Skip to main content
SpringerLink
Log in

Macrocyclic [N5] transition metal complexes: synthesis, characterization and biological activities

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

Novel penta-azamacrocyclic 21-membered [N5] ligand [L] and its transition metal complexes with Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been isolated and characterized. The mode of bonding and overall geometry of the complexes have been inferred through IR, MS, UV–Vis, EPR, 1H NMR spectral studies, molar conductivity, magnetic, thermal and microanalyses, On the basis of above studies, an octahedral geometry has been proposed for all complexes except Pd(II) chloride complex which adopt square planar geometry. The in vitro antitumor activity of the synthesized ligand and some selected complexes against human breast and human hepatocarcinoma cell lines (MCF-7) and (HePG2), respectively has been studied. The results show that the tested compounds are potent antitumor agents. Also the ligand and some selected complexes have been tested for their inhibitory effect on the growth of bacteria: Streptococcus pyogenes as Gram-positive bacteria and Escherichia coli as Gram-negative bacteria. The activity data show that most of the tested compounds exhibit remarkable antibacterial activity against these organisms.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Scheme 2
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Prakash, N.B.: Synthesis and studies of tetraaza macrocyclic complexes of transition metal Ions. J. Phys. Appl. Chem. 1(2), 17–21 (2014)

    Google Scholar 

  2. EL-Gammal, O.A., Bekheit, M.M., El-Brashy, S.A.: Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand. Spectrochim. Acta A 137, 207–219 (2015)

    Article  CAS  Google Scholar 

  3. Chandra, S., Kumar, S.: Synthesis and spectral studies on mononuclear complexes of chromium(III) and manganese(II) with 12-membered tetradentate N2O2, N2S2 and N4 donor macrocyclic ligands. Transit. Met. Chem. 29, 269–275 (2004)

    Article  CAS  Google Scholar 

  4. Chandra, S., Gupta, R., Gupta, N., Bawa, S.S.: Biologically relevant macrocyclic complexes of copper spectral, magnetic, thermal and antibacterial approach. Transit. Met. Chem. 31, 147–151 (2006)

    Article  CAS  Google Scholar 

  5. Rani, S., Kumar, S., Chandra, S.: Spectroscopic and biological approach in the characterization of a novel 14-membered [N4] macrocyclic ligand and its Palladium(II), Platinum(II), Ruthenium(III) and Iridium(III) complexes. Spectrochim. Acta A 118, 244–250 (2014)

    Article  CAS  Google Scholar 

  6. Yernale, N.G., Mathada, M.B.H.: Synthesis, characterization, antimicrobial, DNA cleavage, and In Vitro cytotoxic studies of some Metal complexes of Schiff base ligand derived from thiazole and quinoline moiety. Bioinorg. Chem. 2014, 1–17 (2014)

    Article  Google Scholar 

  7. Shiekh, R.A., Rahman, I.A., Malik, M.A.: Synthesis, spectral, electrochemical and biological studies of nitrogen donor macrocyclic ligand and its transition metal complexes. Int. J. Electrochem. Sci. 7, 12829–12845 (2012)

    CAS  Google Scholar 

  8. Swamy, S.J., Pola, S.: Spectroscopic studies on Co(II), Ni(II), Cu(II) and Zn(II) complexes with N4-macrocylic ligands. Spectrochem. Acta A 70, 929–933 (2008)

    Article  CAS  Google Scholar 

  9. Ghamami, S., Lashgari, A., Ghahremani Gavineh Roudi, R.: Synthesis and characterization of two new hydrazide palladium complexes. Can. J. Basic Appl. Sci. 2(3), 76–80 (2014)

    Google Scholar 

  10. Chandra, S., Pipil, P.: Spectral studies of transition metal complexes with 25, 26 dioxo1,6,12,17,23,24 hexaazacyclohexacosa 1,5,12,16 tetraene macrocyclic ligand (L). J. Chem. Pharma. Res. 5(5), 99–104 (2013)

    CAS  Google Scholar 

  11. Singh, D.P., Kumar, K., Sharma, C.: Antimicrobial active macrocyclic complexes of Cr(III), Mn(III) and Fe(III) with their spectroscopic approach. Eur. J. Med. Chem. 44, 3299–3304 (2009)

