Abstract
AbstractRecrystallization of Cs3P7 from liquid NH3 yields the triammoniate Cs3P7·3 NH3, which loses the weakly bound NH3 of crystallization below 253 K. A low‐temperature crystal‐structure analysis shows that Cs3P7· NH3 consists of a framework of heptaphosphanortricyclane anions P and Cs+ cations with NH3 molecules completing the coordination of the cations. The framework is built from Cs3P7 layers connected by only few Cs…︁P interactions, the interlayer gap being filled by a two‐dimensional network of NH3. The Cs7P7 part of the structure completes a family of alkali‐metal‐polyphosphide substructures which range from [RbP7]2− or [CsP11]2− chains over [Cs2Pn]− layers (n = 7, 11) to now [Cs3P7] frameworks.
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