Some Complexes of Zink (II) and Manganese (II) with Schiff Base derived from Nicotinamide, Synthesis and Characterization, Antibacterial Evaluation

 

Dr. Rana R. Abed, Dr. Amena E. Ahmed

   Department of Chemistry, College of Education of Pure Science, University of Mosul, Iraq.

*Corresponding Author E-mail: ranaalbustani@uomosul.edu.iq

 

ABSTRACT:

Manganese (II) and Zinc (II) Complexes with O-aminobenzylidenenicotinamide were synthesized. And characterized by using physicochemical Technique and spectroscopic analysis such as melting point determination, conductivity measurements, Molar efraction (CHN elemental analysis) and infrared spectroscopy (1H NMR ,13C-NMR), The antibacterial activity of the prepared complexes was screened against several bacterial strains namely S. aureus, E. coli, Proteus mirabilis and P. aeruginosa. The antibacterial screening tests elicit that both complexes besides Schiff bases exhibited promising antibacterial activity against these microorganisms so that they are of improved antibacterial activity than the parent drugs. The above ligand formed ionic complexes having general formulae [M (OABNA)2]X2 in neutral medium having octahedral geometries, M= Mn, Zn, X= Cl, NO3, CH3COO, OABNA = ortho-aminobenzylidenenicotinamide, hexa coordinated mononuclear, complexes were investigated by this study.

 

KEYWORDS:O-aminobenzylidenenicotinamide, Nicotinamide Mn and Zn complexes, Schiff base, antibacterial

 

 


INTRODUCTION:

 "Transition metalions are very essential component of different Organs of animals such as blood, bones, teeth, nerves, some proteins and enzymes are very important metals for health organisms"1."Heterocyclic compounds play a significant role in many biological systems, especially N-donor ligand systems being a component of several vitamins and drugs such as Nicotinamide, chemically 3-pyridine carboxamide is the compound with the chemical formula C6H6N2O (Fig1). Basically, being an amide derivative of nicotinic acid, it also called niacin, nicotinic acid amide and vitamin B3."2." Nicotinamide is a known bioligand that is a reactive moiety of the coenzyme, nicotinamide adenine dinucleotide. it being used for treatment of various diseases (hypercholesteremia, pellagra and treatment of certain psychological disorders) and incorporated into some cosmetics"3

 

 

"Schiff base metal complexes have been widely studied. Complexation of Schiff base derivatives with several metal ions showed the capability of forming metal complexes in which they behaved as bidentate or tridentate ligands depending on the positions and number of electron donating groups4 this type of ligands (Schiff base) stand for fundamental compounds as a consequence of the existence of (-CH=N-) with antiseptic performance, catalysis, anti-oxidative, antifungal, enzymatic reaction, bioinorganic prototyping and magnetism investigations5

 

MATERIAL AND METHODS:

The Starting compounds are: ethanol, dimethylformamide and acetic acid have been supplied from Merck. Nicotinamide, o-aminobenzaldehyde, and all salts have been supplied by Aldrich

 

Preparation of Ligand:

OABNA ligand (O-aminobenzylidenenicotinamide) (Fig. 1) has been prepared according to the literature6 as follows:(10.08gm, 0.082mol) of Nicotinamide was dissolved in absolute ethanol (15ml) has inserted in the refluxing solution of (10gm, 0.082mol) o–aminobenzaldehyde for the related solvent (15ml) in


 

 

 

 

 

Fig. 1: Model structure of ligand

 

 


(100ml round-bottomed flask) with three or four drops of glacial acetic acid5. The mixture was excited in bath water byre fluxing at 70 to 80o C for 4 hours with uninterrupted stirring. The solution color was altered from yellow to orange. Then, evaporation to half their volumes then cooled. The residues were separated by filtration, washed with cold water and re-crystallization using absolute ethanol.6 eq. (1).

 

Preparation of the Complexes:

The reaction of Manganese (II) and Zink (II) is carried out with O-aminobenzylidenenicotinamide ligand in 1:2 molar ratios in neutral medium as follows: eq. (2)

[Zn (OABNA)]Cl2 has been prepared by dissolving of (0.826gm 1.83 x 10-3 mole) of OABNA (O-aminobenzylidenenicotinamide) dissolved in 12ml of ethanol with ZnCl2 (0.25g 1.83 x 10-3 mole) which dissolved in distilled water as (2:1) ratio. The mixture has been refluxed for three hours. Evaporation to about half its volume and then left to cool. The resulting complex was filtered off, washed with cold distilled water followed with diethyl ether and then dried. Complexes with the other Zn & Mn salts have been prepared using same procedure7eq. (2) Fig 2 (Table 1)


 

 

 

 

Fig. 2: Complexes formula

 

Table 1: amounts and formulae of the prepared complexes

No.

