Some new Hofmann-3-phenylpropylamine-type clathrates with chemical formulae of M(3-phenylpropylamine)2 Ni(CN)4. 2G (MNi or Co, G = 1,2-dichlorobenzene or 1,3-dichlorobenzene) have been prepared and their Fourier transform infrared(FT-IR; 4000–400 cm−1), far-infrared (600–100 cm−1) and FT-Raman (4000–60 cm−1) spectra are reported. The ligand molecule, guest molecules, polymeric sheet and metal-ligand bands of the clathrates are assigned in detail. The compounds are also characterized by thermal gravimetric analysis (TGA), differential thermal analysis (DTA), elemental analysis and magnetic susceptibility measurements. From the results, the monodentate 3-phenylpropylamine ligand molecule bonds to the metal atom of |M-Ni(CN)4 | ∞ polymeric layers in the trans-gauche-gauche (TGG) form, and 1,2-dichlorobenzene or 1,3-dichlorobenzene molecules are guested by this structure revealing the inclusion ability of the host complexes. Copyright © 2010 John Wiley & Sons, Ltd.