Journal of Thermal Analysis and Calorimetry

, Volume 136, Issue 4, pp 1467–1480 | Cite as

The mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with coumarilic acid/1,10-phenanthroline

Synthesis, crystal characterization and biological applications
  • Özge Dağlı
  • Dursun Ali KöseEmail author
  • Okan İçten
  • Gülçin Alp Avcı
  • Onur Şahin


The coumarilate (coum) and 1,10-phenanthroline (phen) mixed ligand complexes of Co(II) (1), Ni(II) (2) Cu(II) (3) and Zn(II) (4) were synthesized and structural characterizations were performed by using elemental analysis, magnetic susceptibility, solid-state UV–Vis, FTIR spectra, thermoanalytical TG-DTG/DTA and single-crystal X-ray diffraction methods. The Co(II) and Ni(II) complexes are salt-type compounds, and they have two moles phen ligands bound as bidentate, two moles aqua ligands in coordination sphere and two moles anionic coum ligand outside of the coordination unit as the counter-ion of the molecular structure. At the same time, the Co(II) and Ni(II) complexes have five moles of aqua ligands as hydrated water outside of the molecules. It was obtained that Cu(II) and Zn(II) complex structures contain one mole of phen ligand, two moles coordinated (coum) ligand and a one-mole aqua ligand, and the molecules (Cu(II) and Zn(II)) have fivefold structure and obey square pyramidal geometry. Thermal decomposition of each complex started with dehydration (the first removal is the dehydration of complex Co(II) and Ni(II) as removal of hydrate–aqua molecules), and then, the decomposition of organic parts was observed. The thermal dehydration of the complexes takes place in one (Cu(II) and Zn(II)) or two (Co(II) and Co(II)) steps. The decomposition mechanism, thermal decomposition steps and thermal stability of the investigated complexes provide useful data for the interpretation of their structures. The final decomposition products were found to be metal oxides. Some biological applications (antifungal/antibacterial) were performed using structurally characterized compounds.


Mixed ligand complexes Biological application Coumarilate 1,10-Phenanthroline Crystal structure Thermal properties 



This study was financially supported by Sinop University in Turkey (Project No. SÜB-1901.14-01) and Hitit University Scientific Research Unit (Project No: FEF19004.15.005). The authors acknowledge Scientific and Technological Research Application and Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST diffractometer.