Wt. of OABNA in gram

Salts

Wt. of Salts gm

 %yield

Complexes

1

0.513

Zn(CH3COO) 22H2O

0.25

82

[Zn (OABNA)2] Ac2

2

0.378

Zn(NO3) 26H2O

0.25

86

[Zn (OABNA)2] (NO3)2

3

0.826

ZnCl 2

0.25

77

[Zn (OABNA)2] Cl2

4

0.459

Mn(CH3COO) 24H2O

0.25

75

[Mn (OABNA)2] Ac2

5

o.448

Mn(NO3) 24H2O

0.25

84

[Mn (OABNA)2] (NO3)2

6

0.569

MnCl 2 4H2O

0.25

72

[Mn (OABNA)2] Cl2

 


Analytical and physical measurements:

The ligand and its complexes characterized by using physical and chemical Technique such as melting point determination, conductivity measurements, Molar refraction, (CHN elemental analysis) and spectroscopic analysis such as infrared spectroscopy (1H NMR, 13C-NMR) have been recorded for the ligand by NMR Bruker Ultra Shield 300 MHz in Lester, Shefild University- UK using Deut rated CDCl3., finaly antibacterial activity evaluation.

 

Antimicrobial assay of the complexes:

The antibacterial of Schiff bases were investigated towards multi-drug resistant bacteria and expressed as the diameter of the inhibition zones according to the agar plate diffusion method.8 The multi-drug resistant to antibiotics such as Ampicillin, Cephalexin, Colisin.

 

Four pathogenic microorganisms {Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Proteus mirabilis} were chosen for study the antibacterial activity of the ligands and their complexes.9 All the bacterial strains have been carried out and identified in The Biology Department, College of Education for Pure Science, University of Mosul.

 

RESULTS AND DISCUSSION:

The resulting complexes were yellow solids, air stable, insoluble in water but soluble in DMF the complexes relative molecular weights revealed they had the formula [M(OABNA)2] X2, M = Zn, Mn, OABNA=O-aminobenzylidenenicotinamide, X2= (NO3), (CH3COO)2, Cl2 The ligand is tri dentate. [10] (Table 1). The values of the molar conductivities (142 -170) Ω-1 cm2 mol-1) approached those expected for 1:2. The molar refraction of the complexes in 10-3 M DMF solution was in the range 1.4698x10-4 - 1.4777x10-4. The molar refraction is an additive and constitutive property. It has been used to construct the correct structure of the complexes11. (Table 2), The isolated complexes analyzed for carbon, nitrogen, hydrogen, (CHN), Zn and Mn were determined by flame atomic absorption spectrometry (Table 3) assigned to a monomeric structure, having octahedral geometries (Table 4)

 

Table 2: Some analytical and physical properties

No.

Color

Mp C

ReF. x10-4

M.Wt g/mol

LM*

1

yellow

190

1.4698

631.4

142

2

yellow

198

1.4775

637.4

165

3

yellow

193

1.4777

648.4

170

4

yellow

188

1.4774

620.94

158

5

yellow

185

1.4773

626.94

153

6

yellow

191

1.4872

637.94

164

^M = molar conductance in Ω-1 cm2 mol-1

 

FT-IR:

The infrared spectra of the ligands and the complexes are shown in (Table 4)in o-aminobenzalidinnicotinamide, the band at 3443.39 cm-1was assigned to v(N-H), in complexes the band was observed at lower frequency, which demonstrate that, the nitrogen atom of amine group was coordinated to the metal ion.12

 

The spectra of Schiff-bases showed a strong band in the region 1688.60cm-1 as due to C=N stretching vibration. This band shifted towards a lower frequency, which demonstrate that, the nitrogen of azomethine group was coordinated to the metal ion.12 the bands at 1333.16 cm-1 was assigned to v(C-N), the bands have been shifted to a lower frequency in the synthesized complexes. This indicates that the coordination of the ligand through the nitrogen of the pyridine group12.

 

The other bands in the region 1677.27 cm 1 in ligand and 1675.72-1578.06 - cm 1 in complexes due to υC=O of Carboxyl group that remained unaltered upon coordination indicating that there is no coordination through this group and the metal ion.13

 

The band at 558–548 cm-1 was due touM-N which demonstrated that the all Nitrogen atoms of ligand was coordinated to the metal ion.13


 

Table 3: CHNS analysis, Metal contents of the prepared complexes

S.No.

C% (Exp.) Calc.

H% (Exp.) Calc.

N% (Exp.) Calc.

O% (Exp.) Calc.

Zn% Mn, (Exp.) Calc.

