Four lead(II) complexes featuring pyrazoylisonicotinoylhydrazone ligand paired with various anionic co-ligands (azido, thiocyanato, nitrito, and nitrato) were synthesized and thoroughly examined using structural, analytical, and spectroscopic techniques. These ligands, in their mono-deprotonated state, bind to the lead(II) ion in a tridentate manner through two nitrogen atoms and one oxygen atom. Single-crystal X-ray crystallography revealed the capacity of these molecular complexes to form larger aggregates influenced by the nature of the anion attached to the metal center. In every complex, the lead atom adopts a hemidirectional coordination environment, making it geometrically suited for tetrel bond formation. The crystal structures demonstrate that lead atoms engage in notably short interactions with nitrogen atoms, distances that are shorter than the sum of their van der Waals radii yet exceed the sum of their covalent radii. These tetrel bonds play a pivotal role in weaving the monomeric into self-assembled dimers or extended supramolecular 1D polymers. The formation and characteristics of these intriguing supramolecular structures observed in the solid state of each complex were further explored and validated through density functional theory (DFT) calculations and several computational tools like MEP, NCIPlot, QTAIM, and ELF methods.
