Syntheses and characterizations of two novel networks formed by Keggin clusters and copper-organonitrogen complexes

Two novel heteropolytungstates, [Cu₃Cl(4,4′-bpy)₃]₂[α- SiW₁₂O₄₀] · 4H₂O 1 and {Cu₃(4,4′-bpy)₂(2,2′-bpy)₃} {Cu(2,2′-bpy)₂}{α-SiW₁₂O₄₀} · 0.5(H₂O) · 0.5(2,2′-bpy) 2 (4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine), have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Compound 1 has a unique 2D network, which is composed of cationic trinuclear Cu(I) coordination polymer chains and discrete [α-SiW₁₂O₄₀]^4- polyoxoanions as linkers. Notably, it is rarely that the Cu(I) coordination polymer chains are not isolated but connected together by chlorine atoms. Compound 2 exhibits an unusual 3-D network with sandglasslike 1-D channels, within which are located large spherical polyoxometalate anions [α-SiW₁₂O₄₀]^4-. The crystal data for two compounds are the following: 1, triclinic, space group P over(1, -), a = 10.904(2) Å, b = 15.087(3) Å, c = 15.303(3) Å, α = 116.23(3)°, β = 100.08(3)°, γ = 94.40(3)°, V = 2189.29(80) ų, Z = 1; 2, monoclinic, C₂/c, a = 15.444(3) Å, b = 24.962(5) Å, c = 25.806(5) Å, β = 99.75(3)°, V = 9805(3) ų, Z = 4.