view:20506 Last Update: 2019-1-30
Marzieh Emami, Katarzyna Anna Ślepokura, Monika Trzebiatowska,
Nader Noshiranzadeh and Vasyl Kinzhybalo
Oxyanion clusters with antielectrostatic hydrogen bonding (AEHB) in tetraalkylammonium hypodiphosphates
Organic–inorganic salts of hypodiphosphoric acid with tetraalkylammonium cations have been synthesized and characterized by X-ray crystallography and IR spectroscopy. [(Et4N)ĲH3P2O6)]·0.5H4P2O6·2H2O (1), [(Et4N)2ĲH2P2O6)]·H4P2O6 (2), [(n-Bu4N)ĲH3P2O6)]·0.75H4P2O6 (3), [(n-Bu4N)ĲH3P2O6)]·0.25H4P2O6·0.53H2O (4), [(n-Bu4N)ĲH3P2O6)]·0.25H4P2O6 (5) and [(Et4N)Cl]·0.5H4P2O6·3H2O (6) were obtained in the crystalline form. Their crystal structures reveal the formation of hydrogen-bonded networks (chains and layers) built from hypodiphosphate anions and acid molecules, assisted by water molecules in the hydrates. The networks are embedded in the tetraalkylammonium cations' framework. Free acid molecules are present in all of the studied substances. Compound 5 was formed during a solid state dehydration reaction of 4, which has taken place as single-crystal-to-single-crystal transformation. Water removal is associated with a symmetry increase and structure reconstruction, with the change in the conformation of one of the hypodiphosphate anions, from the usual staggered into a rarely occurring eclipsed conformation. In 1, 3, 4 and 5 the formation of clusters with antielectrostatic hydrogen bonding (AEHB) was observed.