A range of 2-arylaminopyridines (HL) are synthesised readily from bromopyridines and amines using palladium-catalysed amination. Protonolysis reactions of these proligands with ZrX₄ (X = NMe₂, CH₂Ph, CH₂Bu^t) yield zirconium complexes of the type [ML_nX_4−n], several of which have been characterised by X-ray crystallography. Control of metal/ligand stoichiometry and structure is pursued by investigation of the effects on substitution patterns of the pyridine and aryl rings. Some distinct patterns emerged; (i) the 6-methyl position on the pyridine appears to be particularly important with regards to control of stoichiometry, although there are co-ligand effects; (ii) structures of the metal alkyl derivatives [ZrL_n(CH₂R)_4−n] are dominated by aromatic π–π stacking, even when bulky arene substituents are employed at L. This leads to the complexes adopting a C_2v-symmetric core; (iii) the amides [ZrL₂(NMe₂)₂] have structures for which aromatic π–π stacking is unfeasible, and correspondingly C₂-symmetric or similar structures are adopted. All the structural data presented is consistent with a trans influence order at zirconium Me₂N > RCH₂ > py.