Supramolecular complexes [M{NH(CH2)4O}{S2CN(C2H5)22] ∙ CCl4 (M = Zn or 63Cu(II)): Synthesis, structures, spectral and thermal properties

Resumo

Solvated adducts of diethyldithiocarbamate complexes of zinc and copper(II) of the formula [M{NH(CH²)⁴O}{S²CN(C²H⁵)²²] ∙ CCl⁴ (M = Zn (I) and 63Cu (II)) were obtained. ¹³C MAS NMR experiments revealed magnetic nonequivalence in the dithiocarbamate moieties of the adduct isomers, the morpholine heterocycles, and the outer-sphere solvate molecules. The rhombic anisotropy of the EPR parameters of magnetically diluted isotope-substituted complex II is due to the copper polyhedron geometry, which is intermediate between a tetragonal pyramid and a trigonal bipyramid, with the ground state of the unpaired electron resulting from the mixing \(3{d_{{x^2} - {y^{2 - }}}}\) of and \(3{d_{{z^{2 - }}}}\) of copper(II). According to X-ray diffraction data, complex I is a supramolecular complex combining structurally nonequivalent adduct molecules (A and B) and “guest” molecules (CCl₄). In addition, the crystal lattice has an array of channels occupied by outersphere solvate CCl₄ molecules (a structural type of lattice clathrates). An STA study of the thermal properties revealed three main thermolysis steps: desorption of the solvate CCl₄ molecules, elimination of coordinated morpholine molecules, and thermolysis of the dithiocarbamate moiety of the adduct.