The title compound, [Ni(C
2H
8N
2)
3][Ni(C
3HN
3O
2)
2]·H
2O, appears to be a modular associate consisting of two complex counter‐ions, containing bivalent nickel as the central atom in both cases, and a solvent water molecule. The Ni
II ion in the complex cation lies on the
C2 crystallographic axis. Its coordination environment is formed by six N atoms of three ethylenediamine (en) molecules, representing a distorted octahedral geometry. The Ni
II ion in the complex anion occupies a position at the center of inversion. It exhibits a distorted square‐planar coordination geometry formed by four N atoms belonging to the deprotonated oxidoimine and amide groups of the two doubly charged 2‐cyano‐2‐(oxidoimino)acetamidate anions, situated in
trans positions with respect to each other. In the crystal packing, the complex anions are linked by water molecules
via hydrogen bonds between the amide O atoms and water H atoms, forming chains translated along the
a direction. The [Ni(en)
3]
2+ cations fill empty spaces between the translational chains, connecting them by hydrogen bonds between the oxime and amide O atoms of the anions and the amine H atoms of the cations, forming layers along the
ac plane. The water molecules provide connection between layers through N atoms of the cations, thus forming a three‐dimensional modular structure.
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