Chapter Two

Synthesis, Characterization of Semicarbazide

and
Thiosemicarbazide based Ligands and their complexes

Acetophenone semicarbazone (L1)

Acetophenone thiosemicarbazone (L2)
Salicylaldehyde semicarbazone (L3)
Salicylaldehyde thiosemicarbazone (L4)
 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Synthesis, Characterization of Semicarbazide and

Thiosemicarbazide based Ligands and their complexes

This chapter is related to the synthesis, physicochemical properties and spectroscopic

characterization of semicarbazide and thiosemicarbazide based ligands. The

semicarbazide and thiosemicarbazide based ligands, which are used to synthesize the

complexes, are:

Acetophenone semicarbazone (L1)

Acetophenone thiosemicarbazone (L2)

Salicylaldehyde semicarbazone (L3)

Salicylaldehyde thiosemicarbazone (L4)

2.1 Synthesis of ligand Acetophenone semicarbazone (L1)

Acetophenone semicarbazone was synthesized by taking the aqueous solutions

(20 mL) of semicarbazide hydrochloride (1.12g, 0.01 mol) and sodium acetate

(0.82g, 0.01 mol). The mixture was kept on an ice bath and then ethanolic

solution of (20 mL) acetophenone (1.12 mL, 0.01 mol) was added drop wise. The

reaction mixture was stirred vigorously for an hour[287]. On keeping the mixture

for 12 hour, at 0 ºC a yellowish colored compound was separated out. It was

filtered, washed several times with cold EtOH and dried in vacuum over P4O10.

Yield (85.0%), Melting Point: 165 ºC.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.1: Scheme for the synthesis acetophenone semicarbazone (L1)

Characterization of ligand Acetophenone semicarbazone (L1)- Pre-confirmatory

test for synthesis of ligand was done through UV light and IR spectra. The

composition of compound was confirmed by mass spectra, 1H NMR spectra and CHN

analysis. Analytical calculation (%) for = C9H11N3O: C, 61.02%; H, 6.21%; N,

23.72%; Observed value: C, 61.22%; H, 6.25%; N, 23.72%;

Solubility of L1- It is soluble in DMF, THF and EtOH, while insoluble in CHCl3,

CCl4, C6H6 and H2O.

IR Characterization-The IR spectrum of ligand (L1) was recorded as KBr pellets in

the region 4000-400 cm-1 on a FT-IR spectrum BX II spectrophotometer and is

presented in Figure 2.2. The free ligand displays the IR bands at 3479 and 3148 cm-1

corresponding to the vas(NH2), vas(NH), streching vibrations, respectively [288-290].

IR spectrum shows other bands at 1742 and 1584 cm-1.These may be assigned to

v(>C=O) and (>C=N), streching vibrations respectively [291-293].

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.2: IR spectrum of acetophenone semicarbazone (L1)

1
H NMR- The 1H NMR spectrum of ligand (L1) has been recorded in 300 MHz

(CDCl3) and depicted in Figure 2.3. It displayed the signals in up-field and down-field

region according to the shielding and deshielding of protons. 1H NMR signals

appeared in the spectrum are given (ppm) - į 13.25 (s, >NH); į 8.31(s, H2N-CO); į

1.41(s, H3C-C); į 7.20-7.31(m, Ar-H) [294].

Figure 2.3: 1H NMR spectrum of acetophenone semicarbazone (L1)

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Mass Spectra-The base peak obtained at 133(M). Atomic mass of molecule is

calculated as 177 amu for molecular formula (C9H11N3O). Large number of peaks of

varying intensity present in the spectrum corresponds to the 77, 92,103,119 and 160

fragments getting generated during the analysis (Figure 2.4a, and 2.4b).

133
100

77

50

119

177
103
92

160
0
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190

Figure 2.4a: Mass Spectrum of acetophenone semicarbazone (L1)

Figure 2.4b: Fragmentation pattern of ligand acetophenone semicorbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

2.1.1 Synthesis of Zinc(II) complex with Acetophenone semicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of acetophenone semicarbazone (1.77g,

0.02 mol), a hot ethanolic solution (20 mL) of zinc chloride (0.68g, 0.01 mol) was

added dropwise with constant stirring. The mixture was refluxed for 6 hrs on a water

bath at ~80-85 oC. On cooling a white coloured precipitate was separated out. The

same was filtered, washed with 50 % ethanol and dried in vacuum over P4O10. Yield

(64.0%), Melting Point: 240 ºC.

CH3 H
O
N NH2
H3C N
N
N NH2
H O
Reflux 6 h Zn
+ ZnCl2 Cl2
O
o
80-85 C
N
H2N N

H CH3

Acetophenone
Zinc(II) complex of
semicarbazone
Acetophenone semicarbazone

Figure 2.5: Scheme for the synthesis of zinc(II) complex with acetophenone semicarbazone

IR Characterization- On complexation the position of ligand band due to (>C=N),

1584 cm-1, (>C=O), 1742 cm-1 are shifted towards lower side i.e. 1558 cm-1, 1603 cm-1

respectively [295].This indicates, that the coordination take place through the nitrogen

atom of the imine groups and oxygen atom of the ketonic group ( >C=O).

