The crystal structures of three Zn complexes with the peroxodisulfate anion (pds2−) acting as counter‐ion are reported, namely bis(2,2′:6′,2′′‐terpyridine‐κ3N)zinc(II) hexaoxo‐μ‐peroxo‐disulfate(VI) dihydrate N,N‐dimethylformamide solvate, [Zn(C15H11N3)2](S2O8)·2H2O·C3H7NO or [Zn(tpy)2](pds)·2H2O·DMF, (I), bis[2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine‐κ2N2,N4]zinc(II) hexaoxo‐μ‐peroxo‐disulfate(VI) dihydrate, [Zn(C18H12N6)2](S2O8)·2H2O or [Zn(tpt)2](pds)·2H2O, (II), and bis[2,6‐bis(1H‐benzimidazol‐2‐yl‐κN3)pyridine]zinc(II) hexaoxo‐μ‐peroxo‐disulfate(VI) N,N‐dimethylformamide trisolvate, [Zn(C19H13N5)2](S2O8)·3C3H7NO or [Zn(bbp)2](pds)·3DMF, (III), where tpy is 2,2′:6′,2′′‐terpyridine, tpt is 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine, bbp is 2,6‐bis(1H‐benzimidazol‐2‐yl)pyridine and DMF is N,N‐dimethylformamide. The three structures are monomeric and present the Zn cation in a distorted octahedral environment, defined by two chelating tricoordinated ligands at almost right angles to each other. These cationic entities interact with an anionic network composed of hydrogen‐bonded pds2− anions and solvate water and DMF molecules via Coulombic forces, and with each other through a number of π–π and C=C⋯π contacts connecting the aromatic rings. The pds2− anions stabilize the structures in unprecedented counter‐ion behaviour.
