Hydrothermal synthesis, crystal structure and properties of a 3D-framework polyoxometalate assembly:: [Ag(4,4'-bipy)](OH){[Ag(4,4'-bipy]2[PAgW12O40]} • 3.5H2O

A 3D framework assembly based on the Keggin tungstophosphate POM with silver (1) transition metal and N-ligand organic moiety and of formula [Ag(4,4'-bipy)](OH){[Ag(4,4'-bipy)](2)[PAgW12O40]}(.)3.5H(2)O (1) (bipy = bipyridine) has been synthesized by hydrothermal method and structurally characterized. The crystal of 1 belongs to triclinic, space group P-1, Mr = 3857.27, a = 10.2741(3) angstrom, b = 11.3723(4) angstrom, c = 14.0161(5)angstrom, alpha = 85.7249(5)degrees, beta = 72.8795(5)degrees, gamma = 79.9543(5)degrees, V = 1540.61(9) angstrom(3), Z = 1, D-calc = 4.158 Mg m(-3). The final statistics based on F-2 are GOF = 1.045, R-1 = 0.0326 and wR(2) = 0.0843 for I > 2 sigma(1). X-ray diffraction analysis revealed that the molecular structure of 1 consists of a neutral fragment {[Ag-I(4,4'-bipy)](2)[(PAgW12O40)-W-I-O-VI]} [Ag'(4,4'-bipy)](+) cation, hydroxide anion and lattice water molecules. The {[Ag-I(4,4'-bipy)](2)[(PAgW12O40)-W-I-O-VI]} subunits are interconnected through Ag(I) with bipyridine ligands, both surface bridging and terminal oxygen atoms of polyoloanions (POMs) to represent a novel three-dimensional (3D) polymer with 1D elliptic channels. Meanwhile, the [Ag-I(4,4'-bipy)](+) cations are also linked each other to form 1D chains, and embedded in 1D elliptic channels. (c) 2006 Elsevier Inc. All rights reserved.