  1. 1.
    Hattori M, Hada S, Watahiki A, Ihara H, Shu YZ, Kakiuchi N, Mizuno T, Namba T. Studies on dental caries prevention by traditional medicines. X. Antibacterial action of phenolic components from mace against Streptococcus mutans. Chem Pharm Bull. 1986;34(9):3885–93.CrossRefGoogle Scholar
  2. 2.
    Erber S, Ringshandl R, von Angerer E. 2-Phenylbenzo[b]furans: relationship between structure, estrogen receptor affinity and cytostatic activity against mammary tumor cells. Anticancer Drug Des. 1991;6(5):417–26.Google Scholar
  3. 3.
    Cui B, Chai H, Reutrakul V, Farnsworth NR, Cordell GA, Pezzutto JM, Kinghorn AD. Novel cytotoxic 1H-cyclopenta[β]benzofuran lignans from Aglaia elliptica. Tetrahedron. 1997;53:17625–32.CrossRefGoogle Scholar
  4. 4.
    Lee SK, Cui B, Mehta RR, Kinghorn AD, Pezzutto JM. Cytostatic mechanism and antitumor potential of novel 1H-cyclopenta[b]benzofuran lignans isolated from Aglaia elliptica. Chem Biol Interact. 1998;115(3):215–28.CrossRefGoogle Scholar
  5. 5.
    Kodama I, Kamiya K, Toyama J. Amiodarone: ionic and cellular mechanisms of action of the most promising class III agent. Am J Cardiol. 1999;84(9A):20R–8R.CrossRefGoogle Scholar
  6. 6.
    Hayakawa I, Shioya R, Agatsuma T, Furukawa H, Naruto S, Sugano Y. 4-Hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester derivatives as potent anti-tumor agents. Bioorg Med Chem Lett. 2004;14(2):455–8.CrossRefGoogle Scholar
  7. 7.
    Hwang BY, Su BN, Chai H, Mi Q, Kardono LB, Afriastini JJ, Riswan S, Santarsiero BD, Mesecar AD, Wild R, Fairchild CR, Vite GD, Rose WC, Farnsworth NR, Cordell GA, Pezzutto JM, Swanson SM, Kinghorn AD. Silvestrol and episilvestrol, potential anticancer rocaglate derivatives from Aglaia silvestris. J Org Chem. 2004;69(10):3350–8.CrossRefGoogle Scholar
  8. 8.
    Masche UP, Rentsch KM, von Felten A, Meier PJ, Fattinger KE. No clinically relevant effect of Iornoxicam intake on acenocoumarol pharmacokinetics and pharmacodynamics. Eur J Clin Pharmacol. 1999;54(11):865–8.CrossRefGoogle Scholar
  9. 9.
    Karaliota A, Kretsi O, Tzougraki C. Synthesis and characterization of a binuclear coumarin-3-carboxylate copper(II) complex. J Inorg Biochem. 2001;84(1–2):33–7.CrossRefGoogle Scholar
  10. 10.
    Berk N. Synthesis of benzofuran derivative dithiocarbamate esters. MSc thesis, Adıyaman University; 2013.Google Scholar
  11. 11.
    Kleiner HE, Vulimiri SV, Miller L, Johnson WH, Whitman CP, DiGiovanni J. Oral administration of naturally occurring coumarins leads to altered phase I and II enzyme activities and reduced DNA adduct formation by polycyclic aromatic hydrocarbons in various tissues of SENCAR mice. Carcinogenesis. 2001;22(1):73–82.CrossRefGoogle Scholar
  12. 12.
    Tanew A, Ortel B, Rappersberger K, Honigsmann H. 5-Methoxypsoralen (Bergapten) for photochemotherapy. Bioavailability, phototoxicity, and clinical efficacy in psoriasis of a new drug preparation. J Am Acad Dermatol. 1988;18(2):333–8.CrossRefGoogle Scholar
  13. 13.
    Gill J, Heel RC, Fitton A. Amiodarone. An overview of its pharmacological properties, and review of its therapeutic use in cardiac arrhythmias. Drugs. 1992;43(1):69–110.CrossRefGoogle Scholar
  14. 14.
    Köse DA, Öztürk B, Şahin O, Büyükgüngör O. Mixed ligand complexes of coumarilic acid/nicotinamide with transition metal complexes: synthesis and structural investigation. J Therm Anal Calorim. 2014;115(2):1515–24.CrossRefGoogle Scholar
  15. 15.
    Dağlı Ö, Köse DA, Şahin O, Şahin ZS. The synthesis and structural characterization of transition metal coordination complexes of coumarilic acid. J Therm Anal Calorim. 2017;128(3):1373–83.CrossRefGoogle Scholar
  16. 16.
    Mirochnik AG, Bukvetskii BV, Zhikhareva PA, Karasev VE. Crystal structure and luminescence of the [Eu(Phen)(2)(NO3)(3)] complex. The role of the ion-coactivator. Russ J Coord Chem. 2001;27(6):443–8.CrossRefGoogle Scholar
  17. 17.
    de Farias RF, Airoldi C. Some structural features of MoO3-1,10-phenanthroline intercalation compounds. J Phys Chem Solids. 2003;64(11):2199–204.CrossRefGoogle Scholar
  18. 18.
    Leontie L, Druta I, Danac R, Rusu GI. On the electronic transport properties of pyrrolo[1,2-a][1, 10]phenanthroline derivatives in thin films. Synth Met. 2005;155(1):138–45.CrossRefGoogle Scholar
  19. 19.
    Mudasir N, Inoue H. Iron(II) and nickel(II) mixed-ligand complexes containing 1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline. Transit Met Chem. 1999;24(2):210–7.CrossRefGoogle Scholar
  20. 20.
    Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds. Toronto: Wiley; 1997.Google Scholar
  21. 21.
    Köse DA, Gökçe G, Gökçe S, Uzun İ. Bis(N,N-diethylnicotinamide) p-chlorobenzoate complexes of Ni(II), Zn(II) and Cd(II). J Therm Anal Calorim. 2009;95(1):247–51.CrossRefGoogle Scholar
  22. 22.
    Sheldrick GM. A short history of SHELX. Acta Cryst. 2008;A64(1):112–22.CrossRefGoogle Scholar
  23. 23.
    Farrugia LJ. WinGX suite for small-molecule single-crystal crystallography. J Appl Cryst. 1999;32:837–8.CrossRefGoogle Scholar
  24. 24.
    Mercury. version 3.0; CCDC.
  25. 25.
    Spek AL. PLATON—a multipurpose crystallographic tool. Utrecht: Utrecht University; 2005.Google Scholar
  26. 26.
    Köse DA, Şahin O, Büyükgüngör O. Synthesis, spectral, thermal, magnetic and structural study of diaquabis(m-hydroxybenzoato-κO)bis(N,N-diethylnicotinamide-κN)cobalt(II). Eur Chem Bull. 2012;1(6):196–201.Google Scholar
  27. 27.
    Köse DA, Ay AN, Şahin O, Büyükgüngör O. A mononuclear, mixed (salicylato) (nicotinamide) complex of Zn(II) with penta- and hexa-coordination sites: a novel framework structure. J Iran Chem Soc. 2012;9(4):591–7.CrossRefGoogle Scholar
  28. 28.
    Köse DA, Necefoğlu H, Şahin O, Büyükgüngör O. Synthesis, structural, spectroscopic characterization, and structural comparison of 3-hydroxybenzoate and nicotinamide/N,N-diethylnicotinamide mixed ligand complexes with Zn(II). J Therm Anal Calorim. 2012;110(3):1233–41.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • Özge Dağlı
    • 1
  • Dursun Ali Köse
    • 1
    Email author
  • Okan İçten
    • 2
  • Gülçin Alp Avcı
    • 3
  • Onur Şahin
    • 4
  1. 1.Department of ChemistryHitit UniversityÇorumTurkey
  2. 2.Department of ChemistryHacettepe UniversityAnkaraTurkey
  3. 3.Department of Molecular Biology and GeneticsHitit UniversityCorumTurkey
  4. 4.Scientific and Technological Research Application Centre, Sinop UniversitySinopTurkey

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