Molecular structures of (5656)macrotetracyclic 3d metal chelates formed in the M(II) ion-ethanedithioamide-formaldehyde systems according to the density functional theory method

The thermodynamic and geometric parameters of macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN)-coordination of donor sites of the ligand formed upon complexation of the corresponding metal(II) hexacyanoferrates(II) with ethanedithioamide (NH2-C(=S)-C(=S)-NH2) and formaldehyde (H2C(=O)) in gelatin-immobilized matrices, as well as of the 14-membered macrocyclic ligand (chelant) forming these complexes, have been calculated by the OPBE/TZVP density functional theory (DFT) method with the use of the Gaussian 09 program package. The fiveand sixmembered chelate rings formed as a result of template "cross-link" are nonplanar. For the six-membered rings, the deviation from coplanarity is significantly more pronounced. In all complexes, the O1 and O2 oxygen atoms and both six-membered rings are located on different sides of the NNNN plane of the nitrogen donor atoms.