International E-publication: Publish Projects, Dissertation, Theses, Books, Souvenir, Conference Proceeding with ISBN.  International E-Bulletin: Information/News regarding: Academics and Research

Synthesis and Characterization of Salicylaldazine (H2L) and its mixed Ligand complexes [ML(H2O)],[M(LH)2(caf)n] ; M= Zn2+, Cd2+, Ni2+, Cu2+,Co2+, Mn2+, Fe2+; n=1,2 ; Caf= caffeine

Author Affiliations

  • 1Equipe métallation, complexes moléculaires et application, Faculté des sciences, BP 11201 Zitoune, Meknès, MOROCCO
  • 2 L.P.C.M., Faculty of Science and Technology, University Moulay Ismaïl, B. P. 509 Boutalamine, Errachidia, MOROCCO

Res.J.chem.sci., Volume 4, Issue (10), Pages 72-84, October,18 (2014)


The ligand salicylaldazine (H2L) was prepared by condensation of salicylaldehyde and hydrazine in (2/1) molar ratio. The synthesized ligand was investigated using different physical techniques such as infrared, Raman spectroscopy, 1H, 13C NMR and UV-Visible. Transition metal complexes [ML(H2O)];M= Zn2+, Cd2+, Ni2+, Cu2+, Co2+, Mn2+, Fe2+ and the mixed ligand complexes [M(LH)2(caf)n]; M= Zn2+, Cd2+ for n=1 and M= Ni2+, Cu2+, Co2+, Mn2+,Fe2+ for n=2 derived from the ligand have been widely studied. The infrared, Raman and UV-Visible data of the metal complexes show that the ligand is coordinated to the metal ions in a tridentate manner, with NOO donor sites of the azine. It is also found that the geometrical structures of these complexes are tetrahedral. Based on the obtained infrared, Raman, NMR spectroscopy, UV-Visible and literature indications, the ligand is coordinated to the metal in bidentate manner through NO donor sites of the azine and with N9 imidazol of the caffeine. Thus, the mixed ligand complexes [M(LH)2(caf)n] exhibit a distorted pentahedral geometry for n=1; M=Zn2+, Cd2+ and a distorted octahedral geometry for n=2; M= Ni2+, Cu2+, Co2+, Mn2+ , Fe2+.


