Zwei-und dreikernige Fluorooxoanionen des Vanadins. Kristallstrukturen von Cs(NMe4)[V2O2F8(H2O)] und (Na,K)(NMe4)2[V3O3F12] / Di- and Trinuclear Fluorooxoanions of Vanadium. Crystal Structures of Cs(NMe4)[VO2F8(H2O)] and (Na,K)(NMe4)2[V3O3F12]

From aqueous HF solutions the following fluorooxo complexes have been crystallized and characterized: A (NMe [V ] (1), A = Na. K; K (NMe )[V ]·H O (2); Cs(NMe )[V (H O)] (3) and NMe [VOF ] (4). The structures of 1 and 3 have been determined. Crystal data: 1c, hexagonal, space group P6 /m . a = 1695.0(9), c = 1248.1(5) pm. Z = 6: 1803 reflections. R = 0.045. 3, orthorhombic. space group Pnma, a = 2152.8(7), b = 751.5(2), c = 850.7(2) pm, Z = 4; 1379 reflections, R = 0.030. 1 contains a trimeric, cyclic anion with asymmetrically bonded μ-fluoroligands and terminal V = O groups in the same plane; the anion of 3 is a fluorobridged dimer with unequally coordinated vanadium atoms with terminal V = O groups. The preparation of these com pounds establishes the presence of VOF (H O) species in aqueous solutions.