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.6: IR spectrum of zinc(II) complex with acetophenone semicarbazone

1
H NMR- The resonance at į 13.25 ppm, į 8.31 ppm, in the spectrum of ligand (L1)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 13.26 ppm, į 8.32 ppm, respectively, which may be due to

change in electron density at O=C-NH2 substructure by the formation of Zn-O

bond.This indicate, that the coordination take place through nitrogen atom of the

imine groups and oxygen atom of the ketonic groups (>C=O).

Figure 2.7: 1H NMR spectrum of zinc(II) complex with acetophenone semicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

2.1.2 Synthesis of Cadmium(II) complex with Acetophenone semicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of acetophenone semicarbazone (1.77g,

0.02 mol) a hot ethanolic solution (20 mL) of cadmium chloride (0.922g, 0.01 mol)

was added dropwise with constant stirring. The mixture was refluxed for 8 hrs on a

water bath at ~75 to 80 oC. On cooling a white coloured precipitate was separated out.

The same was filtered, washed with 50 % ethanol and dried in vacuum over P4O10.

Yield (95.0%), Melting Point: 225 ºC.

CH3 H
O
N NH2
H3C N
N
N NH2
H O
Cd
Reflux 8 h Cl2
+ CdCl2 O
75-80 oC
N
H2N N

H CH3

Acetophenone Cadmium(II) complex of

semicarbazone Acetophenone semicarbazone

Figure 2.8: Scheme for the synthesis of cadmium(II) complex with acetophenone
semicarbazone

IR Characterization- The position of ligand band due to (>C=N), 1584 cm1 ,

(>C=O), 1742 in complexation these band is shifted towards lower side i.e. 1523 cm-1,

1674 cm-1 respectively. This indicates, that the coordination take place through the

nitrogen atom of the imine groups and oxygen atom of the >C=O group.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.9: IR spectrum of cadmium(II) complex with acetophenone semicarbazone

1
H NMR- The resonance at į 13.25 ppm, į 8.31 ppm, in the spectrum of ligand (L1)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 13.25 ppm, į 8.33 ppm, respectively, which may be due to

change in density at O=C-NH2 substructure by the formation of Cd-O bond. This

indicate, that the coordination take place through nitrogen atom of the imine groups

and oxygen atom of the ketonic groups (>C=O).

Figure 2.10: 1H NMR spectrum of cadmium(II) complex with acetophenone semicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

2.1.3 Synthesis of Mercury(II) complex with Acetophenone semicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of acetophenone semicarbazone (1.77g,

0.02 mol) a hot ethanolic solution (20 mL) of mercury chloride (1.36g, 0.01 mol) was

added dropwise with constant stirring. The mixture was refluxed for 4 hrs on a water

bath at ~70 to 75 oC. On cooling a white coloured precipitate was separated out. The

same was filtered, washed with 50 % ethanol and dried in vacuum over P4O10. Yield

(75.0%), Melting Point: 245 ºC.

O CH3 H

H3C N N NH2
N NH2 N

H O
Reflux 4 h Hg
+ HgCl2 Cl2
o O
70 -75 C
N
H2N N

H CH3
Acetophenone Mercury(II) complex of
semicarbazone Acetophenone semicarbazone
Figure 2.11: Scheme for the synthesis of mercury(II) complex with acetophenone semicarbazone

IR Characterization- On complexation the position of ligand bands due to (>C=N),

1584 cm-1, (>C=O), 1742 cm-1 are shifted towards lower side i.e. 1550 cm-1, 1715 cm-1

respectively. This indicates, that the coordination take place through the nitrogen atom

of the imine groups and oxygen atom of the >C=O group.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.12: IR spectrum of mercury(II) complex acetophenone semicarbazone

1
H NMR- The resonance at į 13.25 ppm, į 8.31 ppm, in the spectrum of ligand (L1)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 13.30 ppm, į 8.41 ppm, respectively, which may be due to

change in density at O=C-NH2 substructure by the formation of Hg-O bond. This

indicates, that the coordination take place through nitrogen atom of the imine groups

and oxygen atom of the ketonic groups (>C=O).

