Structural investigation of group 10 metal complexes with thiosemicarbazone: crystal structure, mass spectrometry, Hirshfeld surface and in vitro antitumor activity


The current work reports the synthesis and structural investigation of three novel complexes with 2-acetyl-pyridine-N(4)-phenylthiosemicarbazone (HL1), [Ni(L1)Cl] (1), [Pd(L1)Cl] (2) and [Pt(L1)PPh3]Cl•2MeOH (3). The compounds were structurally characterized by means of single-crystal X-ray crystallography and spectroscopic techniques. All three complexes exhibit tetracoordinated metal centers in a square planar fashion with the thiosemicarbazone acting as a tridentate NNS-donor atoms. Intermolecular hydrogen bonds and π···π stacking interactions, building supramolecular assemblies in the complexes, were analyzed using the Hirshfeld surface. Mass spectrometry data showed the presence in solution of the characteristic fragmentation with the [M+H]+ molecular ion for all complexes. The thermochemical data, estimated by computational chemistry, allowed elucidate the relative intensity of the peaks present in the mass spectrum of the compounds investigated. The antitumor activity and selectivity of the free thiosemicarbazone ligand and their M(II) complexes (M = Ni, Pd, Pt) were evaluated against MCF-7, PBMC, and healthy cells. All compounds studied showed the death of cancer cells observing a great selectivity for the Ni(II) complex.

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This study is financially supported by the FAPDF (process number 0193.001545/2017), UnB, FINEP/CTINFRA and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001. RLTP and RPO are financially supported by the São Paulo Research Foundation (FAPESP), grants 2011/07623–8 and 2017/24856–2. RLTP is supported by the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (313648/2018–2) through a research fellowship.

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The manuscript was written with contributions from all authors. All authors have approved the final version of the manuscript.

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Correspondence to Claudia C. Gatto.

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Crystallographic data for the structures in this work have been deposited to the Cambridge Crystallographic Data Centre, CCDC 1893403-1893404. Copies of the available material can be obtained free of charge by application to the Director, CCDC, 12 Union Road, Cambridge CH2 1EZ, UK (Fax: +44 1223 336033; E-mail: or Crystallographic data are in CIF files.


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Almeida, C.M., de Carvalho, J.G.M., Fujimori, M. et al. Structural investigation of group 10 metal complexes with thiosemicarbazone: crystal structure, mass spectrometry, Hirshfeld surface and in vitro antitumor activity. Struct Chem (2020).

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  • Metal complexes
  • Thiosemicarbazone
  • Crystal structures
  • Cytotoxicity
  • Human cancer cell