Quantum-chemical simulation of structure of isomeric asymmetric (555)macrotricyclic chelates of 3d elements arising via self-assembly in quaternary systems metal(II)-ethanedithioamide-hydrazinomethanethioamide-ethanedial

We utilized the OPBE/TZVP (GAUSSIAN-09) hybrid density functional method to compute thermodynamic (full energy; standard enthalpy, entropy, and Gibbs energy of formation) and geometry (bond lengths, bond angles, and torsion angles) parameters of (555)macrotricyclic complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with (NSSN) coordination of the ligand donor centers. Such complexes can be formed upon interaction of hexacyanoferrate(II) of the listed metals, ethanedithioamide, hydrazinomethanethioamide, and ethanedial in gelatin-immobilized matrix implants. Complexes of Cu(II) and Zn(II) are slightly nonplanar, the other complexes are almost flat. In all cases the additionally formed five-membered cycle is practically flat.