Hybrid Inorganic−Metalorganic Compounds Containing Copper(II)-Monosubstituted Keggin Polyanions and Polymeric Copper(I) Complexes.

Four hybrid inorganic−metalorganic compounds containing copper(II)-monosubstituted Keggin polyoxotungstates,
K3[CuI(4,4‘-bpy)]3[SiW11CuIIO39]·11H2O (1), (paraquat)3[SiW11CuIIO39]·6H2O (2; paraquat = N,N‘-dimethyl-4,4‘-bipyridinium), K3[CuI(4,4‘-bpy)]3[GeW11CuIIO39]·11H2O (3), and Na2[CuI(4,4‘-bpy)]3[PW11CuIIO39(H2O)]·4H2O (4), have
been synthesized under autogenous pressure hydrothermal conditions and characterized by elemental analysis
and infrared spectroscopy (FT-IR). The crystal structures of 1, 2, and 4 have been established by single-crystal
X-ray diffraction. The crystal packings are characterized by the presence of monodimensional extended entities: 
either the polymeric polyanion [SiW11CuO39]n6n- (2), the cationic [Cu(4,4‘-bpy)]nn+ chain (4), or both simultaneously
as in compound 1, where the inorganic and metalorganic sublattices are mutually perpendicular. To asses the
influence of packing in the copper(I) complex structural diversity found in compounds 1 and 4, a search in the CSD
database has been performed and the resulting geometrical features have been analyzed and compared with
experimental crystallographic data and DFT calculations.