The exfoliation process of one-dimensional KNiPS4 showed that the breaking of 1/∞[NiPS4]− chains in polar solvent was followed by the formation of cyclic [Ni3P3S12]3− trianions. From DMF–KNiPS4 solutions, metathesis experiments were successfully carried out, but, up to now, K+ had only been exchanged by bigger isotropic organic cations such as PPh4+, (CH3)4N+ and (C2H5)4N+. After recrystallization, each metathesis compound presents the cyclic [Ni3P3S12]3− trianion. An exchange by anisotropic cations is possible by adding a cryptand molecule that fits the size of K+. Following this procedure, three new nickel thiophosphate complexes have been synthesized: [Ni3P3S12][K-(222-cryptand)]3 (I), [Ni3P3S12][K(222-cryptand)]2[C9N1H22] (II) and [Ni3P3S12][CH3(CH2)11N(CH3)3]3 (III). The structures of I and II have been fully determined from single crystal X-ray diffraction analysis. They show the occurrence of the [Ni3P3S12]3− trimer within the solid. I and II crystallize in the P212121 space group. 31P solid state NMR experiments hint at the presence of polyanions in III, maybe trianionic in nature.