Figure 2.13: 1H NMR spectrum of mercury(II) complex acetophenone semicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

2.2 Synthesis of ligand Acetophenone thiosemicarbazone(L2)

To a hot ethanolic solutions (20 mL) of thiosemicarbazide (0.91g, 0.01 mol) an ethanolic

solution of acetophenone (1.12 mL, 0.01 mol) was added with constant stirring in the

presence of few drops of acetic acid. The mixture was refluxed at ~80 ±5 oC. On cooling,

a cream coloured compound was separated out. It was filtered, washed several times with

cold ethanol and dried in vacuum over P4O10. Yield (75.0%), Melting Point: 181 ºC

Figure 2.14: Scheme for the synthesis of acetophenone thiosemicarbazone (L2)

Characterization of ligand Acetophenone thiosemicarbazone (L2)- Pre-confirmatory

test for synthesis of ligand was done through UV light and IR spectra. The composition of

compound was confirmed by mass spectra, 1H NMR spectra and CHN analysis.

Analytical Calculation (%) for = C9H11N3S: C, 55.06%; H, 5.76%; N, 21.76%; and

observed values: C, 55.22%; H, 5.58%; N, 21.72%;

Solubility of L2- It is soluble in DMF, THF, Ethanol and Methanol while insoluble in

CHCl3, CCl4, C6H5 and H2O.

IR Characterization- The IR spectrum of ligand (L2) is given in Figure 2.15. The

spectrum exhibits the IR bands at 3372, 3263 and 3178 cm-1due to vas(NH2), vs(NH2),

streching and vas(NH) vibration of free NH2 groups.[296].The spectrum also shows

bands at 1510 and 845 cm-1[297-299] due to v(>C=N) and v(>C=S) groups

respectively.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.15: IR spectrum of acetophenone thiosemicarbazone (L2)

1
H NMR- The 1H NMR spectrum of ligand (L2) has been recorded in 300 MHz

(CDCl3) and depicted in Figure 2.16 and it displayed the signals in up-field and down-

field region according to the shielding and deshielding of protons. 1H NMR signals

appeared in the spectrum are given (ppm) - į 10.01(s, >NH); į 8.17 (s, H2N-CO); į

2.38 (s, H3C-C); į 7.38-7.79 (m, Ar-H)

Figure 2.16: 1H NMR spectrum of acetophenone thiosemicarbazone (L2)

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Mass Spectra- The base peak obtained at 193(M). Atomic mass of molecule is

calculated as 193 amu for molecular formula (C9H11N3O). Large number of peaks of

varying intensity present in the spectrum corresponds to the 77, 92, 118,133,178 and

193 fragments getting generated during the analysis (Figure 2.17a and 2.17b).

Figure 2.17a: Mass Spectrum of acetophenone thiosemicarbazone (L2)

Figure 2.17b: Fragmentation pattern of acetophenone thiosemicarbazone

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2.2.1 Synthesis of Zinc(II) complex with Acetophenone thiosemicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of acetophenone thiosemicarbazone (1.93g,

0.02 mol) a hot ethanolic solution (20 mL) of zinc chloride (0.68g, 0.01 mol) was added

dropwise with constant stirring. The mixture was refluxed for 6 hrs at ~75 to 80 oC. On

cooling a white coloured precipitate was separated out. The same was filtered, washed

with 50% ethanol and dried in vacuum over P4O10. Yield (55.0%), Melting Point: 260 ºC

CH3 H

N NH2
S N

H3 C N S
N NH2 Zn
H Reflux 6 h Cl2
ZnCl2 S
+
75 - 80 oC N
H2N N

H CH3

Acetophenone Zinc(II) complex of

thiosemicarbazone Acetophenonethiosemicarbazone

Figure 2.18: Scheme for the synthesis of zinc(II) complex with acetophenone thiosemicarbazone

IR Characterization- On complexation the position of ligand bands due to (>C=N),

1510 cm-1 (>C=S), 845 cm-1 are shifted towards lower side i.e. 1492 cm-1, 834 cm-1

respectively. This indicates, that the coordination take place through the nitrogen atom

of the imine groups and sulphur atom of the >C=S group.

Figure 2.19: IR spectrum of zinc(II) complex with acetophenone thiosemicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

1
H NMR- The resonance at į 10.01 ppm, į 8.17 ppm, in the spectrum of ligand (L2)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted downfield to į 10.11 ppm, į 8.275 ppm, respectively, which may be due to

change in density at S=C-NH2 substructure by the formation of Zn-S bond. This

indicates that the coordination take place through nitrogen atom of the imine groups

and sulphur atom of the >C=S groups.

Figure 2.20: 1H NMR spectrum of zinc(II) complex with acetophenone thiosemicarbazone

2.2.2 Synthesis of Cadmium(II) complex with Acetophenone thiosemicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of acetophenone thiosemicarbazone

(1.93g, 0.02 mol) a hot ethanolic solution (20 mL) of cadmium chloride (0.922g, 0.01

mol) was added dropwise with constant stirring. The mixture was refluxed for 8 hrs

on a water bath at ~75 to 85 oC. On cooling a white coloured precipitate was separated

out. The same was filtered, washed with 50% ethanol and dried in vacuum over P4O10.

