Synthesis, Characterization and Antimicrobial Activity of Fe (III) Complexes with Tartaric Acid/Succinic Acid and Heterocyclic Amines

Md. Kudrat E. Zahan^{1, *}, Md. Abdul Alim Al Bari², Md. Abul Bashar¹, Laila Arjuman Banu¹, M. M. Haque¹, M. Saidul Islam¹

¹Department of Chemistry, University of Rajshahi, Rajshahi, Bangladesh

²Department of Pharmacy, University of Rajshahi, Rajshahi, Bangladesh

Abstract

The synthesis and characterization of mixed ligand complexes of Fe (III) with tartaric acid/succinic acid and heterocyclic amines. These complexes were characterized on the basis of elemental analysis, conductometric, magnetic measurements, UV-vis, IR spectral studies. All the complexes were found electrolytic and paramagnetic in nature with high spin octahedral structure. The synthesized complexes showed moderate to strong antimicrobial activity.

Keywords

Mixed Ligand Complex, Electronic Spectra, Antimicrobial Activity, Heterocyclic Amines, Tartaric Acid, Succinic Acid

Received: June 27, 2015
Accepted: July 8, 2015
Published online: July 22, 2015

@ 2015 The Authors. Published by American Institute of Science. This Open Access article is under the CC BY-NC license. http://creativecommons.org/licenses/by-nc/4.0/

1. Introduction

Tartaric acid is a muscle toxin, which acts by inhibiting the production of malic acid and in high doses causes paralysis and death (Gold and Zahm 1943). It is used in the medical fields (Addington et al., 1998) and acting as a preservative after fermentation (Salgado et al., 2010). Salts of tartaric acid (Rochelle salt) used as mild laxative and tartaric dihydrazides utilized as agrochemicals (Kinoshita et al., 1997). Derivatives of tartaric acid are frequently used, widely available and inexpensive acid resolving agents for the separation of racemic mixtures via diastereoisomeric salt (Jacues et al., 1981), (Ilmarinen et al., 2001) or supramolecular compound formations (Nemak et al., 1996 and Casba et al., 2000).

Succinic acid, derived from fermentation of agricultural carbohydrates, has a specialty chemical market in industries producing food and pharmaceutical products, surfactants and detergents, green solvents and biodegradable plastics, and ingredients to stimulate animal and plant growth (Zeikus et al., 1999). Succinic acid (Suc) is involved in the citric acid or tricarboxylic acid (TCA) cycle and the glyoxalate cycle. It is synthesized in almost all microbial, plant, and animal cells (Song and Lee 2006). Suc is a bidentate ligand. In coordination chemistry, it forms strong complexes with many metal ions (Gandham and Rao 2012).

Recently, we studied electronic properties of N₂O₄ Schiff base ligand containing metal complexes of Cd(II), Pd(II), Hg(II) and Zr(IV) (kudrat et al., 2013, Anarul et al., 2014 and Laila Arjuman Banu et al., 2015) also synthesis and characterization of mixed ligand coordinating Co(II), Cu(II), Ni(II), Cr(III) and Fe(III) complexes with amino acid and heterocyclic amines (Bashar et al., 2014, Bashar et al., 2014, Bashar et al, 2015 and Kudrat et al., 2015). In this study, we described a systematic study of preparation and characterization of mixed ligand Fe(III) metal complexes with tartaric acid or succinic acid and hetero cyclic amines also their functions as antimicrobial actions.

2. Experimental

2.1. Materials

All chemicals were commercial products and were used as supplied. Melting points of all metal complexes were measured by an electro thermal melting point apparatus model no. AZ6512. The SHERWOOD SCIENTIFIC Magnetic Susceptibility Balance was used for magnetic moment measurements. Infrared spectra (KBr) were recorded in a SIMADZU FTIR- 8400 (Japan) spectrophotometer in the range 4000 – 400 cm^–1.

2.2. General Method for the Preparation of the Complexes

General method for preparation of the Fe(III) complexes of [Fe(Tar)L₄]Cl and [Fe(Succ)L₄]Cl; Where, L = Pyridine, Quinoline, and Iso-quinoline and 2-Picoline, Tar=Tartaric acid and Succ = Succinic acid.

An ethanolic solution of Fe(III) chloride (1 m mole) and deprotonated tartaric acid (1 m mole) or succinic acid (1 m mol ) were mixed with constant stirring but no precipitate was observed. Then 25 ml of an ethanolic solution of L (4 m mole) was added to the resulting mixture and heat on a magnetic regulator hot plate with constant stirring. The volume of the solution was reduced to one half and allowed to cool. The precipitate formed and were filtered, washed several times with ethanol and then dried in a desiccator over anhydrous CaCl₂.

3. Results and Discussion

All the complexes are stable at room temperature. The Fe(III) complexes are insoluble in common organic solvents but are soluble in DMSO, DMF and CHCl₃.

