International Journal of Materials Science and Applications
Volume 4, Issue 4, July 2015, Pages: 225-228

Mixed Ligand Complexes of Co(II) and Ni(II) Containing Organic Acids and Amine Bases as Primary and Secondary Ligands

Md. Sher Ali1, Md. Kudrat-E-Zahan2, 4, *, Md. Masuqul Haque2, Md. Abdul Alim3, Md. Mofasserul Alam1, Jesmin Ara Shompa1, M. S. Islam2

1Inorganic Research Laboratory, Department of Chemistry, University of Rajshahi, Rajshahi, Bangladesh

2Department of Chemistry, Faculty of Science, University of Rajshahi, Rajshahi, Bangladesh

3Department of Analytical and Environmental Chemistry, Bangabandhu Sheikh Mujibur Rahman Science & Technology University, Gopalganj, Bangladesh

4Department of Chemistry, University of Rajshahi, Rajshahi, Bangladesh

Email address:

(Md. Kudrat-E-Zahan)

To cite this article:

Md. Sher Ali, Md. Kudrat-E-Zahan, Md. Masuqul Haque, Md. Abdul Alim, Md. Mofasserul Alam, Jesmin Ara Shompa, M. S. Islam. Mixed Ligand Complexes of Co(II) and Ni(II) Containing Organic Acids and Amine Bases as Primary and Secondary Ligands. International Journal of Materials Science and Applications. Vol. 4, No. 4, 2015, pp. 225-228. doi: 10.11648/j.ijmsa.20150404.11


Abstract: The synthesis and characterization of mixed ligand complexes of Co(II) and Ni(II) have been described. Organic dibasic acid, malic acid plays role as primary ligand and Heterocyclic amine bases play role as secondary ligands in the complexes. Melting points, Elemental analysis, Magnetic susceptibility measurements, IR, UV and 1H-NMRspectral analysis were used in determining their physico-chemical properties. The prepared complexes of Co(II) and Ni(II) were found to form octahedral structure.

Keywords: Mixed Ligand Complexes, Organic Acids, Amine Bases


1. Introduction

The bonding nature of the α-amino acid complexes of Co(II) ion and their spectroscopic investigation have been the subject of much interest since long time perhaps because of their biochemical importance. A knowledge of the interaction between biologically active molecules and metals is needed when preparing biomaterials or considering certain aspects of biocompatibility. The study of model species such as the simple amino acids can assist in the interpretation of more complex system. Amino acid has the neutral donor N at one end and acidic replaceable H at the other end and are sufficient length to span two adjacent coordinating site and the resulting complexes is a non-electrolyte chelate or inner complex compound. Such metal chelates are characterized by great thermal stability [1], are intensely colored, insoluble in water but soluble in organic solvents are of practical importance. Amino acids form complexes with metal atoms and exhibit significant biological and enzymatic activities [2]. The synthesis, spectrochemical properties, structure, stability, thermochemical study, and characterization of complexes of Ni(II) with histidine, glycine, alanine, and other amino acids have previously been reported [3–9]. Standard molar enthalpies of formation of glycine and alanine in the gaseous phase on the basis of theoretical calculations have also been studied [10].

Recently, we studied few mixed ligand complexes containing heterocyclic amine as secondary ligands and few Schiff base containing complexes [11-20]. We report here, the synthesis and characterization of several new mixed ligand complexes of Co(II) and Ni(II) with Organic dibasic acid, malic acid as primary ligand and Heterocyclic amine bases as secondary ligands.

2. Experimental

2.1. Reagents and Chemicals

All the reagents used were of analytical or chemical grade purity. Solvents were purified and dried according to the standard procedures.

2.2. Physical Measurements

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 the present study. Infrared spectra (KBr) were recorded in a SIMADZU FTIR- 8400 (Japan) spectrophotometer in the range 4000– 400 cm–1. The absorbance’s of the complexes were recorded on SHIMUDZU Spectrophotometer (Model UV-1800). Carbon, hydrogen, nitrogen analysis and 1H NMR were carried out from the Liverpool University, Liverpool, England.

2.3. General Method for the Preparation of the Complexes

An ethanolic solution (just dissolved) of M(II) chloride salts (2 m.mol) and ethanolic potassium hydroxide solution (just dissolved) of malic acid (4 m.mol) were mixed and gently heating with stirring for half an hour. No precipitate was observed, and then secondary ligand (Pyridine/2-Aminopyridine) in calculated ratio was added and stirred until complex precipitated. The precipitates were filtered, washed several times with alcohol and then dried in vacuum desiccator over phosphorus pentaoxide (P2O5).

