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Single crystals of the title polyoxometallate-based organic&#8211;inorganic hybrid, [Cu(C12H8N2)2]4[SiW12O40], were grown under hydrothermal conditions. The discrete [SiW12O40]4&#8722; anions are of the Keggin type and are packed in a slightly distorted orthorhombic F-centred mode, with the complex [CuI(phen)2]+ cations (phen is 1,10-phenanthroline) located in the voids of this arrangement. The four independent CuI cations are situated in the centres of more or less distorted tetrahedra made up of N atoms from the phen ligands. The anions and cations are linked together via weak hydrogen-bonding interactions, forming an extended three-dimensional network. Additional stabilization is achieved via &#960;&#8211;&#960; interactions between different phen molecules of adjacent [CuI(phen)2]+ cations with shortest distances between 3.416 and 3.499&#8197;&#197;

An ionic organic–inorganic hybrid: tetrakis[bis(1,10-phenanthroline)copper(I)] dodecatungstophosphate(V)