3.1. Elemental Analysis and Conductivity Measurement

The molar conductance of 10^-3M solution of the complexes in DMF was measured at 28°C. The molar conductance values are in the range 132.55 to 166.30 W^–1 cm² mole^-1 (Table 1). The molar conductance values (Table 1) indicate that the compounds are 1:1 electrolytic in nature. Some physical and chemical properties are shown in table 1. The obtained elemental data were in good agreement with the calculated value (Table 2).

Table 1. Physical properties of Fe(III) complexes.

Where Py = Pyridine, Q= Quinoline, IQ= Iso-quinoline, 2-Pic= 2-Picoline,Tar=Tartaric acid and Succ = Succinic acid

Table 2. Data of the elemental analysis of the complexes.

Where Py = Pyridine, Q= Quinoline, IQ= Iso-quinoline, 2-Pic= 2-Picoline, Tar=Tartaric acid and Succ = Succinic acid.

3.2. IR Spectral Studies

The IR spectrum of the complexes showed characteristic bands at around 1466 cm^-1, 2910 cm^-1, 1615 cm^-1, 1303 cm^-1, 552 cm^-1, and 486 cm^-1 corresponding to the n(C=N), n(CH), n(C=O) n(C-O) n(M-O) n(M-N) stretching frequencies, respectively (Table 3). The ligand Tartaric acid co-ordinates to the Fe(III) ion through the carboxylic acid group as the n(M-O) and n(C-O) bands of the complex present in IR spectra. The free hetero amine ligand shows n(C=N) band at 1815 cm^-1. The lowering of the stretching frequency suggested that the heterocyclic amine bonded to metal through the nitrogen atom. The bands of the complexes at 412 cm^-1 is undoubtedly to the (M - N) modes.In case of first four complexes, the presence of IR band at 3400 cm^-1indicated that the OH group did not make bond to the metal ion.

Table 3. Selected IR spectral data of the complexes.

Where, Py = Pyridine, Q= Quinoline, IQ= Iso-quinoline, 2-Pic= 2-Picoline, Tar=Tartaric acid and Succ = Succinic acid

3.3. Magnetic Moment and Electronic Spectra

The observed values of effective magnetic moments (m_eff) of the complexes at room temperature are given in table 1. The magnetic moment of Fe (III) complexes varies from 5.58 to 5.99 B.M. corresponding to five unpaired electrons which indicated that all the complexes are in high spin octahedral structure.

All the compounds under investigation are found to be paramagnetic and their electronic spectra are also given in table 4. The electronic spectra of the Fe(III) complexes gave three bands at (423-437) nm, (346-358) nm, and (305-315) nm, which are caused by ⁶A_1g → ⁴Eg(G) , ⁶A_1g → ⁴T_2g(D)and ⁶A_1g → ⁴Eg (D) and charge transfer band respectively suggesting the octahedral stereo-chemistry.

Table 4. Selected electronic spectral data for the complexes in nm.

Where, Py = Pyridine, Q= Quinoline, IQ= Iso-quinoline, 2-Pic= 2-Picoline, Tar=Tartaric acid and Succ = Succinic acid

4. Antibacterial and Antifungal Screening

Metal complexes play an important role in regulating biological activities. The disk diffusion method was employed for the in vitro study of antibacterial effects against one Gram positive and two Gram negative bacteria. On the other hand antifungal activities of the metal complexes against two pathogenic fungi Candida albicuas (Human Pathogens) and Aspergillus species (Plant Pathogens) were measured. The results revealed that the complexes are more microbial toxic than the free metal ions or ligands (Md. Kudrat-E-Zahan et al., 2015). Fe(III) complexes showed moderate to strong antimicrobial activity as shown in table 5 and 6.

Table 5. Antibacterial activity of the synthesized complexes.

Where, Q= Quinoline, IQ= Iso-quinoline, Tar=Tartaric acid and Succ = Succinic acid

Table 6. Antifungal activitiy the synthesized complexes.

Where, Q= Quinoline, IQ= Iso-quinoline, Tar=Tartaric acid and Succ = Succinic acid

5. Conclusion

Elemental analysis correspond to metal: ligand stoichiometry for Fe(III) complexes are 1:1:4. Magnetic susceptibility measurement indicated the paramagnetic nature of the complexes. The IR spectral data shows the ligand coordinate with the metal through O and N atoms. The electronic spectral data are in conformity with the transitions of octahedral Fe(III) complexes. Based on these facts structure of complex have been proposed as shown in Figure 1 and 2.

Figure 1. Propsed structure of [Fe(tar)L₄]Cl complexes Where, L = Pyridine, Quinoline, Isoquinoline and 2-Picoline.

Figure 2. Proposed structure of [Fe(Succ)L₄]Cl complexes Where, L = Pyridine, Quinoline, Iso-quinoline and 2-Picoline.

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