Stabilization of Zn(IV) and N12 backbone in Zn(N12): A quantum-chemical study by DFT method

The potential existence of a zinc–nitrogen compound with Zn : N = 1 : 12, a ratio previously unknown for these elements, was shown using three versions of density functional theory (DFT): DFT M06/TZVP, DFT B3PW91/TZVP, and DFT OPBE/TZVP. Its structural parameters were determined: the group of ZnN 4 atoms has a tetragonal-pyramidal geometry with a significant (exceeding 60°) deviation from coplanarity, and the bond lengths between the nitrogen atoms and the zinc atom exhibit slight variations. The group of N4 atoms is also non-coplanar, and the non-bond angles in it, formed by three neighboring atoms, deviate very significantly from 90°. A similar non-coplanarity occurs in the four five-membered rings, each containing the metal atom and four nitrogen atoms. The thermodynamic parameters and NBO values were calculated. The results obtained using the above three quantum-chemical methods are in good agreement.