Skip to main content
SpringerLink
Log in

Copper(II) complexes with semicarbazones: synthesis, characterization and noncovalent interactions in their crystal structures

  • Regular Article
  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

The present work reports the synthesis and structural elucidation of six novel copper(II) complexes with 2-acetylpyridine semicarbazone (HL1) and 2-acetylpyridine N(4)-phenyl semicarbazone (HL2). In all compounds, the semicarbazone ligands were find tridentate with NNO-donor atoms. The single crystal X-ray diffraction analysis showed the influences of the different copper salt starting reagent in the crystal structures. A packing architectures analysis has been undertaken to delineate the role of relevant noncovalent interactions. The π···π stacking interactions and hydrogen bonds were analyzed using the Hirshfeld surface and fingerprint plots. In addition, the compounds were also characterized by physicochemical and spectroscopic methods.

Graphic abstract

A new ligand and six copper(II) complexes of semicarbazone derivatives have been synthesized and their crystal structures have been studied. Spectroscopy experiments and Hirshfeld Surface were analyzed.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9

Similar content being viewed by others

References

  1. Pal R, Kumar V, Gupta A and Beniwal V 2014 Synthesis, Characterization and DNA Photocleavage Study of a Novel Dehydroacetic Acid Based Hydrazone Schiff’s Base and Its Metal Complexes Med. Chem. Res. 23 3327

    Article  CAS  Google Scholar 

  2. Padhyé S and Kauffman G B 1985 Transition Metal Complexes of Semicarbazones and Thiosemicarbazones Coord. Chem. Rev. 63 127

    Article  Google Scholar 

  3. Abu-Dief A M and Mohamed I M A 2015 A Review on Versatile Applications of Transition Metal Complexes Incorporating Schiff Bases Beni-Suef Univ. J. Basic Appl. Sci. 4 119

    Article  Google Scholar 

  4. Casas J S, García-Tasende M S and Sordo J 2000 Main Group Metal Complexes of Semicarbazones and Thiosemicarbazones. A Structural Review Coord. Chem. Rev. 209 197

  5. Beraldo H 2004 Semicarbazonas e Tiossemicarbazonas: O Amplo Perfil Farmacológico e Usos Clínicos Quim. Nova. 27 461

    Article  CAS  Google Scholar 

  6. Beraldo H and Gambinob D 2004 The Wide Pharmacological Versatility of Semicarbazones, Thiosemicarbazones and Their Metal Complexes Mini-Rev. Med. Chem. 4 31

    Article  CAS  Google Scholar 

  7. More M S, Joshi P G, Mishra Y K and Khanna P K 2019 Metal Complexes Driven from Schiff Bases and Semicarbazones for Biomedical and Allied Applications: A Review Mater. Today Chem. 14 100195

    Article  CAS  Google Scholar 

  8. Salem N M H, Rashad A R, El Sayed L, Foro S, Haase W and Iskander M F 2015 Synthesis, Characterization, Molecular Structure and Supramolecular Architectures of Some Copper(II) Complexes Derived from Salicylaldehyde Semicarbazone Inorg. Chim. Acta 432 231

    Article  CAS  Google Scholar 

  9. Shaabani B, Khandar A A, Mahmoudi F, Maestro M A, Balula S S and Cunha-Silva L 2013 Novel Binuclear Cu(II) Complexes Combining a Semicarbazone Schiff Base with Distinct Bridging Ligands: Structure and Antimicrobial Activity Polyhedron 57 118

    Article  CAS  Google Scholar 

  10. Abdolhi N, Aghaei M, Soltani A, Mighani H, Ghaemi E A, Javan M, Khalaji A, Sharbati S, Shafipour M and Balakheyli H 2019 Synthesis and Antibacterial Activities of Novel Hg(II) and Zn(II) Complexes of Bis(Thiosemicarbazone) Acenaphthenequinone Loaded to MWCNTs J. Struct. Chem. 60 845