3. Results and Discussion

3.1. Elemental Analysis and Conductivity Measurement

The analytical data and their physical properties of the complexes are tabulated in tables 1 and 2 respectively. The analytical data are in good agreement with the proposed empirical formula of the prepared complexes. The molar conductance of 10−3 M solution of the complexes in DMSO were measured at 30°C. The molar conductance values (Table 2), lies in the range 107.73-102.61 indicating electrolytic nature of the complexes.

3.2. Magnetic Moment and Electronic Spectra

The observed values of effective magnetic moment (meff) of the complexes at room temperature are given in Table 2. The magnetic moment values of the complexes 1.79 to 5.57 B.M indicate that these complexes were paramagnetic. In nature suggesting that there were no changes in the oxidation states of the metal ions upon complexation.

The Co(II) complexes possesses magnetic moment in the range 4.98 to 5.57 B.M. in agreement with octahedral geometry. The three transitions observed in the electronic spectra of the Co(II) complexes indicate the octahedral environment around the metal ion. The electronic spectra showed strong peak between 315 to 590 nm assignable to the transitions 4T1g ® 4A2g (F) and 4T1g ® 4T2g (F).

The electronic spectra of Ni(II) complexes showed peaks characteristic of octahedral geometry. The reflectance spectra both types of complexes consist of bands range between 312 to 545 nm assignable to the transitions 3A2g® 3T2g and 3A2g® 3T1g (F) respectively. The range of magnetic moment between 2.85 to 3.78 B.M. in agreement with octahedral geometry of the complexes

3.3. Infrared Spectral Spectra

Salient features of the IR spectra of the complexes are tabulated in the Table 4. The complexes display bands 1645-1598 and 1427-1303 cm-1 due to n(C=O) and n(C-O) stretching respectively, significantly lower than that of free ligand n(C=O) = 1700and n(C-O) = 1600 cm-1indicating the coordination of metal ion through its carboxylate anion. The symmetric stretching of n(COO) frequencies are observed at 1473-1403 cm-1. The disappearance of the n(O-H) mode observed in the free phthalic acid and amino acid molecule clearly indicate the loss of proton for O-H group upon coordination, revealing those acids are dinegative bidentate ligand coordinating through the carboxylate anion. The complexes showed n(N-H) bands at 3445-3166cm-1 which are significantly lower than the free ligand (amine base bands from 3100-3400 cm-1), clearly suggests the coordination of amino groups through nitrogen atoms of amino base. The in-plane and out-of-plane ring deformation modes of heterocyclic amines observed at 668 and 639 cm-1 respectively undergo a positive shift in mixed ligand complexes confirming their coordination through nitrogen. The presence of metal nitrogen bonding in the complexes are evident from the appearance of n(M-N) modes at 388-359 cm-1 and 379-418 cm-1 respectively in the spectra of the complexes.

3.4. 1H NMR Spectra

The 1H NMR spectra of the complex 2K+[Co(MaH)2(Py)2]2- was recorded in DMSO-d6 solution at room temperature. Complex 2K+[Co(II)(MaH)2(Py)2]2-: 8.67-8.54 (m, 4H, Ar-H), 8.09-8.06 (m, 2H, Ar-H), 7.30-7.28 (m, 4H, Ar-H), 5.12 (brs, 2H, -CHOH), 3.71-3.56 (m, 2H, CH), 2.21 (d, 4H, J = 6.4 -CH2).

Protons of pure pyridine molecule, showed peaks for the ortho hydrogen at δ = 8.47 ppm. But after complexation with the Co(II) ion the same protons have detected at δ = 8.67-8.54 ppm. From the nature of the 1H NMR spectra of the proposed complex it is clear that the N atom in pyridine ring has involved in complexation. The same effect has observed for the protons of malic acid. According to the peak heights of the protons in 1H NMR spectra of complex molecule it can be assumed that malic acid have taken part in complexation with the metal ion. Because, ten protons of pyridine and eight protons of malic acid molecule are found in the same spectra of the complex.

Table 1. Analytical data of Co(II) and Ni(II) complexes.

Complexes Yield% M% C% H% N%
2K+[Co(II)(MaH)2(2-Apy)2]2- 71 16.70 (16.60) 23.05 (24.01) 2.43 (2.97) 6.28 (6.78)
2K+[Co(II)(MaH)2(Py)2]2- 75 10.78 (10.02) 45.89 (46.04) 4.79 (4.45) 4.38 (4.94)
2K+[Ni(II)(MaH)2(2-Apy)2]2- 72 10.12 (10.02) 27.69 (27.80) 2.06 (2.18) 5.11 (5.23)
2K+[Ni(II)(MaH) 2(Py)2]2- 67 9.69 (9.75) 40.59 (40.65) 3.75 (3.80) 4.76 (4.88)

MaH = Malic Acid, Py = Pyridine, 2-Apy = 2- Aminopyridine

Table 2. Physical properties of Co(II) and Ni(II) complexes.

