The compounds [(M@18c6)(2)][TII4](.)2H(2)O, M = TI, (NH4,NH3), (H3O, H2O) (cubic, Fd (3) over bar; a = 1481.00 pm, for M = 0.5 TI, a = 1304.65 pm for M = (NH4,NH3), a = 1313.67 pm for M = (H3O,H2O)) can be obtained from solution in the presence of traces of transition metal halides (like copper and mercury halides). Apparently the transition metal cations work as a template in the form of tetrahedral [MX4] units during the synthesis of the supramolecular host architecture. That the compounds are versatile host lattices for tetrahedrally coordinated transition metal units becomes obvious by the large group of known host-guest complex compounds, [((MX4)-X-II)(M-I@18c6)(4)][TIX4](2)(.)nH(2)O (M-II = Cu, Co, Zn, Mn; M-I = NH4+, Rb, TI; X = Cl, Br).