The reaction between the NiA(ClO 4 ) 2 and NaHL 2 {where A ¼ 14ane [N 4 ], the macrocyclic ligands derived from the product of template condensation of 2,6-diacetylpyridine with aliphatic 3,3 0 -diaminodipropylamine, NH 2 (CH 2 ) 3 NH(CH 2 ) 3 NH 2 ; and L ¼ 2-cyano-2-isonitrosoacetamide anion, ACO À (amidecyanoxime, NC-C(NO)-C(O)NH 2 À )} 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 3 À units are connected to form the [NaNi 2 L 6 ] À anion by the presence of a central sodium cation. The latter is located between two NiL À 3 anions and has an octahedral NaO 6 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.