Abstract: | The dipyridyl‐type building blocks 4‐amino‐3,5‐bis(pyridin‐3‐yl)‐1,2,4‐triazole (3‐bpt) and 4,4′‐bipyridine (bpy) have been used to assemble with ZnII in the presence of trithiocyanuric acid (ttcH3) to afford two coordination compounds, namely bis4‐amino‐3,5‐bis(pyridin‐3‐yl)‐1,2,4‐triazole‐κN3]bis(trithiocyanurato‐κ2N,S)zinc(II), Zn(C3H2N3S3)2(C12H10N6)2]·2H2O, (1), and catena‐polybis(trithiocyanurato‐κ2N,S)zinc(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] 4,4′‐bipyridine monosolvate], {Zn2(C3H2N3S3)4(C10H8N2)3]·C10H8N2}n, (2). Single‐crystal X‐ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one‐dimensional chain coordination motif. In both complexes, the central ZnII cation adopts an octahedral geometry, coordinated by four N‐ and two S‐donor atoms. Notably, trithiocyanurate (ttcH2?) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3‐bpt co‐ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4′‐bipyridine (bpy) ligand in (2) adopts a bidentate–bridging coordination mode. The different coordination characters of the different N‐donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three‐dimensional supramolecular networks for (1) and (2) arise through intermolecular N—H...S and N—H...N hydrogen bonds. Both complexes have been further characterized by FT–IR spectroscopy and elemental analyses. |