An investigation into the co-ordination chemistry of tris(6-pivaloylamino-2-pyridylmethyl)amine (TPPA) shows a preference for capped octahedral geometry when no additional donors are present. This tripodal ligand yields capped octahedral complexes upon co-ordination to a series of first row transition metals when the counter-ion is a perchlorate, bromide or iodide ion. The exact geometry has been confirmed by shape mapping calculations. The largest variation from the capped octahedral geometry is observed in the case of nickel(ii), indicating a greater octahedral preference of this metal ion.