    Article  CAS  Google Scholar 

  12. Wainwright, K.P.: Applications for polyaza macrocycles with nitrogen-attached pendant arms. Adv. Inorg. Chem. 52, 293–334 (2001)

    Article  CAS  Google Scholar 

  13. Swamy, S.J., Veerapratap, B., Nagaraju, D., Suresh, K., Someshwar, P.: Non-template synthesis of ‘N4’ di- and tetra-amide macrocyclic ligand with variable ring sizes. Tetrahedron 59, 10093–10096 (2003)

    Article  CAS  Google Scholar 

  14. Kedy, S., Almhna, N., Kandil, F.: Synthesis and characterization of new macrocyclic Schiff bases by the reaction of: 1,7-Bis (6-methoxy-2-formylphenyl)-1,7-dioxaheptane and their use in solvent extraction of metals. Arab. J. Chem. 8, 93–99 (2015)

    Article  CAS  Google Scholar 

  15. Fernandes, A.S., Cabral, M.F., Costa, J., Castro, M., Michael, R.D., Drew, G.B., Félix, V.: Two macrocyclic pentaaza compounds containing pyridine evaluated as novel chelating agents in copper(II) and nickel(II) overload. J. Inorg. Biochem. 105, 410–419 (2011)

    Article  CAS  Google Scholar 

  16. El-Boraey, H.A., Serag El-Din, A.A.: Transition metal complexes of a new 15-membered [N5] penta-azamacrocyclic ligand with their spectral and anticancer studies. Spectrochim. Acta A 132, 663–671 (2014)

    Article  CAS  Google Scholar 

  17. Chandra, S., Gupta, L.K.: Spectroscopic approach in characterization of chromium(III), manganese(II), iron(III) and copper(II) complexes with a nitrogen donor tetradentate, 14-membered azamacrocyclic ligand. Spectrochim. Acta A 61, 2139–2144 (2005)

    Article  Google Scholar 

  18. Timmons, J.C., Hubin, T.J.: Preparations and applications of synthetic linked azamacrocycle ligands and complexes. Coord. Chem. Rev. 254, 1661–1685 (2010)

    Article  CAS  Google Scholar 

  19. El-Boraey, H.A., Emam, S.M., Tolan, D.A., El-Nahas, A.M.: Structural studies and anticancer activity of a novel (N6O4) macrocyclic ligand and its Cu(II) complexes Spectrochim. Acta A 78, 360–370 (2011)

    Article  Google Scholar 

  20. El-Boraey, H.A.: Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic Characterization and anticancer activity. Spectrochim. Acta A 97, 255–262 (2012)

    Article  CAS  Google Scholar 

  21. Kang, D., Seo, J., Lee, S.Y., Lee, J.Y., Choi, K.S., Lee, S.S.: First dicadmium(II) complex of tripodal amide ligand with one edge-sharing monocapped octahedral geometry. Inorg. Chem. 10, 1425–1428 (2007)

    CAS  Google Scholar 

  22. Soliman, A., El-Medani, S., Ali, O.: Thermal study of chromium and molybdenum complexes with some nitrogen and nitrogen-oxygen donor ligands. J. Therm. Anal. Calorim. 83(2), 385–392 (2006)

    Article  CAS  Google Scholar 

  23. Ajlouni, A.M., Taha, Z.A., Al-Hassan, K.A., Abu Anzeh, A.M.: Synthesis, characterization, luminescence properties and antioxidant activity of Ln(III) complexes with a new aryl amide bridging ligand. J. Lumin. 132, 1357–1363 (2012)

    Article  CAS  Google Scholar 

  24. Tyagi, M., Chandra, S., Akhtar, J., Chand, D.: Macrocyclic Schiff base ligand and its complexes: inhibitory activity against plantpathogenic fungi. Spectrochim. Acta A 118, 1056–1061 (2014)

    Article  CAS  Google Scholar 

  25. Abou-Hussein, A.A., Linert, W.: Synthesis, spectroscopic studies and inhibitory activity against bacteria and fungi of acyclic and macrocyclic transition metal complexes containing a triamine coumarine Schiff base ligand. Spectrochim. Acta A 141, 223–232 (2015)

