Abstract

1-R-Tetrazoles (R ​= ​Et, i-Pr, t-Bu) were found to react with copper(II) tetrafluoroborate hexahydrate and copper(II) nitrate tetrahydrate giving the complexes [Cu2L8(H2O)2]X4, where L ​= ​1-R-tetrazole, X ​= ​BF4− or NO3−. Single crystal X-ray analysis showed that the complexes comprised dinuclear cations [Cu2L8(H2O)2]4+, with six tetrazole ligands showing monodentate N4-coordination, and two ones providing N3,N4 bridges between the copper(II) cations; water molecules complete the distorted octahedral coordination of metal ions. Magnetic susceptibility measurements revealed that the copper(II) ions were very weakly antiferromagnetically coupled. Сomplex [Сu2L8(H2O)2](BF4)4 (L ​= ​1-isopropyltetrazole) was found to exhibit a temperature induced reversible single-crystal to single-crystal polymorphic phase transition. For this complex, adiabatic calorimetry was used to find the standard thermodynamic characteristics of this transition as well as the standard thermodynamic functions of the compound in the temperature range of 80–370 ​K. Additionally, mononuclear complex of the composition [CuL6](BF4)2 (L ​= ​1-ethyltetrazole) was obtained during the investigation and structurally characterized.

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