  1. Kolb V.M., Kuffel A. C. and Spiwek H.O., On the Mechanism of Formation of Azines from Hydrazones: Steric Hindrance to Formation of Hydrazones but not Azines, J. Org. Chem., 54, 2771 (1989)
  2. Dakova B. Y., Evers M. J. and Christiaens, The Reactivity of Selenium Dioxide Towards Aromatic Aldehydes Hydrazones, Azines and Phenylhydrazones: Carbonyl Regeneration and a New One-Pot Oxidation of Aldehydes to Aromatic Acids, L. R. Bull. Soc. Chim. Belg., 96, 219-224 (1987)
  3. Christopher J. A. and Jennifer M. P. Stereoselective azine formation in the decomposition of phenyldiazomethanes, J. Am. Chem. Soc.,111(5), 1795–1799 (1989)
  4. H. Loghmani-Khouzani, M. M. M. Sadeghi, J. Safari and O. Sabzi-Fini, synthesis of azines from carbonyl compounds in a solvent free, J. Sci. I. R. Iran, 12( 3), (2001)
  5. Suschitzky H., Walrond E. R. and Hull R. Synthesis of heterocyclic compounds, Part 34. Reactions of chlorosulphonyl isocyanate with carbon–nitrogen double bondsJ. Chem. Soc. Perkin Trans., 1, 47-52 (1977)
  6. Kolb V. M. and Hua D. H., syn-Anti isomerism in the opiate hydrazones and azines derived from naloxone, naltrexone, and oxymorphoneJ. Org. Chem., (49)20, 3824 –3828 (1984)
  7. Kolb V.M., Kuffel A.C., Spiwek H.O., Janota T.E., On the mechanism of formation of azines from hydrazones, J. Org. Chem., 54(11), 2771–2775 (1989)
  8. Bell T.W. and Papoulis A.T., Ion-Selective Hydrazone–Azine Tautomerism of a 14-Membered Macrocylic Ligand, Angew.Chem. Int. Ed. Engl. 31(6), 749-751 (1992)
  9. P. Espinet, J. Etxebarria, M. Marcos, J. Perez and A. Remon, J.L. Serrano, A Novel Approach to Ferroelectric Liquid Crystals: the First Organotransition Metal Compound Displaying This Behavior, Angew. Chem. Int. Ed. Engl. 28(8), 1065–1066 (1989)
  10. Dudis D.S., Yeates A.T., Kost D., Smith D.A. and Medrano J., Iodine-doped polyazines: evidence against bipolarons and nitrenium ions, J. Am. Chem. Soc., 115-8770 (1993)
  11. M. El M. Hamidi, L. Kacha, S. M. Bouzzine, M. El Amane, Theoretical study of the geometrical and electronicproperties of N. N'-di(Ortho-Substituted benzyl) Hydrazine, Mor. J. Chem., 2(3), 225-235 (2014)
  12. C.S. Marvel and P. V. Bonsignore, Heat Stability Studies on Chelates from Schiff Bases and Polyazines of Salicylaldehyde Derivatives, J. Am. chem. Soc., 81(11), 2668–2670 (1959)
  13. M.M. Abo Aly, Infrared and Raman spectra of some symmetric azines, Spectrochimica Acta Part A,55, 1711– 1714 (1999)
  14. B.A. El Sayed, M.M.Abo Aly, A.A.A. Emara and S.M.E. Khalil, Synthesis and structural study of the ligand o-OH acetophenone azine and its Cu(II), Ni(II), Co(II) and Zn(II) complexes, Vibrational Spectroscopy, 3093-100 (2002)
  15. Milan Melnik, Binuclear Caffeine Adducts of Cu(II) acetate and Cu(II) chloracetates with Unusually High Antiferromagnetic Interaction, 43, 3035-3038 (1981)
  16. Barone J.J. and H.R. Roberts, Caffeine Consumption Food Chemistry and Toxicology, 34, and National coffee Association, National soft drink Association, Teacouncil of the USA and information provided by food beverage and pharmaceutical companies, (1996)
  17. . Esimone, C.O., FBC, Okoye, CS Nworu and AgubataIn Vitro Interaction between Caffeine and some Penicillin Antibiotics Against Staphylococcus Aureus, Tropical Journal of Pharmaceutical Research, 7, 969-974, (2008)
  18. Youn J.H., E.A. Gulve and J.O. Holloszy, Calcium Stimulates Glucose Transport in Skeletal Muscles bya Partway Independent of Contraction, Am J Physiol, 260,C555-561, (1991)
  19. M. El Amane Y., Kennouche M., Fahim M., Choukrad, Synthèse et caractérisation des arylazines et de leurs complexes du cuivre II et de Nickel II, International Meeting on Molecular Chemistry and Development, p118, Marrakesh, (2010)
  20. Tolansky S., Multiple Beam Interference Microscopy of Metals, Academic Press, London, 55 (1970)
  21. Revanasiddappa M., Suresh T., Syed Khasim, Raghavendra S.C., Basavaraja C. and Angadi S.D., Transition Metal Complexes of 1, 4 (2-Hydroxyphenyl -1-yl) Diimmino Azine, Synthesis, Characterization and Antimicrobial Studies, E-Journal of Chemistry, 5(2), 395-403, (2008)
