The geometries of (5676)macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination of the chelant donor sites, formed through template processes in the M(II)–3,3,8,8-tetramethyl-4,7-diazadecanedihydrazone-1,10-butanedione-2,3 systems have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. The bond lengths and angles and selected nonbonded angles in these complexes with the MN4 chelate core have been determined. It has been demonstrated that none of the chelate rings is planar: the smallest deviation from coplanarity is always observed for the five-membered rings and the largest, for the six-membered rings not identical to each other. The seven-membered ring resulting from the template cross-linking exhibits deviations from coplanarity intermediate between those for the five- and six-membered rings.