Yield (95.0%), Melting Point: 281 ºC

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

S CH3 H

N NH2
H3C N N
N NH2
S
H Cd
Reflux 8 h Cl2
+ CdCl2 S
o
75 - 85 C
N
H2N N

H CH3
Acetophenone
thiosemicarbazone Cadmium(II)complex of
Acetophenonethiosemicarbazone

Figure 2.21: Scheme for the synthesis of cadmium(II) complex with acetophenone
thiosemicarbazone

IR Characterization- On complexation the position of ligand band due to (>C=N),

1510 cm-1, (>C=S), 845 cm-1 is shifted to lower wave number to1490 cm-1, 832 cm-1

respectively. This indicate that the coordination take place through the nitrogen atom

of the imine groups and sulphur atom of the >C=S group.

Figure 2.22: IR spectrum of cadmium(II) complex with ATS

1
H NMR- The resonance at į 10.01 ppm, į 8.17 ppm, in the spectrum of ligand (L2) was

assigned to the N-NH, NH2 respectively. After metal chelation these resonance shifted

downfield to į 10.38 ppm, į 8.37 ppm, respectively, which may due to change in density

at S=C-NH2 substructure by the formation of Cd-S bond. This indicate, that the

coordination take place through nitrogen atom of the imine groups and sulphur atom of

the >C=S groups.

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Figure 2.23: 1H NMR spectrum of cadmium(II) complex with acetophenone thiosemicarbazone

2.2.3 Synthesis of Mercury(II) complex with Acetophenone thiosemicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of acetophenone thiosemicarbazone

(1.93g, 0.02 mol) a hot ethanolic solution (20 mL) of mercury chloride (01.36g, 0.01

mol) was added dropwise with constant stirring. The mixture was refluxed for 4 hrs

on a water bath at ~80 to 85 oC. On cooling a black coloured precipitate was separated

out. The same was filtered, washed with 50% ethanol and dried in vacuum over P4O10.

Yield (85.0%), Melting Point: 240 ºC

S CH3 H

H3C N N NH2
N
N NH2
H S
Reflux 4 h Hg
HgCl2 Cl2
+ S
80 to 85 oC
N
H2N N

H CH3

Acetophenone Mercury (II)complex of

thiosemicarbazone Acetophenonethiosemicarbazone

Figure 2.24: Scheme for the synthesis of mercury(II) complex with acetophenone thiosemicarbazone

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IR Characterization- The complexation resulted in shifting of the ligand band due to

(>C=N) 1510 cm-1, (>C=S) 845 cm-1 to lower wave number 1493 cm-1, 834 cm-1

respectively. This indicates that the coordination take place through the nitrogen atom of the

imine groups and sulphur atom of the >C=S group.

Figure 2.25: IR spectrum of mercury(II) complex with acetophenone thiosemicarbazone

1
H NMR- The resonance at į 10.01 ppm, į 8.17 ppm, in the spectrum of ligand (L2) was

assigned to the N-NH, NH2 respectively. After metal chelation these resonance shifted

downfield to į 10.21 ppm, į 8.37 ppm, respectively, which may be due to change in density

at S=C-NH2 substructure by the formation of Hg-S bond. This indicate that the coordination

take place through nitrogen atom of the imine groups and sulphur atom of the >C=S groups.

Figure 2.26: 1H NMR spectrum of mercury(II) complex with ATC

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2.3 Synthesis of ligand salicylaldehyde semicarbazone (L3)

Salicylaldehyde semicarbazone was synthesized by taking the aqueous solutions (20 mL) of

semicarbazide hydrochloride (1.12g, 0.01 mol) and sodium acetate (0.82g, 0.01 mol).The

mixture was kept on an ice bath and then ethanolic solutions (20 mL) salicylaldehyde (1.1

mL, 0.01 mol), was added dropwise with constant stirring. The reaction mixture was stirred

vigorously for an hour. On keeping the mixture for 18 hour, at 0 °C a yellowish coloured

compound was separated out. It was filtered, washed several times with cold EtOH and

dried in vacuum over P4O10. Yield (95.0%), Melting Point: 225 ºC

Figure 2.27: Scheme for the synthesis of ligand salicylaldehyde semicarbazone (L3)

Characterization of ligand Salicylaldehyde semicarbazone (L3)- A preliminary test for

synthesized ionophore was done by recording the melting point of the complex formed,

TLC, UV and IR spectra. The composition of compound was confirmed by IR, mass

spectra, 1H NMR spectra and elemental analysis. Analytical calculation (%) for C8H9N3O2:

C, 53.63%; H, 5.06%; N, 23.76%; was found values C, 53.53%; H, 5.16%; N, 23.66%;

Solubility of L3- It is soluble in DMF, THF, DMSO, EtOH and CH3OH while

insoluble in CHCl3, CCl4, C6H6 and H2O.