Complexes Colour Melting point ̊C (± 0.52) Molar conductance W cm2 mol-1 Magnetic moment meff (B.M.)
2K+[Co(II)(MaH)2(2-Apy)2]2- Brown 275 106.02 5.57
2K+[Co(II)(MaH)2(Py)2]2- Green 230 102.61 5.47
2K+[Ni(II)(MaH)2(2-Apy)2]2- Green 290 107.73 3.60
2K+[Ni(II)(MaH)2(Py)2]2- L.Green 260 103.36 2.98

MaH = Malic Acid, Py = Pyridine, 2-Apy = 2- Amino pyridine

Table 3. Electronic spectral data of Co(II) and Ni(II) complexes.

Complexes lmax (n.m)
2K+[Co(II)(MaH)2(2-Apy)]2- 385 448 578
2K+[Co(II)(MaH)2(Py)2]2- 371 459 587
2K+[Ni(II)(MaH)2(2-Apy)2]2- 341 443 530
2K+[Ni(II)(MaH)2(py)2]2- 332 431 545

MaH = Malic Acid, Py = Pyridine, 2-Apy = 2- Amino pyridine

Table 4. IR spectral data of Co(II) and Ni(II) complexes.

Complexes n(N-H) cm-1 n(C=O) cm-1 n(M-N) cm-1 n(C-O) cm-1 n(COO-) Symmetry cm-1 Aromatic ring cm-1
2K+[Co(II)(MaH)2(2-Apy)2]2- 3367 1624 381 1323 1421 897
2K+[Co(II)(MaH)2(Py)2]2- 3316 1632 387 1303 1403 827
2K+[Ni(II)(MaH)2(2-Apy)2] 2- 3198 1625 376 1340 1449 840
2K+[Ni(II)(MaH)2(Py)2]2- 3335 1559 388 1356 1415 851

MaH = Malic Acid, Py = Pyridine, 2-Apy = 2- Amino pyridine

4. Conclusion

Elemental analysis correspond to metal: ligand stoichiometry for Co(II) and Ni(II) complexes are 1:2:2. Magnetic susceptibility measurement shows that the complexes are paramagnetic. The IR spectral data shows that the ligands coordinate to the metal through O and N atoms. The electronic spectral data are in conformity with the transitions of octahedral complexes. The 1H-NMR studies of the complex indicates two pyridine and two malic acid molecules coordinate with Co(II) metal ion and represents the complex as 2K+ [Co(II)(MaH)2(Py)2]2-. Based on the above analysis the structure of complex 2K+ [Co(II)(MaH)2(Py)2]2-has been proposed as shown in Fig. 1.

Figure 1. Structure of the complex 2K+ [Co(II)(MaH)2(Py)2]2-.


