Crystal Structures of Alkali Metal Peroxodiphosphates |
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Authors: | Oliver Oeckler Dr Lydia Montbrun |
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Institution: | Munich, Ludwig‐Maximilians‐Universit?t, Department of Chemistry and Biochemistry |
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Abstract: | Peroxodiphosphates of alkali metals can be prepared from K4P2O8, which is synthesized by electrolysis, in metathesis reactions with the corresponding perchlorates. Single crystals have been obtained by diffusion of methanol into aqueous solutions of the peroxodiphosphates. The crystal structures of Li4P2O8·4H2O (P21/n; a = 8.057(2) Å, b = 5.074(1) Å, c = 12.288(3) Å, β = 100.53(2)°; V = 493.9(2) Å3; Z = 2), Na4P2O8·18H2O (at 130 K: P61; a = 9.0984(14) Å, c = 49.926(13) Å; V = 3579.2(12) Å3; Z = 6) and K4P2O8 (P21/c; a = 5.9041(15) Å, b = 10.254(2) Å, c = 7.356(2) Å, β = 99.05(3)°; V = 439.79(18) Å3; Z = 2) have been determined by X‐ray diffraction. In the Li salt the cations are tetrahedrally coordinated by one water molecule and three oxygen atoms of the anions, whereas the Na salt is characterized by binuclear Na2(H2O)9]2+ complexes. At low temperatures, the latter undergoes a phase transition from a structure with disordered anions to a completely ordered phase. K4P2O8 is solvent‐free and exhibits irregular cation coordination. The structure of the peroxodiphosphate anion is very similar in all compounds; the mean O–O distance is 1.49(1) Å. In addition, the structure determination of K4(HPO4)2·3H2O2 (P21/n; a = 6.076(1) Å, b = 6.579(1) Å, c = 17.215(2) Å, β = 99.73(1)°; V = 678.26(17) Å3; Z = 2), which can be mistaken for K4P2O8, is presented. |
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Keywords: | Peroxodiphosphates Crystal structures Phase transitions |
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