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Synthesis and characterization of copper, nickel, cobalt, zinc complexes with 4-nitro-3-pyrazolecarboxylic acid ligand


In the continuation of our systematic research of pyrazole coordination compounds, complexes of Cu(II), Ni(II), Co(II) and Zn(II) with 4-nitro-3-pyrazolecarboxylic acid ligand (L) were synthesized in the reaction of warm ethanolic solutions of the ligand and CuCl2·2H2O, Ni(CH3COO)2, CoCl2·6H2O and Zn(CH3COO)2, mixed in the metal-to-ligand ratio of 1:2. As the compounds could not be obtained in the form suitable for single-crystal structure analysis, their bis(ligand) structures, ML2 (M = CuII, NiII, CoII and ZnII) were proposed on the basis of elemental analysis, IR spectrometry, conductometric and TG–MS measurements. The low conductivity of the compounds additionally supports the deprotonation of the ligand and the formation of neutral complexes. The solvent content was calculated using the thermogravimetric (TG) data. According to TG data, the copper(II) compound crystallizes with 8 while nickel(II) complex with 4 water molecules, CuL2·8H2O, NiL2·4H2O. Complexes of Co(II) and Zn(II) contain 1 and 1.5 water molecules. Despite the differences in solvation properties, the high similarity in the course of the decomposition refers to the similar coordination mode of the organic ligand. The crystal and molecular structures of HL·H2O and NH4[LHL] were determined by single-crystal X-ray structure analysis. Biological research based on determining the inhibition effect of commercial fungicide Cabrio top, ligand, and all newly synthesized complexes on Ph. viticola has been carried out using the phytosanitary method.

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A Hungary-Montenegro Intergovernmental Science and Technology Cooperation Programme Grant is acknowledged (TÉT_15-1-2016-0036). I. M. Szilágyi thanks for a János Bolyai Research Fellowship of the Hungarian Academy of Sciences and an ÚNKP-17-4-IV-BME-188 Grant supported by the ÚNKP-17-4-IV New National Excellence Program of the Ministry of Human Capacities, Hungary. A K 124212 Grant and an NRDI Grant 123631 are acknowledged. The research within Project No. VEKOP-2.3.2-16-2017-00013 was supported by the European Union and the State of Hungary, co-financed by the European Regional Development Fund.

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Correspondence to Željko Jaćimović.

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Jaćimović, Ž., Kosović, M., Kastratović, V. et al. Synthesis and characterization of copper, nickel, cobalt, zinc complexes with 4-nitro-3-pyrazolecarboxylic acid ligand. J Therm Anal Calorim 133, 813–821 (2018).

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  • Coordination complexes
  • Pyrazole-type ligand
  • Thermal properties
  • TG–MS