Three new ZnII complexes with the ligand 4′-chloro-2,2′:6′,2ʺ-terpyridine (4′-Cltpy), [Zn(4′-Cltpy)(N3)2] (1), [Zn(4′-Cltpy)(NCS)2] (2) (two 1:1 metal/ligand complexes) and a 1:2 metal/ligand complex, [Zn(4′-Cltpy)2](NO3)2·2H2O (3), have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy and single-crystal X-ray diffraction. The structures of 1 and 2 contain a ZnN5 coordination sphere, which includes coordination from three nitrogen donors of the 4′-Cltpy ligand and two nitrogen atoms of two terminal azide or two terminal thiocyanate ligands, respectively. Addison’s τ value suggests a distorted square pyramidal coordination of ZnII in 1 and intermediate between square pyramidal and trigonal bipyramidal in 2. In the complex cation of 3, the ZnII center is coordinated by six nitrogen atoms from two 4′-Cltpy ligands in a distorted octahedral coordination geometry. In this structure, two non-coordinating nitrate anions serve as counterions, and there are two non-coordinating solvent water molecules. Hirshfeld surface analysis was employed to clarify the nature and extent of intermolecular interactions. In addition, the thermal stabilities of the compounds were evaluated by thermogravimetric analysis (TGA).