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Rb3P6N11 and Cs3P6N11—New Highly Condensed Nitridophosphates by High-Pressure High-Temperature Synthesis

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Abstract

The nitridophosphates Rb3P6N11 and Cs3P6N11 were synthesized by the reaction of the respective alkali azides with P3N5 at 35 kbar and 1300°C using a multianvil assembly. The products were obtained as colorless crystalline powders. According to powder diffractometry it was obvious that Rb3P6N11 and Cs3P6N11 are isotypic to K3P6N11. The crystal structures were refined from powder diffraction data by the Rietveld method using the atomic coordinates of K3P6N11 as starting values (Rb3P6N11, P4132, Z=4, a=1049.74(1) pm; Cs3P6N11, a=1065.15(1) pm).

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    Phosphates present several similarities with silicates linked to the common structural entity formed by the XO4 (X = P, Si) tetrahedron. The progressive substitution of nitrogen for oxygen within the anionic network of metal phosphate compounds leads to the formation of a family of solids: the nitridophosphates [2], for example AP4N7 (A+ = Na, K, Rb, Cs) [3], A3P6N11 (A+ = Rb, Cs) [4], BaAP6N12 (A+ = Ca, Sr) and BaP2N4 [5]. The phosphorus-based tetrahedra can be fully nitrided in the ternary nitrides Mg2PN3, LiPN2 or Li7PN4 (PN4 tetrahedra), partially in the oxynitride PON (PO2N2 tetrahedra) and showing a large domain of compositions in nitrided phosphate glasses (PO4−xNx tetrahedra) [6–8].

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