IR Characterization- The IR spectrum of ligand L3 is given in Figure 2.28. The spectrum

shows the IR bands at 3494, 3153 and 3055 cm-1due to vas(NH2), vs(NH2), stretching and

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

vas(NH) vibration of free NH2 groups respectively[300].The spectrum also shows bands at

3278, 1697 and 1590 cm-1 -[301-307] due to v(Phenolic-OH), v (>C=O) and v (>C=N)

groups respectively.

Figure 2.28: IR spectrum of ligand salicylaldehyde semicarbazone (L3)

1
H NMR- The 1H NMR spectrum of ligand (L3) has been recorded in 300 MHz

(CDCl3) and depicted in Figure 2.29. It displayed the signals in up-field and down-

field region according to the shielding and deshielding of protons. 1H NMR signals

appeared in the spectrum are given (ppm) - į 9.51 (s, >NH); į 8.35 (s, H2N-CO); į

2.41 (s, H3C-C); į 7.22-7.68 (m, Ar-H); į 4.4 (Ar-OH).

Figure 2.29: 1H NMR spectrum of ligand salicylaldehyde semicarbazone

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Mass Spectra- The base peak obtained at 179(M). Atomic mass of molecule is

calculated as 179 amu for molecular formula (C8H9N3O2). Large number of peaks of

varying intensity present in the spectrum corresponds to 44, 76, 120,135 and 179

fragments getting generated during the analysis (Figure 2.30a and 2.30b).

Figure 2.30a: Mass spectrum of ligand salicylaldehyde semicarbazone (L3)

Figure 2.30b: Fragmentation pattern of salicylaldehyde semicarbazone

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2.3.1 Synthesis of Zinc(II) complex with Salicylaldehyde semicarbazone

To hot ethanolic solution (20 mL 1:1 v/v) of salicylaldehyde semicarbazone (1.79g,

0.01 mol) a hot ethanolic solution (20 mL) of zinc chloride (1.36g, 0.01 mol) was added

with dropwise with constant stirring. The mixture was refluxed for 6 hrs at ~75-80 ºC .

On cooling a white colored precipitate was separated out. The same was filtered,

washed with 50% ethanol and dried in vacuum over P4O10. Yield (90.0%), Melting

Point: 254 ºC

OH H H O Cl

C N N C NH2 Reflux 6 h Zn
O O
+ ZnCl2
75-80 ºC C N N C NH2 Cl

H H

Salicylaldehyde semicarbazone Zinc(II) complex with

Salicylaldehyde semicarbazone

Figure 2.31: Scheme for the synthesis of zinc(II) complex with salicylaldehyde semicarbazone

IR Characterization- A medium intensity band in the i.r. spectrum of the ligand

at 3278 cm-1 is assigned to an intramolecular hydrogen bond v(O-H). This band is

absent in the spectrum of the complex, indicating that the phenolic-OH group is

deprotonated. In complex a new peak corresponding to phenolic v(C-O) is

observed at 1290 cm-1. The position of ligand band due to (>C=N), 1590 cm-1 and

(>C=O), 1697 cm-1 is shifted towards lower side to 1545 cm-1, 1647 cm-1

respectively, indicating the coordination through the nitrogen atom of the imine

group and oxygen atoms of the ketonic (>C=O) and phenolic -OH groups.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.32 IR spectrum of zinc(II) complex with salicylaldehyde semicarbazone

1
H NMR- The resonance at į 9.51 ppm, į 8.35 ppm, in the spectrum of ligand (L3)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted downfield to į 9.65 ppm, į 8.42 ppm, respectively. Disappearance of the –

OH protons in the spectrum of the complex supported the deprotonation of the

phenolic group. The zinc complex show only the charge transfer transition which

can be assigned to charge transfer from the ligand to the metal and vice versa. This

is due to change in density at O=C-NH2 substructure by the formation of Zn-O bond.

This indicating coordination through nitrogen atom of the imine groups and oxygen

atom of the ketonic (>C=O) and O-C6H5 groups.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.33: 1H NMR spectrum of zinc(II) complex with salicylaldehyde semicarbazone

2.3.2 Synthesis of Cadmium(II) complex with Salicylaldehyde semicarbazone

To hot ethanolic solution (20 mL 1:1 v/v) of salicylaldehyde semicarbazone (1.79g, 0.01

mol) a hot ethanolic solution (20 mL) of cadmium chloride (1.83g, 0.01 mol) was added

dropwise with constant stirring. The mixture was refluxed for 6 hrs at ~75-80 ºC .On

cooling a white colored precipitate separated out. The same was filtered, washed with

50% ethanol and dried in vacuum over P4O10. Yield (55.0%), Melting Point: 250 ºC

Cl
OH H H O
Cd
C N N C NH2 O O
Reflux 6 h
+ CdCl2 C N N C NH2 Cl
75-80 ºC
H H

Cadmium(II) complex with

Salicylaldehyde semicarbazone Salicylaldehyde semicarbazone

Figure 2.34: Scheme for the synthesis of cadmium(II) complex with salicylaldehyde semicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

IR Characterization- The i.r. spectrum of the ligand appeared at 3278 cm-1 assigned to an

intramolecular hydrogen bonding v(O-H). On complexation this band is absent in the

spectrum of the complex, this indicating that the phenolic-OH group is deprotonated and

coordination take place with phenolic oxygen in group. In complex a new peak

corresponding to phenolic v(C-O) is observed at 1292 cm-1. The position of band due to

(>C=N), 1590 cm-1 and (>C=O), 1697 cm-1 is shifted towards lower side to 1467 cm-1, 1646

cm-1 respectively. This indicate, that the coordination take place through the nitrogen atom

of the imine groups and oxygen atoms of the ketonic (>C=O) and phenolic (–OH) group.