  22. Esref Tas Veli, T. Kasumov, Omer Sahin and Mustafa Ozdemir, Transition metal complexes with tridentate salicylaldimine derived from 3,5-di--butylsalicylaldehyde, Trans. Met. Chem., 27(4), 442-446 (2002)
  23. Dunkers J., Zarate E.A. and Ishida H., Crystal structure and hydrogen bonding characteristics of N,N-bis(3,5-dimethyl-2-hydroxybenzyl)methylamine: a benzoxazine dimer, J. Phys. Chem., 100, 13514-13520 (1996)
  24. Braiz R., Bremard C., Laureyns J., Merlin J.C., XVII European Congress on Molecular Spectroscopy, Madrid, Spain, 137 (1985)
  25. Kettle. S.F.A, Coordination compounds, Thomas Nelson and Sons, London, 165 (1975)
  26. Patel I.A. and Thaker B.T., Manganese(III) complexes with hexadentate schiff bases derived from heterocyclic beta- diketones and triethylene tetramine, Indian J Chem., 38A,427-433 (1999)
  27. Nakamoto K., Infrared and Raman Spectra of inorganic and coordination compound 3rd Edition, Wile, New York, (1997)
  28. Jain A.K., Goyal R.N., and Agarwal D.D., Physico-chemical studies on some metal chelates of 5,5 dimethylcyclohexane-2-(2-hydroxyphenyl)hydrazono 1,3 dione (DCPHD), J. Inorganic Nuclear Chem., 43(9), 2005-2009, (1981)
  29. Sohreh Nafisi, Delaram Sadraii Shamloo, Nasser Mohajerani and Akram Omidi, A comparative study of caffeine and theophylline binding to Mg(II) and Ca(II) ions : studied by FTIR and UV spectroscopic methods, Journal of Molecular Structure, 608, 1-7 (2002)
  30. Fatih Ucu, Adnan Saglam and Vesile Guclu, Molecular structures and vibrational frequencies of xanthine and its methyl derivatives (caffeine and theobromine) by ab initio Hartree–Fock and density functional theory calculations Spectrochimica Acta Part A67, 342–349 (2007)
  31. Amane Mohamed EL and Hamdani Hicham EL, Synthesis and Characterization of caffeine Complexes [M (caf) 4X2] M =Ni(II), Cu(II), Zn(II), Cd(II) X = SCN-, CN-; caf : caffeine, Res. J. Chem. Sci.Vol., 4(2), 42-48, (2014)
  32. Carrano C.J., Carrano M.W., Sharma K., Backes G. and Loehr T.S., Resonance Raman spectra of high- and low-spin ferric phenolates. Models for dioxygenases and nitrile hydratase, Inorg. Chem., 29(10), 1865 –1870 (1990)
  33. H.F. Al-amary, M. Sc. Thesis., Benghazi: Garyunis University, (2004)
  34. Lever A.B.P., Inorganic electronic spectroscopy, New York Elsevier Pub. Co., Amsterdam, (1968)
  35. Bojidarka Ivanova, Gold(III) Complex of Caeine: Synthesis, Isolation and Spectroscopic Characterization, Turk.J. Chem, 31, 97-103 (2007)
  36. Vasishta D. Bhatt and Samat R. Ram, Synthesis of Dinuclear Schiff Base Complexes of Mn(II), Fe(II) and Zn(II) via Inter-Complex Reaction, Chem Sci Trans., 2(3),797-804 (2013)
  37. Taghreed Hashim Al-Noor, Ahmed T. AL- Jeboori , Rasha. L. Sadawi, Synthesis and Characterization of Complexes of Schiff Base [1, 2-Diphenyl -2- 2-{[1-(3-Amino-Phenyl)-Ethylidene]-Hydrazono Methyl}-Phenol] with Mn(II), Fe(II), Co(II), Cu(II), Zn(II), Cd(II), Ni(II), and Hg(II) Ions, Chemical and Process Engineering Research, 13, (2013)
  38. Monther.Y. Al. Janabi, The physical Methods in Inorganic Chemistry, (1983)
  39. O. I. H. Al-Ajrawy,Preparation, Characterization of Mn(II),Mn(III), and Mn(IV) Complexes with Schiff Base Ligands Derived from Salicylic acid Hydrazide have N,O Donors and Biological Activity Study,Al-Anbar J. Vet. Sci., 4(2), 129-135 (2011)
  40. Lobana, T.S., Cheema, H.S. and Sandhu, S.S., Chemistry of iron complexes IV: Spectroscopic, magnetic and other properties of complexes of iron iodide and iron(II) tetracarbonyl iodide, Polyhedron, 4(4), 717-721, (1985)
  41. Abdul Wajid, Naushad Zubair and Rahul B. Mohod, Synthetic, spectral, magnetic and antibacterial studies of schiff base transition metal complexes of bis-[(1-(5-chloro-2-hydroxyphenyl) ethanone)-diaminopropane]Journal of Chemical and Pharmaceutical Research, 5(4), 133-137 (2013)
  42. Rao N.S., Reddy M.G., Studies on the synthesis, characterisation and antimicrobial activity of new Co(II), Ni(II) and Zn(II) complexes of Schiff base derived from ninhydrin and glycine., Biol. Met. 3(1), 19-23 (1990)
  43. AS Aswar; NS Bhave, Electrical Properties of Some Polymeric Complexes, Asian J. Chem., 2(4), 363-367 (1990)