Acta Cryst. (2012). C68, i71-i82 [ doi:10.1107/S010827011204317X ]
Abstract: The synthesis and crystal structures of a series of six crystalline potassium salts of hypodiphosphoric acid, H4P2O6, are reported, namely potassium hydrogen phosphonophosphonate, K+·H3P2O6-, (I), dipotassium dihydrogen hypodiphosphate monohydrate, 2K+·H2P2O62-·H2O, (II), dipotassium dihydrogen hypodiphosphate dihydrate, 2K+·H2P2O62-·2H2O, (III), pentapotassium hydrogen hypodiphosphate dihydrogen hypodiphosphate dihydrate, 5K+·HP2O63-·H2P2O62-·2H2O, (IV), tripotassium hydrogen hypodiphosphate tetrahydrate, 3K+·HP2O63-·4H2O, (V), and tetrapotassium hypodiphosphate tetrahydrate, 4K+·P2O64-·4H2O, (VI). All the hypodiphosphate anions, viz. H3P2O6-, H2P2O62-, HP2O63- and P2O64-, adopt a staggered conformation. The P-P bond lengths [2.1722 (7)-2.1892 (10) Å] do not depend on the basicity of the anion. The compounds are organized into different types of one-, two- or three-dimensional polymeric hydrogen-bonded networks, or simply exist in the form of isolated or dimeric units. The coordination numbers of the K+ cations range from 6 to 9, and the cationic sublattices are polymeric one-, two- or three-dimensional networks, or isolated [KO6] or dimeric [K2O12] polyhedra.
Formula: K+·H3O6P2-, 2K+·H2P2O62-·H2O, 2K+·H2P2O62-·2H2O, 5K+·HP2O63-·H2P2O62-·2H2O, 3K+·HP2O63-·4H2O and 4K+·P2O64-·4H2O
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