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Title: New hypodiphosphates of the alkali metals: Synthesis, crystal structure and vibrational spectra of the hypodiphosphates(IV) M{sub 2}[(H{sub 2}P{sub 2}O{sub 6})(H{sub 4}P{sub 2}O{sub 6})] (M=Rb and Cs)

The new hypodiphosphates(IV) Rb{sub 2}[(H{sub 2}P{sub 2}O{sub 6})(H{sub 4}P{sub 2}O{sub 6})] (1) and Cs{sub 2}[(H{sub 2}P{sub 2}O{sub 6})(H{sub 4}P{sub 2}O{sub 6})] (2) were synthesized by soft chemistry reactions from aqueous solutions of hypophosphoric acid and the corresponding heavy alkali-metal carbonates. Their crystal structures were determined by single crystal X-ray diffraction. Both compounds crystallize isotypic in the triclinic space group P-1 with one formula unit in the unit cell. The structures are built up by discrete (H{sub 2}P{sub 2}O{sub 6}){sup 2-} and (H{sub 4}P{sub 2}O{sub 6}) units in staggered conformation for the P{sub 2}O{sub 6} skeleton and the corresponding alkali-metal cations. In the (H{sub 2}P{sub 2}O{sub 6}){sup 2-} ion the hydrogen atoms are in a 'trans-trans' conformation. O{center_dot}H-O hydrogen bonds between the (H{sub 2}P{sub 2}O{sub 6}){sup 2-} and (H{sub 4}P{sub 2}O{sub 6}) groups consolidate the structures into a three-dimensional network. The FT-Raman and {sup 31}P and {sup 1}H and MAS NMR spectra of the title compounds have been recorded and interpreted, especially with respect to their assignment to the (H{sub 2}P{sub 2}O{sub 6}){sup 2-} and (H{sub 4}P{sub 2}O{sub 6}) groups. Thermogravimetric data of 2 have been interpreted in terms of a thermal decomposition model. - Graphical Abstract: The layered compounds Rb{submore » 2}[(H{sub 2}P{sub 2}O{sub 6})(H{sub 4}P{sub 2}O{sub 6})] and Cs{sub 2}[(H{sub 2}P{sub 2}O{sub 6})(H{sub 4}P{sub 2}O{sub 6})] have been synthesized and investigated. Both crystallize isotypic. The structures are built up by discrete (H{sub 2}P{sub 2}O{sub 6}){sup 2-} and (H{sub 4}P{sub 2}O{sub 6}) units and the corresponding alkali-metal cations. Highlights: Black-Right-Pointing-Pointer Synthesis and single-crystal structure of new alkali hypodiphosphates. Black-Right-Pointing-Pointer Structures are characterized by [(H{sub 2}P{sub 2}O{sub 6})(H{sub 4}P{sub 2}O{sub 6})]{sup 2-} units and M{sup +} cations. Black-Right-Pointing-Pointer (H{sub 2}P{sub 2}O{sub 6}){sup 2-} and (H{sub 4}P{sub 2}O{sub 6}) units are linked by short hydrogen bonds. Black-Right-Pointing-Pointer Both compounds are characterized by {sup 31}P MAS-NMR spectra.« less
Authors:
 [1] ; ;  [2] ;  [1]
  1. Institut fuer Anorganische und Analytische Chemie der TU Clausthal, Paul-Ernst-Strasse 4, D-38678 Clausthal-Zellerfeld (Germany)
  2. Institut fuer Physikalische Chemie and Graduate School of Chemistry, Westfaelische Wilhelms-Universitaet Muenster, Corrensstr. 28/30, D-48149 Muenster (Germany)
Publication Date:
OSTI Identifier:
22149851
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 194; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKALI METALS; AQUEOUS SOLUTIONS; CARBON SULFIDES; CATIONS; CESIUM SULFIDES; CHEMICAL PREPARATION; CRYSTAL STRUCTURE; HYDROGEN; MONOCRYSTALS; NMR SPECTRA; NUCLEAR MAGNETIC RESONANCE; PHOSPHORUS 31; RAMAN SPECTRA; RUBIDIUM SULFIDES; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION