Cl
[C21H16N2O2S](L-V) 360.09 225 66 69.60(69.98) 4.11(4.47) 07.12(7.77) -- -- -- --
[Co(C21H16N2O2S)2Cl2] 850.00 >300 65 59.01(59.30) 3.56(3.79) 6.44(6.59) 6.88(6.93) 8.10(8.34) 4.82 16.52
[Ni(C21H16N2O2S)2Cl2] 850.46 289 69 52.00(52.32) 3.69(3.79) 6.44(6.59) 6.88(6.93) 8.20(8.34) 2.84 17.23
[Cu(C21H16N2O2S)2Cl2] 855.31 >300 65 58.77(58.98) 3.56(3.77) 6.45(6.55) 7.20(7.43) 8.11(8.29) 1.88 15.22
[Zn(C21H16N2O2S)Cl2] 496.71 280 56 50.62(50.78) 3.13(3.25) 5.16(6.64) 12.92(13.16) 14.02(14.27) __ 14.56
[Cd(C21H16N2O2S)Cl2] 543.75 291 66 46.20(46.39) 2.88(2.97) 5.04(5.15) 20.42(20.67) 12.90(13.04) ---- 15.23
[Hg(C21H16N2O2S)Cl2] 631.92 >300 70 39.82(39.91) 2.41(2.55) 4.22(4.43) 31.55(31.74) 11.02(11.22) ---- 16.54
† ohm-1 cm2 mole-1

Table-3.6. Elemental analysis and physical characteristics of Ligand [L-VI] and its metal complexes

Empirical formula
Mol.
Wt.
M.P Yield
(%)
Elemental analysis (%) found(calculated) eff M †
(C) B.M
C H N M Cl
[C26H18N4O3](L-VI) 434.5 229 68 71.74(71.88) 03.95(4.18) 11.89(12.90) -- ---- -- --
[Co(C26H17N4O3)2] 925.8 >300 65 67.20(67.48) 3.68(3.70) 12.05(12.10) 6.20(6.34) ---- 3.01 11.00
[Ni(C26H17N4O3)2] 925.6 >300 66 67.38(67.48) 3.59(3.70) 11.87(12.11) 6.26(6.34) ---- 2.95 12.70
[Cu(C26H17N4O3)2] 930.4 >300 72 66.02(67.13) 3.58(3.68) 11.88(12.04) 6.67(6.83) ---- 1.94 11.25
[Zn(C26H17N4O3)Cl] 534.45 >300 68 57.92(58.45) 3.08(3.21) 10.10(10.49) 11.11(12.24) 6.35(6.64) __ 17.45
[Cd(C26H17N4O3)Cl] 581.30 >300 71 53.44(53.72) 2.56(2.95) 9.51(9.64) 19.10(19.34) 5.88(6.10) ---- 14.85
[Hg(C26H17N4O3)Cl] 669.48 >300 82 45.88(46.64) 2.11(2.56) 8.20(8.37) 18.66(18.79) 5.22(5.30) ---- 11.65
† ohm-1 cm2 mole-1

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Table-3.7. Elemental analysis and physical characteristics of Ligand [L-VII] and its metal complexes

Empirical formula
Mol.
Wt.
M.P Yield
(%)
Elemental analysis (%) found(calculated) eff M †
(C) B.M
C H N M Cl
[C21H13N3O3](L-VII) 355.4 228 69 70.74(70.98) 03.48(3.69) 11.67(11.83) -- --- -- --
[Co(C21H13N3O3)2Cl2] 868.6 >300 68 60.01(60.84) 3.33(3.48) 9.52(9.68) 6.63(6.78) 7.92(8.16) 3.08 10.08
[Ni(C21H13N3O3)2Cl2] 868.4 >300 66 60.59(60.86) 332(3.48) 9.52(9.68) 6.55(6.76) 8.03(8.17) 2.54 14.14
[Cu(C21H13N3O3)2Cl2] 873.2 >300 63 60.22(60.52) 3.12(3.46) 6.25(9.62) 7.11(7.28) 8.02(8.12) 1.82 16.00
[Zn(C21H13N3O3)Cl2] 505.7 >300 75 52.10(52.26) 2.81(2.99) 8.10(8.31) 12.88(12.93) 13.88(14.02) __ 17.75
[Cd(C21H13N3O3)Cl2] 552.7 >300 71 47.62(47.81) 2.66(2.74) 7.55(7.60) 20.10(20.34) 12.77(12.83) ---- 10.45
[Hg(C21H13N3O3)Cl2] 640.9 >300 82 41.11(41.23) 2.33(2.36) 6.45(6.56) 31.28(31.30) 11.01(11.06) ---- 10.52
† ohm-1 cm2 mole-1

Table-3.8. Elemental analysis and physical characteristics of Ligand [L-VIII] and its metal complexes

Empirical formula
Mol.
Wt.
M.P Yield
(%)
Elemental analysis (%) found(calculated) eff M †
(C) B.M
C H N M Cl
[C21H16N2O4](L-VIII) 360.4 231 66 69.55(70) 04.09(4.48) 07.80(7.77) -- --- --- --
[Co(C21H16N2O4)2Cl2] 852.6 >300 70 58.89(59.17) 4.00(4.02) 6.47(6. 57) 6.80(6.91) 8.08(8.32) 3.09 10.45
[Ni(C21H16N2O4)2Cl2] 852.3 >300 66 59.00(59.18) 3.88(4.02) 6.22(6.57) 6.77(6.89) 7.94(8.32) 2.80 10.80
[Cu(C21H16N2O4)2Cl2] 857.2 >300 72 58.64(58.85) 3.91(4.00) 6.21(6.54) 7.11(7.41) 8.08(8.27) 1.81 11.78
[Zn(C21H16N2O4)Cl2] 496.7 >300 75 50.38(50.79) 3.10(3.25) 5.21(5.64) 13.00(13.16) 14.015(14.28) __ 09.48
[Cd(C21H16N2O4)Cl2] 543.7 >300 68 46.12(46.39) 2.65(2.97) 4.97(5.15) 20.19(20.68) 12.88(13.04) ---- 09.45
[Hg(C21H16N2O4)Cl2] 496.7 >300 88 50.58(50.79) 3.10(3.25) 5.62(5.64) 13.10(13.16) 14.10(14.28) ---- 08.90
† ohm-1 cm2 mole-1

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
3.5. I. R. spectra of ligands:

Infrared spectroscopy deals with the fact that molecules absorb specific frequencies
which is the characteristic of their molecular structure. In particular, in the Born–
Oppenheimer and harmonic approximations, i.e. when the molecular Hamiltonian
corresponding to the electronic ground state can be approximated by a harmonic oscillator
in the neighborhood of the equilibrium molecular geometry, the resonant frequencies are
associated with the normal modes corresponding to the molecular electronic ground state
potential energy surface. The resonant frequencies are also related to the strength of the
bond and the mass of the atoms at either end of it. Thus, the frequency of the vibrations are
associated with a particular normal mode of motion and a particular bond type. In the
present study the strong bands in the region 31143360 cm-1 were attributed to (NH)
stretch of –CONH- group. These bands shift to higher frequencies in the complexes by
about 7-16 cm-1, thereby indicating non-involvement of ‘NH2’ of –CONH- group in
bonding with metal ions [24-28]. The bands due to (C=O) stretch of –CONH- group
appears in the region 17001657cm-1. These bands shift to lower wavenumber side in all
the complexes by about 20-40 cm-1, indicating participation of the carbonyl oxygen in
coordination [29-32]. Medium to strong intensity bands appearing in the region 16231594
cm-1 are assigned to (C=N) stretch of azomethine group. These bands shift to lower
wavenumber side in all the complexes by about 21-50 cm-1, indicating the participation of
azomethine nitrogen in bonding with metal ion [33-36]. The medium to strong intensity
bands observed in the region 1061-1226 cm-1 are attributed to (COC) stretching
vibration of benzofuran ring in the free ligands. These bands remain unaltered in the metal
complexes indicating non-participation of the furan ring oxygen atom in the bonding with
metal ions [37-39]. In the far IR spectra of the complexes, the bands in the region 595-503
cm-1 and 476-425 cm-1assigned to M-O and M-N stretching vibrations respectively in all
the complexes [40-42]. The IR spectral analysis of ligand and their metal complexes gives
valuable information about the nature of metal ligand bond, molecular symmetry,
electronic distribution and stability of the complexes [36, 43-46]. Metals on coordination
with ligands causes changes in vibrational frequencies of the ligands, appearance or

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes
disappearance of old bands, splitting of the degenerate modes due to the lowering of
symmetry or intensification of spectra in the complexes [47].
In the present investigation, the frequency shift, splitting, change in intensity of the
ligand bands caused by the complex formation when they coordinate to the metal ion has
been discussed. The important infrared frequencies of the ligands and their corresponding
metal complexes have been presented in the Table-(3.9 to 3.16) and typical IR spectra of
few complexes are represented in Figure (3.3-3.32).

Literature survey show that many workers have reported (C=N) stretching
vibrations of Schiff bases in various regions. N. Raman et.al. [48], have assigned C=N
band in the range 16201560 cm-1. In the complexes these bands appear in the range 1600
1530 cm-1 these bands are shifted to lower wave number by 10  5 cm-1 indicating the
coordination through azomethine nitrogen. Subrammaniyam et.al. [49], have reported that
the bands due to (C=N) stretch appears around 1620 cm-1 in the case of
salicylaldiminobiacetyl monohydrazones.
Caroline Jubert et.al. [50], have reported bands in the region 16001580 cm-1 to
(C=N) stretch in Schiff bases. Patel et.al. [51], and G. S. Biradar et.al. [52], have reported
marked changes in (C=N) stretching vibrations on complexes formation. Zhang et.al.
[53], have reported that the band pertaining to (C=N) stretch shows considerable low
frequency shift and is located in the region 16001580 cm-1 in the complexes. The shift of
the order of about 2030 cm-1 to lower frequency is suggestive of coordination of (C=N)
stretch to the metal via nitrogen atom. The interpretation of these shifts depends upon the
attribution of the observed frequency to (C=N) stretching vibrations.

Based on these reports, the present Schiff bases show the band in the region 1608-
1569 cm-1 due to (C=N) vibrations. These bands in complex shift to the lower frequency
side about 20 (60 cm-1 and appear in the region 1559-1474 cm-1 indicating involvement of
azomethine nitrogen in bonding with metal ions.

56 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 In view of the above reports in our present study the bands observed in the region
16231594 cm-1 are assigned to (C=N). These bands shifts by 20 – 40 cm-1 in the
complexes indicating Ligand coordinates through ‘N’ atom with the metal ion.
K. B. Gudasi. et. al. [54] have reported the (C=O) stretching frequency at 1653
cm-1 and this frequency shift to lower wavenumber in complexes by 20-13 cm-1 indicating
coordination through the oxygen atom. Caroline et.al. [50], have reported bands in the
region 16601640 cm-1 to (C=O) stretch in Schiff base. Rao et.al. [55], have assigned NH2
deformation and (C=O) stretch of CONH2 group in the region 17281600 cm-1, various
workers [56, 57], have assigned (C=O) stretching frequency in the region 17001600 cm-
. A. J. Abdulghani et. al. [58] have reported the (C=O) stretching frequency in the region
1

1735 1695 cm-1 these frequency shifts to a lower value in the complexes by 3 to 27 cm-1
showing coordination through the oxygen atom. Al. Amiery et. al [59] have reported (C=O)
stretching frequency at 1725 cm-1 this frequency shift to lower values in the complexes by
38 to 20 cm-1. M. Ummathur et. al. [60] have reported (C=O) stretching frequency in the
region 1644-1646 cm-1 these frequency shifts to a lower value in complexes by 41-43 cm-1
showing complexation through oxygen atom. A. A. H. Kadhum et al. [61] have reported
(C=O) stretching frequency at 1709 cm-1 and this frequency has shifted to a lower value by
8-16 cm-1 in the complexes [62].
In view of the above reports in our present study the bands observed in the region
17001657cm-1 are assigned to (C=O) stretching. These bands shifts by 20 – 40 cm-1 in
the complexes indicating Ligand coordinates through ‘O’ atom with the metal ion.

Survey of literature has shown that very little work has been done on the
complexing behavior of furan ring oxygen. Few workers who have worked in this field
have assigned the furan ring (COC) stretch in benzofurans around 1230 cm-1. A. J.
Abdulghani et. al. [58] have reported (COC) stretching frequency around 1149 cm-1,
Joseph and Somayajalu et. al. [63, 64], have assigned the (COC) stretching vibration
band in the region 11301020 cm-1.
In view of these assignments the medium to strong intensity bands observed in the
region 1250-1109 cm-1 are attributed to (COC) stretching vibration of benzofuran ring

57 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
in the free ligands. These bands show no shift in the complexes suggesting non-
participation of ‘O’ of (COC) stretching group.

M. R. Maurya et.al. [65], and A. Zabin Samy [66], has reported the (NN) stretch
of hydrazine residue in the region 930840 cm-1 and this band also shift to higher wave
number side indicating involvement of one of the nitrogen in bonding. B. Singh et.al. [67],
have assigned (NN) stretching vibrations in the region 10351025cm-1 in free ligands.
This band shifts to the higher frequency side by about 2040 cm-1 in the complexes
indicating an association of one of the nitrogen atom of hydrazine moiety in bonding with
metal ions.
In view of the above reports in our present study the bands observed in the region
1037-1150 cm-1 are assigned to (N-N) stretching vibrations. These bands shift to the
higher wave number side by about 10-15 cm-1 in the case of complexes indicating
involvement of one of the nitrogen atom in bonding with metal ions [68].