    Article  CAS  Google Scholar 

  26. Chandra, S., Qanungo, K., Sharma, S.K.: Synthesis, molecular modeling and spectroscopic characterization of nickel(II), copper(II), complexes of new 16-membered mixed-donor macrocyclic Schiff base ligand incorporating a pendant alcohol function. Spectrochim. Acta A 79, 1326–1330 (2011)

    Article  CAS  Google Scholar 

  27. Chandra, S., Sharma, A.K.: Nickel(II) and copper(II) complexes with Schiff base ligand 2,6-diacetylpyridine bis(carbohydrazone): synthesis and IR, mass,1H NMR, electronic and EPR spectral studies. Spectrochim. Acta A 72, 851–857 (2009)

    Article  Google Scholar 

  28. Chandra, S., Ruchi, S.: Synthesis, spectroscopic characterization, molecular modeling and antimicrobial activities of Mn(II), Co(II), Ni(II), Cu(II) complexes containing the tetradentate aza Schiff base ligand. Spectrochim. Acta A 103, 338–348 (2013)

    Article  CAS  Google Scholar 

  29. El-Gammal, H.A., El-Boraey, O.A.: New 15-membered tetraaza (N4) macrocyclic ligand and its transition metal complexes: Spectral, magnetic, thermal and anticancer activity. Spectrochim. Acta A 138, 553–562 (2015)

    Article  Google Scholar 

  30. Skehan, P., Storeng, R., Scudiero, D., Monks, A., Mahon, J.M., Vistica, D., Warren, J.T., Bokesch, H., Kenney, S., Boyd, M.R.: New colorimetric cytotoxicity assay for anticancer-drug screening. J. Natl. Cancer Inst. 82, 1107–1112 (1990)

    Article  CAS  Google Scholar 

  31. Wikler, M.A., Cockerill, F. R., Bush, K., Dudley, M.N., Eliopoulos, G.M., Hardy, D.J., Hecht, D.W., Ferraro, M.J., Swenson, J.M., Hindler, J.F., Patel, J.B., Powell, M. , Turnidge, J.D., Weinstein, M.P., Zimmer, B.L.: Method for dilution antimicrobial susceptibility tests for bacteria that grow aerobically, approved standard-eighth edition. M07-A8 CLSI: 940 West Valley Road,Suite 1400, Wayne, Pennsylvania 29(2), 1087–1898 (2009) USA; ISBN: 1-56238-689-1

  32. Bayoumi, H.A., Alaghaz, A.M.A., Aljahdali, M.S.: Cu(II), Ni(II), Co(II) and Cr(III) Complexes with N2O2-Chelating Schiff’s base ligand incorporating azo and sulfonamide moieties: spectroscopic, electrochemical behavior and thermal decomposition studies. Int. J. Electrochem Sci. 8, 9399–9413 (2013)

    CAS  Google Scholar 

  33. El-Asmy, A.A., Al-Abdeen, A.Z., El-Maaty, W.M., Mostafa, M.M.: Synthesis and spectroscopic studies of 2,5-hexanedione bis(isonicotinylhydrazone) and its first raw transition metal complexes. Spectrochim. Acta A 75, 1516–1522 (2010)

    Article  Google Scholar 

  34. Chandra, S., Gupta, L.K.: Mass, EPR, IR and electronic spectroscopic studies on newly synthesized macrocyclic ligand and its transition metal complexes. Spectrochim. Acta A 62, 1125–1130 (2005)

    Article  Google Scholar 

  35. Masoud, M.S., Khalil, E.A., Hindawy, A.M., Ali, A.E., Mohamed, E.F.: Spectroscopic studies on some azo compounds and their cobalt, copper and nickel complexes. Spectrochim. Acta A 60, 2807–2817 (2004)

    Article  Google Scholar 

  36. Mohamed, G.G., Ibrahim, N.A., Attia, H.A.E.: Spectroscopic studies on some azo compounds and their cobalt, copper and nickel complexes. Spectrochim. Acta A 72, 610–615 (2009)

