Analysis of the weak interactions within the crystal structures of 33 complexes of various 4′-aromatic derivatives of 2,2′:6′,2″-terpyridine (tpy) shows that interactions that exceed dispersion are dominated, as expected, by cation⋯anion contacts but are associated with both ligand–ligand and ligand–solvent contacts, sometimes multicentred, in generally complicated arrays, probably largely determined by dispersion interactions between stacked aromatic units. With V(V) as the coordinating cation, there is evidence that the polarisation of the ligand results in an interaction exceeding dispersion at a carbon bound to nitrogen with oxygen or fluorine, an interaction unseen in the structures of M(II) (M = Fe, Co, Ni, Cu, Zn, Ru and Cd) complexes, except when 1,2,3-trimethoxyphenyl substituents are present in the 4′-tpy.
