The layered Ni(CnH2n+1NH2)2Ni(CN)4acts as a host structure for amines, yielding Ni-(CnH2n+1NH2)2Ni(CN)4,xCnH2n+1NH2(with 0 ≤ x ≤ 0.4 and 12 ≤ n ≤ 16) which are easily prepared by various procedures including solid–solid reaction. The guest can be removed and re-included; it can be replaced by aromatics. Phase transitions of the clathrate (with amines as guest) occur in the range 55–85 °C, obviously related to the transitions previously observed in the parent compound Ni(CnH2n+1NH2)2Ni(CN)4.