Synthesis and structure investigations on iodocuprates(I) .17. Crystal structures of polymeric iodo-thiocyanato metallates(I) with heterocubane-like structure units: [(C2H5)(4)N+](2)(3)(infinity)[Cu4I4(SCN)(4/2)(2-)]center dot 2(CH3)(2)CO and [(C2H5)(4)N+](2)(2)(infinity)[Ag4I4(SCN)(4/2)(2-)]center dot(CH3)(2)CO

The reaction of CuSCN and AgSCN with (C2H5)(4)NI in acetone results in the formation of new Iodo-thiocyanato cuprates(I) or argentates(I) with polymeric anion lattices and areas of holes in which the cations and solvent molecules are inserted. [(C2H5)(4)N+](2 infinity)(3)[Cu4I4(SCN)(4/2)(2-)] . 2(CH3)(2)CO 1 crystallizes in the monoclinic space group P2(1) with a = 1205.7(1), b = 2489.1(3), c = 1238.0(1) pm; beta = 93.04(1)degrees; V = 3710.1(8) . 10(6) pm(3); Z = 2. Two different, negatively charged heterocubane units [Cu4I4(SCN)(4/2)(2-)] are three-dimensionally connected by 1,3-mu-thiocyanato ligands forming a crystal structure with hose-shaped channels where cations and acetone molecules are placed. [(C2H5)(4)N+](2 infinity)(2)[Ag4I4(SCN)(4/2)(2-)] . (CH3)(2)CO 2 crystallized in the orthorhombic space group C222(1) with a = 1206.7(1), b = 1398.2(1), c = 2318.8(2) pm; V = 3912.4(7) . 10(6) pm(3); Z = 8. In this compound 1,3-mu-thiocyanato-bridged heterocubane units [Ag4I4(SCN)4/22-] form a layer structure with channel-shaped cavities vertical to them. Within these hollows there is again place for the cations and acetone molecules.