Synthesis, X-ray Structure and Hirshfeld Surface Analysis of Zn(II) and Cd(II) Complexes with s-Triazine Hydrazone Ligand

Abstract

The two group IIB complexes [Cd(DMPT)Cl2] (6) and [Zn(DMPT)Cl2] (7) of the tridentate ligand (DMPT), 2,4-bis(morpholin-4-yl)-6-[(E)-2-[1-(pyridin-2-yl) ethylidene]hydrazin-1-yl]-1,3,5-triazine were synthesized, and their structural aspects were elucidated with the aid of X-ray crystallography. Both complexes crystallized in the monoclinic crystal system, with P21/n as a space group. The unit cell parameters for 6 are a = 14.1563(9) Å, b = 9.4389(6) Å, c = 16.5381(11) Å and β = 91.589(5)° while the respective values for 7 are 11.3735(14), 13.8707(13), 14.9956(16), and 111.646(2)°. The unit cell volume is slightly less (2198.9(4) Å3) in complex 7 compared to complex 6 (2209.0(2) Å3). Both complexes have a penta-coordination environment around the metal ion, where the DMPT ligand acts as a neutral tridentate NNN-chelate via the pyridine, hydrazone, and one of the s-triazine N-atoms. The penta-coordination environment of the Cd(II) in complex 6 is close to a square pyramidal configuration with some distortion. On the other hand, the ZnN3Cl2 coordination environment is highly distorted and located intermediately between the trigonal bipyramidal and square pyramids. Supramolecular structure analysis of 6 with the aid of Hirshfeld calculations indicated the importance of the Cl…H, O…H, and C…H interactions. Their percentages were calculated to be 20.9, 9.1, and 8.7%, respectively. For 7, the Cl…H, O…H, C…H, and N…H contacts are the most important. Their percentages are 20.3, 9.0, 7.0, and 8.4%, respectively. In both complexes, the major intermolecular interaction is the hydrogen–hydrogen interactions which contributed 45.5 and 46.6%, respectively.