Abstract: | The synthesis and characterization of two new dinuclear nickel(II) complexes, namely bis{μ‐3‐2‐(dimethylamino)ethylimino]butan‐2‐one oximato}dinickel(II) bis(perchlorate) acetonitrile solvate, Ni2(C8H16N3O)2](ClO4)2·CH3CN, (I), and bis{μ‐3‐2‐(dimethylamino)ethylimino]‐3‐phenylpropan‐2‐one oximato}dinickel(II) bis(perchlorate), Ni2(C13H18N3O)2](ClO4)2, (II), are reported. Single‐crystal X‐ray analyses of the complexes reveal that the nickel(II) ions are in square‐planar N3O environments and form six‐membered (NiNO)2 metallacycles. The cation in (II) possesses crystallographically imposed inversion symmetry. |