In- this study, synthesis of two new heteronuclear tetracyanonickelate(II) clathrates based on 4-aminopyridine (4AP) and guest water (H2O) molecule and investigation of their structural properties were reported. These clathrates were characterized by using vibration spectroscopy, elemental, thermal analysis and single crystal X-ray diffraction (SC-XRD) techniques. Examining the elemental and spectral data of these clathrates, it was observed that the formulas [Zn(II)(4AP)(2)Ni(mu-CN)(2)(CN)(2)]center dot 6H(2)O and [Cu(II)(4AP)(4)Ni(mu-CN)(2)(CN)(2)]center dot H2O were defined their structures. General information about the structural properties of these clathrates in single crystal form has been obtained by considering the changes in the characteristic peaks of the cyanide group and the 4AP that formed them. The thermal behaviors of these clathrates were obtained by examining the temperature-dependent changes of their masses. The magnetic susceptibilities of these clathrates in single crystal form were measured with a Gouy balance. According to the data obtained using SC-XRD technique, the heterometallic [Zn(II)(4AP)(2)Ni(mu-CN)(2)(CN)(2)]center dot 6H(2)O compound has Cmcm and the heterometallic [Cu(II)(4AP)(4)Ni(mu-CN)(2)(CN)(2)]center dot H2O compound has crystal structures in the C2/c space group.