Figure 2.35: IR spectrum of cadmium(II) complex with salicylaldehyde semicarbazone

1
H NMR- The resonance at į 9.51 ppm, į 8.35 ppm, in the spectrum of ligand (L3)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 9.67 ppm, į 8.49 ppm, respectively. Disappearance of the –

OH protons in the spectrum of the complex supported the deprotonation of the

phenolic group. The cadmium complex show only the charge transfer transition which

can be assigned to charge transfer from the ligand to the metal and vice versa. Which

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

may due to change in density at O=C-NH2 substructure by the formation of Cd-O

bond. This indicate, that the coordination take place through nitrogen atom of the

imine groups and oxygen atom of the ketonic (>C=O) and O-C6H5 groups.

Figure 2.36: 1H NMR spectrum of cadmium(II) complex with salicylaldehyde semicarbazone

2.3.3 Synthesis of Mercury(II) complex with Salicylaldehyde semicarbazone

To a hot ethanolic solution (20 mL 1:1 v/v) of salicylaldehyde semicarbazone (1.79g,

0.01 mol) a hot ethanolic solution (20 mL) of mercury chloride (2.71g, 0.01 mol) was

added dropwise with constant stirring. The mixture was refluxed for 12 hrs at ~75-80 ºC .

On cooling a white colored precipitate was separated out. The same was filtered, washed

with 50% ethanol and dried in vacuum over P4O10. Yield (88.0%), Melting Point: 274 ºC

OH H H O Cl

C N N C NH2 Hg
Reflux 12 h O O
+ HgCl2
75-80 ºC C N N C NH2 Cl
H H

Salicylaldehyde semicarbazone Mercury(II) complex with

salicylaldehyde semicarbazone

Figure 2.37: Scheme for the synthesis of mercury(II) complex with salicylaldehyde semicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

IR Characterization- A medium intensity band in the i.r. spectrum of the ligand

appeared at 3278 cm-1 assigned to an intramolecular hydrogen bond v(O-H). The

absence of this band in spectrum of the complex indicates that the phenolic-OH group

is deprotonated. In complex a new peak corresponding to phenolic v(C-O) is observed

at 1357 cm-1.The position of band due to (>C=N), 1590 cm-1 and (>C=O), 1697 cm-1

is shifted towards lower side to 1522 cm1, 1621 cm-1 respectively. This indicate, that

the coordination take place through the nitrogen atom of the imine groups and oxygen

atoms of the ketonic (>C=O) and phenolic (-OH) group.

Figure 2.38: IR spectrum of mercury(II) complex with salicylaldehyde semicarbazone

1
H NMR- The resonance at į 9.51 ppm, į 8.35 ppm, in the spectrum of ligand (L3)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 9.75 ppm, į 8.46 ppm, respectively. Disappearance of the –

OH protons in the spectrum of the complex supported the deprotonation of the

phenolic group. The mercury complex show only the charge transfer transition which

can be assigned to charge transfer from the ligand to the metal and vice versa. Which

may due to change in density at O=C-NH2 substructure by the formation of Hg-O

bond. This indicate, that the coordination take place through nitrogen atom of the

imine groups and oxygen atom of the ketonic (>C=O) and O-C6H5 groups.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.39: 1H NMR spectrum of mercury(II) complex with salicylaldehyde semicarbazone

2.4 Synthesis of ligand salicylaldehyde thiosemicarbazone (L4)

To hot ethanolic solutions (20 mL) of thiosemicarbazide (0.91g, 0.01 mol) an ethanolic

solutions salicylaldehyde (1.31 mL, 0.01 mol) was added with constant starring in the

presence of few drops of acetic acid. This mixture was refluxed at ~80 ±5 0C. On

cooling a yellowish coloured compound was separated out. It was filtered, washed

several times with cold EtOH and dried in vacuum over P4O10. Yield (75.0%), Melting

Point: 184ºC

Figure 2.40: Scheme for the synthesis ligand salicylaldehyde thiosemicarbazone (L4)

Characterization of ligand salicylaldehyde thiosemicarbazone (L4)- A preliminary

test for synthesized ionophore was done by recording the melting point of the

complex formed, TLC and UV spectra. The composition of compound was confirmed

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

by IR, mass spectra, 1H NMR spectra and elemental analysis. Analytical calculation

(%) for C8H9N3OS: C, 49.21%; H, 4.65%; N, 21.52%; and observed values C,

49.11%; H, 4.60%; N, 21.50%;

Solubility of L4- It is soluble in DMF, THF, DMSO, EtOH and Methanol while

insoluble in CHCl3, CCl4, C6H6 and H2O.

