Structural and Spectral Effects of Anion-Cation Interaction in Mixed Salts of P−W−M Heteropolyacids. Crystal Structure of Cs5 [PCo(H2 O)W11 O39 ]·3H2 O
Journal of Structural Chemistry
, E-ISSN: 1573-8779
Institute of Inorganic Chemistry
Institute of Catalysis, Siberian Branch, Academy of Sciences of the USSR
GIPKh Scientific-Production Association
The x-ray structure is solved for tetragonal crystals of the heteropoly salt (HPS) Css[PCo(H20)WIIO~9]'3H20 (I), space group P42/ncm, a = b = 20.810(7), c = 10.397-(2) ~, Z = 4. The structure contains a Keggin heteropolyanion (HPA). The W and Co atoms are statistically disordered over 12 positions. The HPA itself adopts two orientations related by a center of symmetry. Besides I, the tetramethyl- (II) and tetrabutylammonium (III) HPS are also obtained. Raman and IR spectra of I-III demonstrated that the influence of the cation on the position and relative intensities of the bands is comparable to and sometimes greater than the analogous influence from changing the HPA composition.