An extremely bent cyanide coordination at a dinickel scaffold is reported. Preorganization of two nickel ions is achieved by means of a compartmental dinucleating pyrazolate ligand L-, setting up a bimetallic coordination pocket with constrained metal-metal separation. The mixed-spin dinickel(II) complex [LNi2(CN)(MeCN)](ClO4)(2) (1) has been characterized by X-ray diffraction. The MeCN bound to the high-spin nickel(II) ion can be removed or replaced by other ligands, e.g., by the cyanide ligand of a tetracyanonickelate(II) moiety to give the starlike nonanuclear complex {[LNi2(CN)](4)[Ni(CN)(4)]}(ClO4)(6) (2) that contains four of the constrained pyrazolate-based dinickel(II) fragments grouped around a central tetracyanonickelate(II) unit, as revealed by X-ray crystallography. Spectral and electrochemical properties of I and 2 are reported, and the formation of reduced mixed-valent (NiNiII)-Ni-I species is investigated by IR and UV/vis spectroelectrochemistry.