1

(57.87) 57.01

(7.01) 6.52

(14.10) 13.30

(15.10)15.20

(11.08)10.35

2

(49.30) 48.94

(3.67) 3.13

(17.95)17.57

(19.00) 20.08

(15.10)10.26

3

(47.91) 48.11

(4.20) 3.08

(13.61)12.95)

(5.00)4.93

(10.10)10.08

4

)57.11)57.97

(4.30) 4.18

(14.00)18.03

(16.01) 15.46

(9.30)8.84

5

(50.33) 49.76

(4.22)3.19

(16.91) 17.86

(20.09)20.41

(8.17)8.76

6

)50.03( 48.90

3.90) 3.13)

(14.25)13,16

(5.35) 5.01

(910)8.61

 

Table 4: Some Important Bands in FT- IR Spectra of the ligand and Their Complexes

No

uNH

C=N u

uC-N

C-Hu

uC=O

uM-N

L

3443.39

1586.15

1333.16

3080.79

1677.27

-

1

3356.19

1513.72

1095.92

3211.29

1675.72

545

2

3363.76

1524.44

1096.16

3077.03

1593.20

551

3

3356.28

1514.97

1089.43

3192.18

1578.06

558

4

3341.12

1520.73

1108.66

3170.14

1673.16

552

5

3367.91

1518.48

1093.59

3173.26

1593.55

554

6

3359.31

1522.93

1097.21

3161.04

1589.43

548

 


1HNMR:

Spectra of the ligand in CDCl3 as internal reference were measured. The results of H1 NMR spectra supported the structure of the ligand under investigation [13].

 

1HNMR (CDCl3, 400MHz):

.δ=7.50 (S, 1H, H-C=N), δ=7.24 (m, Ar-H), δ= 1.63 (S, 2H, NH2) (Fig.3).

13C- NMR:

13C- NMR (CDCl3, 400MHz):

δ= 199.0 (C=O), δ=139.0 (C= N), δ= 134.0, 129.2, 128.7, 127.5 (C of Ar) (Fig.4).

 


 

Fig. 3: 1H-NMR (OABNA)                                                                         Fig. 4: 13C- NMR (OABNA)

 


Microorganisms tested:

For all the compounds, DMF were used for screening of antimicrobial activity. In vitro, antimicrobial activity of the different Schiff bases was studied against pathogenic microbial strains by the Agar well diffusion method14. Nutrient aga rwas used for the antibacterial susceptibility test respectively. the antibacterial is also known to attack the cell in defferent methods such as inhibiting the growth of microorganisms by affecting special target sites like the synthesis of cell wall, protein and nucleic acid or by inhibiting the action of the cell membrane, binding of the sulfhydryl groups of the cell enzymes with the complexes" 14. The OABNA and number of complexes have antibacterial activity against the bacteria. As metal ion preferentially bind to –N=C, NH2, N of ring in ligand effecting the cell enzyme more strongly. "It is important to assume that the ligand and complexes screened were involved in competitive equilibria involving the –C=N- group of the cell enzyme. Therefore, we concluded that some of the compounds aquire biological activity. If this is the case, "15(Table 5) (Fig. 5).


 

Table 5: Antibacterial activity (inhibition zone) of different concentrations of the ligands and complexes (μg/ml)

Compound

Psudomonus auruginosa

Proteus mirabilis

Escherichia coli

Staphylococcus aureus

Cons\μg

125

250

500

125

250

500

125

250

500

125

250

500

OABNA

10

15

22

10

15

21

9

17

20

9

15

21

1

7

10

15

8

11

18

7

13

18

7

12

18

2

8

12

20

9

13

13

9

14

20

8

15

19

3

7

9

18

6

11

18

7

12

19

7

12

21

4

9

13

16

7

12

17

6

7

9

6

8

11

5

6

8

10

6

12

19

6

14

21

6

9

16

6

10

15

15

6

9

10

-

6

6

8

13

17

Ax25

-

-

-

9

CIPS

20

15

15

20

 

Fig. 5: (inhibition zone) of ligand and complexes


 

CONCLUSIONS:

In the present study, new Schiff base derived from Nicotinamide with o-aminobenzaldehyde was synthesized and characterized the structures of the metal complexes as well as Schiff bases were proved by elemental analysis, NMR and FTIR spectra. The results showed that Schiff base ligand coordinate with metal ions through the N atoms of azomethine, amine and pyridine as tri dentate ligand and octahedral geometry of all complexes are presented. Which is advocated by the FT-IR spectra, the composite complexes were studied as antibacterial and the results showed that all complexes have a various activity against bacteria.

 

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Received on 20.04.2020            Modified on 28.06.2020

Accepted on 20.07.2020           © RJPT All right reserved

Research J. Pharm. and Tech 2021; 14(3):1711-1715.

DOI: 10.5958/0974-360X.2021.00304.8