References

  1. M. Mori, M. Shibata, E. Kyuno, and M. Kanaya, Preparation and Absorption Spectra of the Cobalt(III) Complexes of Amino Acids, Bull. Chem. Soc. Jpn. 1961; 34(12): 1837-1842.
  2. Perrin D.D., Agarwal R.P., Metal ions in biological systems. Ed. Sigel H.C., Vol. 2, p. 167, Marcel Dekker, New York 1973.
  3. Saxena VK, Gupta M, Srivastava MN.,Synthesis and Characterization of Complexes of Copper(II), Nickel(II), Cobalt(II) and Zinc(II) with Histidine and Glycine or Alanine,Synth React Inorg Met Org Chem. 1996; 26: 1661-1676.
  4. Awni Khatib, Fathi Aqra, Studies on crystals of d-, l-, and dl-alaninato nickel(II) complexes, Trans. Metal Chem., 2009; 34(7): 787-790.
  5. Vimal Kumar Saxenaa, Madhu Guptaa & M. N. Srivastavaa, Synthesis and Characterization of Complexes of Copper(II), Nickel(II), Cobalt(II) and Zinc(II) with Histidine and Glycine or Alanine, Synth React Inorg. and Metal-Org. Chem. 1996; 26(10) 1661-1676.
  6. Di YY, Chen JT, Tan ZC. Low-temperature heat capacities and standard molar enthalpy of formation of the solid-state coordination compound trans-Cu(Ala)2(s) (Ala = l-α-alanine) Thermochimica Acta., 2008; 471: 70-73.
  7. Abdul Alim, Md. Kudrat-E-Zahan, Md. Masuqul Haque, MTH Tarafder. Synthesis and Characterization of Some Metal Complexes of Cu(II), Ni(II), Zn(II), Cd(II), Sn(II), Co(II), Sb(III) AND Fe(III) Containing Bidentate Schiff Base of Smdtc. Science Journal of Chemistry. 2015; 3(3): 35-39.
  8. Md. Kudrat-E-Zahan, Md. Masuqul Haque, Lokonuzzaman Ahmmed, M. Sher Ali, Md. Saidul Islam. Studies on the Mixed Ligand Complexes of Co(II), Ni(II) and Cu(II) with Phthalimide and Heterocyclic Amines. International Journal of Materials Science and Applications. 2015: 4(2); 120-123.
  9. Misbah ur Rehman, Muhammad Imran, Muhammad Arif. Synthesis, Characterization and in Vitro Antimicrobial Studies of Schiff-Bases Derived from Acetylacetone and Amino Acids and their Oxovanadium(IV) Complexes. Am. J. App. Chem., 2013; 1(4): 59-66.
  10. Dorofeeva OV, Ryzhova ON., Revision of standard molar enthalpies of formation of glycine and l-alanine in the gaseous phase on the basis of theoretical calculations. J Chem Thermodyn., 2009; 41(4): 433-438.
  11. Laila Arjuman Banu, M.S.Islam, M.Abdul Alim Al-Bari and Md.Kudrat-E-Zahan, Synthesis and characterization with antibacterial, antifungal, cytotoxicity studies on the Co(II), Ni(II) And Cu(II) complexes of tridentate ONO coordinating schiff bases and heterocyclic amines. Int. Jour. Recent Adv. Multi. Res. 2015; 02(01): 145-148.
  12. Md. Kudrat-E-Zahan, Md. Abul Bashar, Md. Faruk Hossen, and M. Saidul Islam. Synthesis, Spectroscopic, Magnetic and Biological Activity of Cr(III) and Fe(III) Complexes with Amino Acids and Heterocyclic Amines. Asian J. Res. Chem, 2015; 8(2): 74-76.
  13. Md. Abul Bashar, Md. Abdul Mannan, Md. Faruk Hossen, M. Saidul Islam and Md. Kudrat-E-Zahan. The synthesis, characterization and biological activity investigation of mixed ligand Coordinated Ni(II) Complexes. Asian J. Res. Chem, 2015; 8(1): 55-58.
  14. Md. Abdul Latif, Md. Anarul Islam and Md.Kudrat-E-Zahan, Synthesis, Structure andAntimicrobial studies of four new N2O4 schiff base containing complexes of Ag(I), Cr(III), Fe(III) and Sb(III) metal ions. Intern. J. Recent Adv. Multi. Res., 2015; 02(02): 206-208.
  15. Md. Abul Bashar, Shejuty aktar, Md. Abdul Alim Al-Bari, Md. Faruk Hossen, M. Saidul Islam and Md. Kudrat-E-Zahan. Synthesis, Characterization and Antimicrobial Activity of Amino acids and Heterocyclic amines Coordinating Cu(II) Complexes. Asian J. Res. Chem, 2014; 7(11): 909-912.
  16. Md. Shiraj-U-Ddaula, Md. Anarul Islam, Shejuty aktar, Md. Khairul Islam, Md. Abdul Alim Al-Bari, Md. Masuqul Haque and Md.Kudrat-E-Zahan. Synthesis, Characterization and Antimicrobial activity of Cd(II), Ni(II), Co(II) and Zr(IV) metal complexes of Schiff base ligand derived from diethylenetriamine and isatin. Asian J. Res. Chem, 2014; 7(7): 619-621.
  17. Md. Abul Bashar, Shejuty aktar, Md. Jahangir Alam, Md. Faruk Hossen, M. Saidul Islam and Md. Kudrat-E-Zahan. Studies on synthesis, characterization and biological activity of mixed ligand Coordinating Co(II) Complexes. Asian J. Res. Chem, 2014; 7(12): 1016-1018.
  18. Md.Anarul Islam, Roksana khatun, M.Monirul Islam and Md.Kudrat-E-Zahan, Synthesis, spectroscopic monitoring and biological activities of N2O4 schiff base ligand containing metal complexes of Cd(II), Pd(II), Hg(II) and Zr(IV). Asian J. Res. Chem, 2014; 7(2): 163-165.
  19. Md.Kudrat-E-Zahan and Hiroshi Sakiyama, Synthesis and spectral properties of dinuclear Bis(acetylacetonato)nickel(II)aqua complex, Asian J. Res. Chem, 2013; 6(11): 1072-1074.
  20. Md.Kudrat-E-Zahan, M. S. Islam and Md.Abul Bashar. Synthesis, Characterization and antimicrobial activity of Some Metal Complexes of Mn(II), Fe(III) Co(II), Ni(II), Cu(II) and Sb(III) Containing Bidentate Schiff base of SMDTC, Russ. Jour of gen. Chem. 2015; 85(3): 667-672.

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