3.5.1. I. R. spectra of ligand [L-I]:

The Infrared spectra of the ligand [L-I] and its metal complexes have been depicted
in (Figure-3.3 to Figure-3.6) and I.R. assignments are listed in (Table-3.9). The IR
spectrum of the ligand compared with those of IR spectra of the metal complexes. The
broad band observed in the ligand at 3444 cm-1 is attributed to ν(OH) stretching frequency
of phenolic group. The band observed at 3360 cm-1 may be assigned to ν(N-H) stretching
vibration of the primary amide group in the ligand and this value is unchanged or slightly
shifted to higher frequency in the spectra of the complexes indicating that the NH2 group
is not involved in coordination. The strong band observed at 1665cm-1 is assigned to
ν(C=O) stretch of amide group undergo negative shift by 20 – 30 cm-1 in the complexes
indicating the involvement of carbonyl group in coordination. The Schiff base shows strong
to medium intensity band at 1581 cm-1 due to ν(C=N) stretching vibrations, this band
undergoes negative shifts in the spectra of the complexes showing involvement of the
azomethine group in the coordination with the metal ions . The band at 1192 cm -1 is
assigned to ν(C-O-C) stretch of the furan ring in free ligand. This band is unchanged on

58 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
complexation indicating non-involvement of the furan ring oxygen in the bonding. In the
far IR spectra of the complexes, the bands in the region 536 -520 cm-1 and 457 - 420 cm-1
assigned to M-O and M-N stretching vibrations in all the complexes. All the above value
indicates that the ligand acts as the bidentate, with azomethine nitrogen and carbonyl
oxygen atom as a donor sites.

Table-3.9: The characterization bands of the infrared spectrum of Schiff -base ligand [L-I] and
its Metal Complexes in cm-1

Legand/Complex ν(C=O) ν(C=N) ν(C-O-C) ν(M-O) ν(M-N) ν(M-Cl)

(L-I) 1665 1581 1192 --- --- ---
Cobalt(II) 1623 1525 1193 528 457 ---
Nickel(II) 1655 1578 1182 530 431 ---
Copper(II) 1646 1559 1190 532 434 ---
Zinc(II) 1648 1559 1181 530 445 377
Cadmium(II) 1650 1575 1179 536 459 365
Mercury(II) 1657 1567 1177 529 420 365

59 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Figure – 3.3: IR Spectrum of the Ligand [L-I]

2. (3360 cm-1), 14. (1665 cm-1), 17. (1581 cm-1), 26. (1168 cm-1)

60 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 70.0

65 584,68
905,66
948,66 717,65 511,65

3068,63 1019,63
60 1261,62 1069,62 528,62
1229,61 806,61
1308,61 766,61
1209,59 688,59
3316,58 1141,58
55 1159,57
1338,56
1382,55
1193,54
1107,53
50
%T 1444,51

1471,48
45 1525,48 1401,49

40

35

30.0 1623,32
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-11

Figure – 3.4: IR Spectrum of the M=Co(II) complex of the Ligand [L-I]

61 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Figure – 3.5: IR Spectrum of the M=Zn(II) complex of the Ligand [L-I]

13. (1648 cm-1), 15. (1559 cm-1), 24. (1181 cm-1), 36. (530 cm-1)

62 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 Figure – 3.6: IR Spectrum of the M=Ni(II) complex of the Ligand [L-I]

6. (1655 cm-1), 9. (1578 cm-1), 21. (1182 cm-1), 32. (530 cm-1)

63 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
3.5.2. I.R. spectra of ligand [L-II]:

The Infrared spectra of the ligand [L-II] and its metal complexes have been depicted
in (Figure-3.7 to Figure-3.9) and I.R. assignments are listed in Table- (3.10). A
comparative interpretation of IR spectral data suggests that ligand acts as a bidentate ligand
in the investigated complexes, using carbonyl oxygen and azomethine nitrogen as donor
atoms. The IR spectrum of the ligand (L) shows the strong band at 3327 cm-1 attributed to
ν (N-H) stretching vibrations of the NH2 group, which is unchanged or shifted to high
wavenumber side in the complexes indicating non-involvement of the nitrogen atom of
NH2 group. The band at 1658 cm-1 is due to the ν (C=N) stretch and this frequency shifted
to a lower value in the complex confirming the involvement of the (C=N) in the
coordination with the metal ions. The stretching vibrational band of the carbonyl group of
a ligand lies at 1682 cm-1 frequency. This band shifts to the lower frequency side in all the
complexes and become weaker in some cases. This suggests the coordination of the C=O
group with metal ions. Further the bonding is supported by the appearance of new bands
in the 426-482, 329-389 regions are assigned to ν(M-N) and ν(M-O) vibrations
respectively. This indicates that carbonyl oxygen and azomethine nitrogen atoms are
involved in coordination.