    Article  CAS  Google Scholar 

  11. Muleta F, Alansi T and Eswaramoorthy R 2019 A Review on Synthesis, Characterization Methods and Biological Activities of Semicarbazone, Thiosemicarbazone and Their Transition Metal Complexes J. Nat. Sci. Res. 9 33

    Google Scholar 

  12. Cavalcanti de Queiroz A, Alves M A, Barreiro E J, Lima L M and Alexandre-Moreira M S 2019 Semicarbazone Derivatives as Promising Therapeutic Alternatives in Leishmaniasis Exp. Parasitol. 201 57

    Article  CAS  Google Scholar 

  13. Todorović T R, Vukašinović J, Portalone G, Suleiman S, Gligorijević N, Bjelogrlić S, Jovanović K, Radulović S, Anđelković K, Cassar A, Filipović N R and Schembri-Wismayer P 2017 (Chalcogen)Semicarbazones and Their Cobalt Complexes Differentiate HL-60 Myeloid Leukaemia Cells and Are Cytotoxic towards Tumor Cell Lines MedChemComm 8 103

    Article  Google Scholar 

  14. Machado I, Fernández S, Becco L, Garat B, Gancheff J S, Rey A and Gambino D 2014 New Fac-Tricarbonyl Rhenium(I) Semicarbazone Complexes: Synthesis, Characterization, and Biological Evaluation J. Coord. Chem. 67 1835

    Article  CAS  Google Scholar 

  15. Santini C, Pellei M, Gandin V, Porchia M, Tisato F and Marzano C 2014 Advances in Copper Complexes as Anticancer Agents Chem. Rev. 114 815

    Article  CAS  Google Scholar 

  16. Qi J, Liang S, Gou Y, Zhang Z, Zhou Z, Yang F and Liang H 2015 Synthesis of Four Binuclear Copper(II) Complexes: Structure, Anticancer Properties and Anticancer Mechanism Eur. J. Med. Chem. 96 360

    Article  CAS  Google Scholar 

  17. Venkatachalam T K, Bernhardt P V, Noble C J, Fletcher N, Pierens G K, Thurecht K J and Reutens D C 2016 Synthesis, Characterization and Biological Activities of Semicarbazones and Their Copper Complexes J. Inorg. Biochem. 162 295

    Article  CAS  Google Scholar 

  18. Marzano C, Pellei M and Santini F T 2009. Copper Complexes as Anticancer Agents Anticancer Agents Med. Chem. 9 185

  19. Murphy B and Hathaway B 2003 The Stereochemistry of the Copper(II) Ion in the Solid-State—Some Recent Perspectives Linking the Jahn–Teller Effect, Vibronic Coupling, Structure Correlation Analysis, Structural Pathways and Comparative X-Ray Crystallography Coord. Chem. Rev. 243 237

    Article  CAS  Google Scholar 

  20. Duncan C and White A R 2012 Copper Complexes as Therapeutic Agents Metallomics 4 127

    CAS  PubMed  Google Scholar 

  21. Tiago F S, Santiago P H O, Amaral M M P, Martins J B L and Gatto C C 2016 New Cu(II) Complex with Acetylpyridine Benzoyl Hydrazone: Experimental and Theoretical Analysis J. Coord. Chem. 69 330

    Article  CAS  Google Scholar 

  22. Gatto C C, Miguel P M, Almeida C M, Santiago P H O, Paier C R K and Pessoa C 2017 A Copper(II) Complex of a Semicarbazone: Crystal Structure, Spectroscopic Analysis and Cytotoxicity against Human Cancer Cell Lines Transit. Met. Chem. 42 503

    Article  CAS  Google Scholar 

  23. Pérez-Rebolledo A, Piro O, Castellano E E, Teixeira L R, Batista A A and Beraldo H 2006 Metal Complexes of 2-Benzoylpyridine Semicarbazone: Spectral, Electrochemical and Structural Studies J. Mol. Struct. 794 18

    Article  Google Scholar 

  24. Gatto C C, Lima I J and Chagas M A S 2017 Supramolecular Architectures and Crystal Structures of Gold(III) Compounds with Semicarbazones Supramol. Chem. 29 296

    Article  CAS  Google Scholar 

  25. Sheldrick G M 1997 SADABS, Program for Empirical Absorption Correction of Area Detector Data: University of Göttingen: Germany. SHELXS-97. Program for Crystal Structure Resolution. University of Göttingen, Göttingen: Germany 1997

  26. Sheldrick G M 1997 SHELXS-97. Program for Crystal Structure Resolution.University of Göttingen, Göttingen, Germany. Program for Empirical Absorption Correction of Area Detector Data: University of Göttingen: Germany 1997

  27. Sheldrick G M 2015 Crystal Structure Refinement with SHELXL Acta Crystallogr. Sect. C Struct. Chem. 71 3

    Article  Google Scholar 

  28. Farrugia L J 1997 Programa de Representação Das Elipsóides Da Estrutura Cristalina. Appll. Crystalogr. 30 565

    Article  CAS  Google Scholar 

  29. Farrugia L J 2012 WinGX and ORTEP for Windows: An Update J. Appl. Crystallogr. 45 849

    Article  CAS  Google Scholar 

  30. Spackman M A and McKinnon J J 2002 Fingerprinting Intermolecular Interactions in Molecular Crystals CrystEngComm 4 378

    Article  CAS  Google Scholar 

  31. Spackman M A and Jayatilaka D 2009 Hirshfeld Surface Analysis CrystEngComm 11 19

    Article  CAS  Google Scholar 

  32. Turner M J, McKinnor J J, Wolff S K, et al 2017 CrystalExplorer17 2017

  33. Siji V L, Kumar M R S, Suma S and Kurup M R P 2010 Synthesis, Characterization and Physiochemical Information, along with Antimicrobial Studies of Some Metal Complexes Derived from an ON Donor Semicarbazone Ligand Spectrochim. Acta Part A 76 22

  34. Gil-García R, Fraile R, Donnadieu B, Madariaga G, Januskaitis V, Rovira J, González L, Borrás J, Arnáiz F J and García-Tojal J 2013 Desulfurization Processes of Thiosemicarbazonecopper(Ii) Derivatives in Acidic and Basic Aqueous Media New J. Chem. 37 3568

    Article  Google Scholar 

  35. Gil-García R, Ugalde M, Busto N, Lozano H J, Leal J M, Pérez B, Madariaga G, Insausti M, Lezama L, Sanz R, Gómez-Sainz L M, García B and García-Tojal J 2016 Selectivity of a Thiosemicarbazonatocopper(Ii) Complex towards Duplex RNA. Relevant Noncovalent Interactions Both in Solid State and Solution Dalton Trans. 45 18704

  36. Kunnath R J, Sithambaresan M, Aravindakshan A A, Natarajan A, Kurup M R P 2016. The Ligating Versatility of Pseudohalides like Thiocyanate and Cyanate in Copper(II) Complexes of 2-Benzoylpyridine Semicarbazone: Monomer, Dimer and Polymer Polyhedron 113 73

    Article  CAS  Google Scholar 

  37. Gil-García R, Gómez-Saiz P, Díez-Gómez V, Donnadieu B, Insausti M, Lezama L and García-Tojal J 2013 Polymorphism and Magnetic Properties in Thiosemicarbazonecopper(II)-Sulfate Compounds Polyhedron 54 243

    Article  Google Scholar 

  38. Garbelini E R, Hörner M, Boneberger Behm M, Evans D J and Nunes F S 2008 Synthesis and Crystal Structures of Bis(1-{(E)-2-Pyridinylmethylidene}-Semicarbazone)Iron(II) and -Copper(II) Diperchlorate Monohydrates Z. Anorg. Allg. Chemie. 634 1801

    Article  CAS  Google Scholar 

  39. Addison A W, Rao T N, Reedijk J, van Rijn J and Verschoor G C 1984 Synthesis, Structure, and Spectroscopic Properties of Copper(II) Compounds Containing Nitrogen-Sulphur Donor Ligands; the Crystal and Molecular Structure of Aqua[1,7-Bis(N-Methylbenzimidazol-2[Prime or Minute]-Yl)-2,6-Dithiaheptane]Copper(II) Perchlorate J. Chem. Soc. Dalton Trans. 7 1349