    Article  Google Scholar 

  37. Jayaseelan, P., Prasad, S., Vedanayaki, S., Rajavel, R.: Synthesis, characterization, anti-microbial, DNA binding and cleavage studies of Schiff base metal complexes. Arab. J. Chem. (2011). doi:10.1016/j.arabjc.2011.07.029

    Google Scholar 

  38. Abd El-halim, H.F., Omar, M.M., Mohamed, G.G.: Synthesis, structural, thermal studies and biological activity of a tridentate Schiff base ligand and their transition metal complexes. Spectrochim. Acta A 78, 36–44 (2011)

    Article  Google Scholar 

  39. Venkatachalam, G., Ramesh, R.: Ruthenium(III) bis-bidentate Schiff base complexes mediated transfer hydrogenation of imines. Inorg. Chem. Commun. 9, 703–707 (2006)

    Article  CAS  Google Scholar 

  40. Geeta, B., Shravankumar, K., Muralidhar Reddy, P., Ravikrishna, E., Sarangapani, M., Krishna Reddya, K., Ravinder, V.: Binuclear cobalt(II), nickel(II), copper(II) and palladium(II) complexes of a new Schiff-base as ligand: Synthesis, structural characterization, and antibacterial activity. Spectrochim. Acta A 77, 911–915 (2010)

    Article  CAS  Google Scholar 

  41. Gurumoorthy, P., Ravichandran, J., Karthikeyan, N., Palani, P., Kalilur Rahiman, A.: Template synthesis of polyaza macrocyclic copper(II) and nickel(II) complexes: spectral characterization and antimicrobial studies. Bull. Korean Chem. Soc. 33(7), 2279–2286 (2012)

    Article  CAS  Google Scholar 

  42. Kavitha, N., Anantha Lakshmi, P.V.: Synthesis, characterization and thermogravimetric analysis of Co(II), Ni(II), Cu(II) and Zn(II) complexes supported by ONNO tetradentate Schiff base ligand derived from hydrazino benzoxazine. J. Saudi Chem. Soc. (2015). doi:10.1016/j.jscs.2015.01.003

    Google Scholar 

  43. Kivelson, D., Neiman, R.: ESR line shapes in glasses of copper complexes. J. Chem. Phys. 35, 149–155 (1961)

    Article  CAS  Google Scholar 

  44. Hathaway, B.J., Billing, D.E.: The electronic properties and stereochemistry of mononuclear complexes of the copper(II) ion. Coord. Chem. Rev. 5, 143–207 (1970)

    Article  CAS  Google Scholar 

  45. Arish, D., Sivasankaran Nair, M.: Synthesis, characterization and biological studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with pyrral-L-histidinate. Arab. J. Chem. 5, 179–186 (2012)

    Article  CAS  Google Scholar 

  46. Osman, A.H.: Synthesis and characterization of cobalt(II) and nickel(II) complexes of some Schiff bases derived from 3-hydrazino-6-methyl[1,2,4] triazin-5(4H)one. Transit. Metal Chem. 31, 35–41 (2006)

    Article  CAS  Google Scholar 

  47. El-Boraey, H.A.: Structural and thermal studies of some aroylhydrazone Schiff’s base-transition metal complexes. J. Therm. Anal. Calorim. 81, 339–346 (2005)

    Article  CAS  Google Scholar 

  48. Emam, S.M., El Sayed, I.E., Nassar, N.: Transition metal complexes of neocryptolepine analogues. Part I: synthesis, spectroscopic characterization, and in vitro anticancer activity of copper(II) complexes. Spectrochim. Acta A 138, 942–953 (2015)

    Article  CAS  Google Scholar 

  49. Coats, A.W., Redfern, J.P.: Kinetic parameters from thermogravimetric data. Nature 201, 68–122 (1964)

    Article  CAS  Google Scholar 

  50. Horowitz, H.H., Metzger, G.: A New analysis of thermogravimetric traces. J. Anal. Chem. 35, 1464–1468 (1963)

    Article  CAS  Google Scholar 

  51. Sivakumar, P., Parthiban, K.S., Sivakumar, P., Vinoba, M., Renganathan, S.: Optimization of extraction process and kinetics of sterculia foetida Seed oil and its process augmentation for biodiesel production. Ind. Eng. Chem. Res. 52, 8992–8998 (2012)