Table-3.10: The characterization bands of the infrared spectrum of Schiff -base ligand
[L-II] and its Metal Complexes in cm-1

Ligand/Complex ν(C=O) ν(C=N) ν(M-N) ν(M-O) ν(M-Cl)

[L-II] 1682 1658 --- --- ---
Cobalt(II) 1679 1599 426 372 388
Nickel(II) 1670 1599 450 389 330
Copper(II) 1671 1606 471 386 358
Zinc(II) 1670 1580 436 379 379
Cadmium(II) 1672 1575 482 329 364
Mercury(II) 1676 1578 453 377 359

64 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 55.3
54

52
743 536
627 461
50
896 559
48 862 649

46 984 764
961
44
694
42 818

40 1225 1046
1378 798
38 2926
2969
36 3414 1114
%T 3366
34 3278 1267
3470
3327
32 1475 1318
3153
30 1165

28

26
1426
1598 1347
24

22 1658
1557
20

18
1682
16.0
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1
Description: L I I

Figure- 3.7: IR Spectrum of the Ligand [L-II]

65 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 52.3

50
1874
742 533
627 461

45
2227 896 559
861 649

765
40
693

984
35 961

818

30
%T
801
1225 1047
2926 1378
25 3418 2969
3470
3366 1318 1114
3328 1266
20 3165 1166
1475

1347
15
1583 1428
1599
1652
1628
10
1679 1563
8.0
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1

Description: L C O

Figure-3.8: IR Spectrum of the M=Co(II) complex of the Ligand [L-II]

66 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
 61.0

58
495
56 897 626
560
54 861 649
52 962 764
50 693

48
818
46
1235
44
1046 800
42 2926
2969
%T 40 1113
38 3380 1266
36 3366 1318
3505
1166
34 3329 3155 1474

32
30 1347
28 1425
1599
26
24 1627

22 1562
1670
20.0
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1
Description: L N I

Figure –3.9: IR Spectrum of the M=Ni(II) complex of the Ligand [L-II]

67 | P a g e
Chapter-III: Results and Discussion of Schiff bases and their metal complexes
3.5.3. I.R. Spectra of ligand [L-III]:

The Infrared spectra of the ligand [L-III] and its metal complexes have been

depicted in (Figure-3.10 to Figure-3.13) and I.R. assignments are listed in Table- (3.11).

The IR spectrum of the ligand shows the a medium intensity band at ν(3356) cm-1 in the

free ligands due to ν(-OH) stretch, was absent in the complexes indicating deprotonation

of the Schiff bases prior to coordination. Another strong intensity band observed at 3284

cm-1 attributed to ν (N-H) stretching vibrations of the NH2 group, which is unchanged/shifts

to higher frequency in the complexes indicating non-involvement of the nitrogen atom of

NH2 group. The band at 1680 cm-1 is due to the ν (C=O) stretch and this frequency shifts

to a lower value in the complex confirming the involvement of the (C=O) stretch in the

coordination with the metal ions. The stretching vibrational band of the (C=N) group of a

ligand lies at a frequency of 1609 cm-1 and this band get shifted to the lower frequency in

all the complexes and become weaker in some cases. This suggests the coordination of the

C=N group through metal ions, additionally the bonding is supported by the appearance of

new bands in the complexes those are absent in the ligand spectra in the region 503-560

and 420-436 cm-1 are assigned to ν(M-N) and ν(M-O) stretching vibrations respectively.

This indicates that carbonyl oxygen and azomethine nitrogen atoms are involved in

coordination.

Table-3.11: The characterization bands of the infrared spectrum of Schiff -base

ligand [L-III] and its Metal Complexes in cm-1
Ligand/Complex ν(C=O) ν(C=N) ν(M-N) ν(M-O)
[L-III] 1680 1609 ---- ----
Cobalt(II) 1640 1600 503 425
Nickel(II) 1655 1590 505 420
Copper(II) 1656 1585 560 435
Zinc(II) 1666 1586 535 430
Cadmium(II) 1651 1588 541 432
Mercury(II) 1648 1587 542 436

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Chapter-III: Results and Discussion of Schiff bases and their metal complexes