The reaction between the NiA(ClO₄)₂ and NaHL₂ {where A = 14ane[N₄], the macrocyclic ligands derived from the product of template condensation of 2,6-diacetylpyridine with aliphatic 3,3′-diaminodipropylamine, NH₂(CH₂)₃NH(CH₂)₃NH₂; and L = 2-cyano-2-isonitrosoacetamide anion, ACO⁻ (amidecyanoxime, NC-C(NO)-C(O) )} has led to the formation of a highly unusual trimetallic bis-[ fac-(triscyanoximato) nickel(II)] anionic complex anion instead of the expected Ni(II) macrocyclic complex with coordinated cyanoxime ligands. Two equivalent and symmetric trigonal-prismatic NiL units are connected to form the [NaNi₂L₆]⁻ anion by the presence of a central sodium cation. The latter is located between two NiL anions and has an octahedral NaO₆ geometry comprised of oxygen atoms of the nitroso group of the cyanoxime ligand. The oxime ligand is planar and adopts a cis-anti configuration in the complex.