IR Characterization-The IR spectrum of ligand L4 is given in (Figure 2.41). The

spectrum exhibits the IR band at 3444, 3173 and 2987 cm-1due to vas(NH2), vs(NH2),

streching and vas(NH) vibration of free NH2 groups. The spectrum also shows band at

3320, 1538 and 829 cm-1 due to v(-OH) v(>C=N) and v(>C=S) groups.

Figure 2.41: IR spectrum of ligand salicylaldehyde thiosemicarbazone

1
H NMR- The 1H NMR spectrum of ligand (L4) has been recorded in 300 MHz

(CDCl3) and depicted in Figure 2.42 and it displayed the signals in up-field and down-

field region according to the shielding and deshielding of protons. 1H NMR signals

appeared in the spectrum are given (ppm) - į 10.38 (s, >NH); į 8.42 (s, H2N-CO); į

2.40 (s, H3C-C); į 7.47-7.80 (m, Ar-H); į 3.46 (Ar-OH).

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

Figure 2.42: 1H NMR spectrum of ligand salicylaldehyde thiosemicarbazone

Mass Spectra- The base peak obtained at 195(M) corresponding to cyclic moiety.

Atomic mass of molecule is calculated as 195 amu for molecular formula

(C8H9N3O2). A strong peak at 195 due to the species. Large number of peaks of

varying intensity present in the spectrum correspond the 76, 91,102,120,135,178 and

195 fragments getting generated during the analysis (Figure 2.43a, 2.43b).

Figure 2.43a: Mass spectrum of ligand salicylaldehyde thiosemicarbazone

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Figure 2.43b: Fragmentation pattern of salicylaldehyde thiosemicarbazone

2.4.1 Synthesis of Zinc(II) complex of salicylaldehyde thiosemicarbazone

To a hot ethanolic solution (20 mL) of salicylaldehyde thiosemicarbazone (1.95g, 0.01

mol) a hot solution (20 mL) of zinc chloride (1.36g, 0.01 mol) was added dropwise with

constant stirring. The mixture was refluxed for 9 hrs at ~75-80 ºC .On cooling a white

colored precipitate was separated out. The same was filtered, washed with 50% ethanol

and dried in vacuum over P4O10. Yield (80%), Melting Point: 225 ºC

OH H H S Cl
C N N C NH2 Zn
Reflux 9 h
O S
+ ZnCl2
75-80 ºC C N N C NH2 Cl
H H

Zinc(II) complex with

Salicylaldehyde thiosemicarbazone
salicylaldehyde thiosemicarbazone

Figure 2.44: Scheme for the synthesis of zinc(II) complex with salicylaldehyde thiosemicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

IR Characterization- A medium intensity band in the i.r. spectrum of the ligand at 3320

cm-1 is assigned to an intramolecular hydrogen bond v(O-H). In i.r. spectra of the

complex, absence of this bands shows that the phenolic-OH groups are deprotonated. In

complex a new peak corresponding to phenolic v(C-O) is observed at 1278 cm-1. The

position of ligand band due to (>C=N), 1538 cm-1and (>C=S), 829 cm-1 is shifted towards

lower side to 1500 cm-1, 801 cm-1 respectively. This indicates, that the coordination take

place through the nitrogen atom of the imine groups and sulphur atom of the >C=S and

oxygen atom of the (-OH) group.

Figure 2.45: IR spectrum of zinc(II) complex with salicylaldehyde thiosemicarbazone

1
H NMR- The resonance at į 10.38 ppm, į 8.42 ppm, in the spectrum of ligand (L4)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 10.42 ppm, į 8.48 ppm, respectively. Disappearance of the –

OH protons in the spectrum of the complex supported the deprotonation of the

phenolic group. The zinc complex shows only the charge transfer transition which can

be assigned to charge transfer from the ligand to the metal and vice versa, which may

be due to change in density at O=C-NH2 substructure by the formation of Zn-S bond.

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

This indicate, that the coordination take place through nitrogen atom of the imine

groups sulpher atom of the >C=S and oxygen atom of the O-C6H5 groups.

