Molecular structures of (555)macrotricyclic chelates appearing in 3d-element(ii) ion-hydrazinomethanethioamide-ethanedial systems according to density functional theory calculations

Abstract

Thermodynamic and geometric parameters have been calculated using the hybrid density functional theory method B3LYP with the 6-31G(d) basis set and the Gaussian03 program for the macrotricyclic complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with an (NSSN)-coordinated ligand that can result from the complexation of metal hexacyanoferrates(II) with hydrazinomethanethioamide H2N-HN-C(=S)-NH2 and ethanedial HC(=O)-CH(=O) in gelatin-immobilized matrix implants. Bond lengths and valence and torsion angles in these complexes are reported. The Ni(II) and Cu(II) complexes are practically planar. The Mn(II), Fe(II), and Co(II) complexes are characterized by a small deviation from coplanarity, and the Zn(II) complex is noticeably noncoplanar. The additional five-membered metallacycle resulting from template “joining” is nearly planar in all complexes.