    Article  Google Scholar 

  40. Senthil Raja D, Bhuvanesh N S P and Natarajan K 2011 Effect of N(4)-Phenyl Substitution in 2-Oxo-1,2-Dihydroquinoline-3-Carbaldehyde Semicarbazones on the Structure, DNA/Protein Interaction, and Antioxidative and Cytotoxic Activity of Cu(II) Complexes Inorg. Chem. 50 12852

    Article  Google Scholar 

  41. Layana S R, Saritha, S R, Anitha L, Sithambaresan M, Sudarsanakumar M R and Suma S 2018 Synthesis, Spectral Characterization and Structural Studies of a Novel O, N, O Donor Semicarbazone and Its Binuclear Copper Complex with Hydrogen Bond Stabilized Lattice J. Mol. Struct. 1157 579

    Article  CAS  Google Scholar 

  42. Lee W Y, Lee P P F, Yan Y K and Lau M 2010 Cytotoxic Copper(Ii) Salicylaldehyde Semicarbazone Complexes: Mode of Action and Proteomic Analysis Metallomics 2 694

    Article  CAS  Google Scholar 

  43. Todorović T, Grubišić S, Pregelj M, Jagodič M, Misirlić-Denčić S, Dulović M, Marković I, Klisurić O, Malešević A, Mitić D, Anđelković K and Filipović N 2015 Structural, Magnetic, DFT, and Biological Studies of Mononuclear and Dinuclear CuII Complexes with Bidentate N-Heteroaromatic Schiff Base Ligands Eur. J. Inorg. Chem. 2015 3921

    Article  Google Scholar 

  44. Patel R N, Shukla K K, Singh A, Choudhary M, Chauhan U K and Dwivedi S 2009 Copper(II) Complexes as Superoxide Dismutase Mimics: Synthesis, Characterization, Crystal Structure and Bioactivity of Copper(II) Complexes Inorg. Chim. Acta 362 4891

    Article  CAS  Google Scholar 

  45. Chumakov Y M, Tsapkov V I, Antosyak B Y, Bairac N N, Simonov Y A, Bocelli G, Pahontu E and Gulea A P 2009 Crystal Structures of Copper(II) Nitrate, Copper(II) Chloride, and Copper(II) Perchlorate Complexes with 2-Formylpyridine Semicarbazone Crystallogr. Rep. 54 455

    Article  CAS  Google Scholar 

  46. Leovac V M, Novaković S B, Bogdanović G A, Joksović M D, Mészáros Szécsényi K and Češljević V I 2007 Transition Metal Complexes with Thiosemicarbazide-Based Ligands. Part LVI: Nickel(II) Complex with 1,3-Diphenylpyrazole-4-Carboxaldehyde Thiosemicarbazone and Unusually Deformed Coordination Geometry Polyhedron 26 3783

Download references

Acknowledgements

Financial support received from FAPDF (Process No. 0193.001545/2017). The authors wish to thank for Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001 for fellowships, UnB, FINEP/CTINFRA and FAPDF.

Author information

Authors and Affiliations

  1. Laboratory of Inorganic Synthesis and Crystallography, University of Brasilia (IQ-UnB), Campus Universitário Darcy Ribeiro, CEP 70904970, Brasília, DF, Brazil

    Claudia C Gatto, Francielle C Lima & Patrícia M Miguel

Authors
  1. Claudia C Gatto
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Francielle C Lima
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Patrícia M Miguel
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Claudia C Gatto.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gatto, C.C., Lima, F.C. & Miguel, P.M. Copper(II) complexes with semicarbazones: synthesis, characterization and noncovalent interactions in their crystal structures. J Chem Sci 132, 146 (2020). https://doi.org/10.1007/s12039-020-01847-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s12039-020-01847-5

Keywords

Search

Navigation