This paper reports the solid state structures of two new metallosupramolecular complexes resulting from pseudoterpyridine bis-hydrazone-type 3 and bis-acylhydrazone-type 4 ligands and Zn-II metal ions. The complex 3(2)Zn(II) are quantitatively trapped by crystallization via constitutionally driven selection from binary solutions of 1:1 and 2:1 3:Zn-II (mol: mol). The constitutional internal overlap between the phenyl moieties and the central pyridine moiety clearly plays an important role for internal holding and stabilizing the duplex formation by pi-pi stacking. The crystal 4Zn(II)*4 heterostructure and its packing reported in this paper present uncommon features with many other similar architectures reported by now. This structure shows a relatively new structural concept: the 4Zn(II) complex in which the Zn-II ions are coordinated by one ligand rolling the axial position of the metal ion, further interacting by H-bonding with the free ligand 4 in the crystal, allowing one to obtain 2D-layered architectures