Density functional theory calculation of molecular structures of (5656)macrotetracyclic 3d metal complexes with 4,12-Dithiooxo-1,8-dioxa-3,6,10,13-tetraazacyclotetradecanedione-5,11

Abstract

The geometric parameters of macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination formed by the reaction of corresponding hexacyanoferrates(II) with thiocarbamoylmethanamide H2N-C(=S)-C(=O)-NH2 and formaldehyde in gelatin-immobilized matrices have been calculated by the hybrid B3LYP density functional theory method with the use of the 6-31G(d) basis set and the Gaussian 03 program package. The bond lengths and bond and torsion angles in these complexes have been reported. It has been stated that the additional six-membered chelate rings resulting from template cross-linking are nonplanar and are turned at rather large angles to the two five-membered rings (which are also noncoplanar). In the Fe(II), Co(II), and Ni(II) complexes, the O1 and O2 atoms and both six-membered rings are located on one side of the (NNNN) plane of the donor nitrogen atoms, whereas in the Mn(II), Cu(II), and Zn(II) complexes, they are located on both sides of this plane.