Figure 2.46: 1H NMR spectrum of zinc(II) complex with salicylaldehyde thiosemicarbazone

2.4.2 Synthesis of Cadmium(II) complex with salicylaldehyde thiosemicarbazone

To a hot ethanolic solution (20 mL) of salicylaldehyde thiosemicarbazone (1.95g, 0.01

mol) a hot solution (20 mL) of cadmium chloride (1.83g, 0.01 mol) was added dropwise

with constant stirring. The mixture was refluxed for 8 hrs at ~85-90 ºC. On cooling a

white colored precipitate was separated out. The same was filtered, washed with 50%

ethanol and dried in vacuum over P4O10. Yield (70%), Melting Point: 245 ºC

OH H H S
Cl
C N N C NH2
Cd
Reflux 8 h O S
+ CdCl2
85-90 ºC C N N C NH2 Cl
H H

Salicylaldehyde thiosemicarbazone
Cadmium(II) complex with salicylaldehyde
thiosemicarbazone

Figure 2.47: Scheme for the synthesis of cadmium(II) complex with salicylaldehyde thiosemicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

IR Characterization- A medium intensity band at 3320 cm-1 in i.r. spectra of ligand is

due to intramolecular hydrogen bond v(O-H). This band is absent in the spectra of the

complex, this indicating that the phenolic-OH groups are deprotonated. In complex a

new peak corresponding to phenolic v(C-O) is observed at 1386 cm-1. The position of

ligand band due to (>C=N), 1538 cm-1 and (>C=S), 829 cm-1 shifted towards lower side

to 1489 cm-1 and 828 cm-1 respectively. This indicates, that the coordination take place

through the nitrogen atom of the imine group and sulphur atom of the >C=S and oxygen

atom of the (-OH) group.

Figure 2.48: IR spectrum of cadmium(II)complex with salicylaldehyde thiosemicarbazone

1
H NMR- The resonance at į 10.38 ppm, į 8.42 ppm, in the spectrum of ligand (L4)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 10.38 ppm, į 8.42 ppm, respectively. Disappearance of the –

OH protons in the spectrum of the complex supported the deprotonation of the

phenolic group. The cadmium complex show only the charge transfer transition which

can be assigned to charge transfer from the ligand to the metal and vice versa, which

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

may be due to change in density at O=C-NH2 substructure by the formation of Cd-S

bond. This indicate, that the coordination take place through nitrogen atom of the

imine groups sulpher atom of the >C=S and oxygen atom of the O-C6H5 groups.

Figure 2.49: 1H NMR spectrum of cadmium (II) complex with salicylaldehyde thiosemicarbazone

2.4.3 Synthesis of Mercury(II) complex with Salicylaldehyde semicarbazone

To a ethanolic solution (20 mL) of salicylaldehyde thiosemicarbazone (1.95g, 0.01 mol)

a hot solution (20 mL) of mercury chloride (2.71g, 0.01 mol) was added dropwise with

constant stirring. The mixture was refluxed for 6 hrs at ~70-80 ºC. On cooling a white

colored precipitate was separated out. The same was filtered, washed with 50% ethanol

and dried in vacuum over P4O10. Yield (80%), Melting Point: 265 ºC

OH H H S Cl
C N N C NH2 Hg
Reflux 6 h O S
+ HgCl2
70-80 ºC C N N C NH2 Cl
H H

Salicylaldehyde thiosemicarbazone Mercury(II) complex with

salicylaldehyde thiosemicarbazone

Figure 2.50: Scheme for the synthesis of mercury(II) complex with salicylaldehyde thiosemicarbazone

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

IR Characterization- In i.r. spectrum of the ligand a medium intensity band at 3320

cm-1 is assigned to an intramolecular hydrogen bond v(O-H). On complexation

disappearance of this band indicates that the phenolic-OH groups are deprotonated. In

complex a new peak corresponding to phenolic v(C-O) is observed at 1286 cm-1.The

position of ligand band due to (>C=N), 1538 cm-1 and (>C=S), 829 cm-1 is shifted

towards lower side to 1489 cm-1 and 751 cm-1 respectively. This indicate, that the

coordination take place through the nitrogen atom of the imine groups and sulphur

atom of the >C=S and oxygen atom of the (-OH) group.

Figure 2.51: IR spectrum of mercury(II) complex with salicylaldehyde thiosemicarbazone

1
H NMR- The resonance at į 10.38 ppm, į 8.42 ppm, in the spectrum of ligand (L4)

was assigned to the N-NH, NH2 respectively. After metal chelation these resonance

shifted to downfield to į 10.39 ppm, į 8.59 ppm, respectively. Disappearance of the –

OH protons in the spectrum of the complex supported the deprotonation of the

phenolic group. The mercury complex show only the charge transfer transition which

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 SYNTHESIS, CHARACTERIZATION OF LIGANDS AND THEIR COMPLEXES

can be assigned to charge transfer from the ligand to the metal and vice versa,which

may be due to change in density at O=C-NH2 substructure by the formation of Hg-S

bond. This indicates, that the coordination take place through nitrogen atom of the

imine groups sulpher atom of the >C=S and oxygen atom of the O-C6H5 groups.

Figure 2.52: 1H NMR spectrum of mercury(II) complex with salicylaldehyde thiosemicarbazone

110