Hexalacunary [α-H2 P2 W12 O48 ]12- Wells-Dawson Anion: X-ray Crystal Structural Evidence and Oligomerization to WO(OH2 )4+ -Bridged Dimer and Trimers.

Abstract

We report the first single-crystal X-ray structural evidence of the potassium salt of the hexalacunary [α-H2 P2 W12 O48 ]12- (abbreviated as {P2 W12 }) anion after its discovery by Contant and Ciabrini in 1977. In addition, we observed oligomerization of {P2 W12 } into a {WO(OH2 )}4+ -bridged Pacman-shaped [{WO(OH2 )}(α-HP2 W12 O48 )2 ]22- ({P4 W25 }) dimer and a cyclic [{WO(OH2 )}3 (P2 W12 O48 )3 ]30- ({P6 W39 }) trimer. The three phosphotungstate anions were synthesized through recrystallization of (NH4 )12 [α-H2 P2 W12 O48 ] from slightly alkaline (HOCH2 )3 CNH2 /KCl, CH3 NH3 Cl/KCl, and CH3 NH3 Cl/NH4 Cl solutions. The structure of {P2 W12 } is derived from [α-P2 W18 O62 ]6- that has six tungsten atoms one from each polar group and four from the belt-removed, and the center of the lacunary site is capped by a potassium cation. Structures of {P4 W25 } and {P6 W39 } are constructed by connecting two and three {P2 W12 } units with {WO(OH2 )}4+ , respectively. The isolation of a pure {P6 W39 } phosphotungstate framework without coordination with transition metal cations is unprecedented. Powder X-ray diffraction confirmed the bulk purity of these compounds, indicating that selective crystallization was achieved through the selection of countercations and pH.