    Article  Google Scholar 

  52. Borsato, D., Galvan, D., Pereira, J.L., Orives, J.R., Angilelli, K.G., Coppo, R.L.: Kinetic and thermodynamic parameters of biodiesel oxidation with synthetic antioxidants: simplex centroid mixture design. J. Braz. Chem. Soc. 25(11), 1984–1992 (2014)

    CAS  Google Scholar 

  53. Shier, W.T.: Mammalian cell culture on $5 a day: a laboratory manual of low cost methods. University of the Philippines, Los Banos (1991)

    Google Scholar 

  54. Chandra, S., Gupta, L.K.: Modern spectroscopic techniques in the characterization of Schiff base macrocyclic ligand and its complexes with transition. Spectrochim. Acta A 62, 307–312 (2005)

    Article  Google Scholar 

  55. EL-Asmy, A.A., Rakha, T.H., Abdel-Rhman, M.H., Hassanien, M.M., Al-Mola, A.S.: Synthesis, spectral, thermal and biological studies on N(-)(2,4-dinitro-phenyl)-2-mercaptoacetohydrazide and its metal complexes. Spctrochim. Acta A 136, 1718–1727 (2015)

    Article  CAS  Google Scholar 

  56. Gaber, M., El-Wakiel, N.A., El-Ghamry, H., Fathalla, S.K.: Ni(II), Pd(II) and Pt(II) complexes of (1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol. Structural, spectroscopic, biological, cytotoxicity, antioxidant and DNA binding. Spectrochim. Acta A 139, 396–404 (2015)

    Article  CAS  Google Scholar 

  57. Zafar, H., Kareem, A., Sherwani, A., Mohammad, O., Ansari, M.A., Khan, H.M., Khan, T.A.: Synthesis and characterization of Schiff base octaazamacrocyclic complexes and their biological studies. J. Photochem. Photobiol., B 142, 8–19 (2015)

    Article  CAS  Google Scholar 

  58. Kavitha, P., Rama Chary, M., Singavarapu, B.V.V.A., Laxma Reddy, K.: Synthesis, characterization, biological activity and DNA cleavage studies of tridentate Schiff bases and their Co(II) complexes. J. Saudi Chem. Soc. 20, 69–80 (2016)

    Article  Google Scholar 

  59. Xiao-Yang, Q., Su-Zhi, L., An-Ran, S., Qian-Qian, L., Bin, Z.: Synthesis, crystal structure and cytotoxic activity of a zinc(II) complex of the Schiff base derived from S-benzyldithiocarbazate. Chin. J. Struct. Chem. 31(4), 555–561 (2012)

    Google Scholar 

  60. Tweedy, B.G.: Plant extracts with metal ions as potential antimicrobial agents. Phytopathology 55, 910–914 (1964)

    Google Scholar 

  61. Sonmez, M., Metin, C., Berber, I.: Synthesis, spectroscopic and biological studies on the new symmetric Schiff base derived from 2,6-diformyl-4-methylphenol with N-aminopyrimidine Eur. J. Med. Chem. 45, 1935–1940 (2010)

    Article  Google Scholar 

  62. Singh, D.P., Grover, V., Rathi, P., Jainb, K.: Trivalent transition metal complexes derived from carbohydrazide and dimedone. Arab. J. Chem. (2013). doi:10.1016/j.arabjc.2013.07.004

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Menoufia University, Shebin El-Kom, Egypt

    Hanaa A. El-Boraey, Mogda A. El-Salamony & Abla A. Hathout

Authors
  1. Hanaa A. El-Boraey
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mogda A. El-Salamony
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Abla A. Hathout
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hanaa A. El-Boraey.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 30 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

El-Boraey, H.A., El-Salamony, M.A. & Hathout, A.A. Macrocyclic [N5] transition metal complexes: synthesis, characterization and biological activities. J Incl Phenom Macrocycl Chem 86, 153–166 (2016). https://doi.org/10.1007/s10847-016-0649-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-016-0649-5

Keywords

Search

Navigation