Li₄₇B₃P₁₄N₄₂—A Lithium Nitridoborophosphate with [P₃N₉]¹²⁻, [P₄N₁₀]¹⁰⁻, and the Unprecedented [B₃P₃N₁₃]¹⁵⁻ Ion

Abstract

Abstract Li 47 B 3 P 14 N 42 , the first lithium nitridoborophosphate, is synthesized by two different routes using a Li 3 N flux enabling a complete structure determination by single‐crystal X‐ray diffraction data. Li 47 B 3 P 14 N 42 comprises three different complex anions: a cyclic [P 3 N 9 ] 12− , an adamantane‐like [P 4 N 10 ] 10− , and the novel anion [P 3 B 3 N 13 ] 15− . [P 3 B 3 N 13 ] 15− is the first species with condensed B/N and P/N substructures. Rietveld refinement, 6 Li, 7 Li, 11 B, and 31 P solid‐state NMR spectroscopy, FTIR spectroscopy, EDX measurements, and elemental analyses correspond well with the structure model from single‐crystal XRD. To confirm the mobility of Li + ions, their possible migration pathways were evaluated and the temperature‐dependent conductivity was determined by impedance spectroscopy. With the Li 3 N flux route we gained access to a new class of lithium nitridoborophosphates, which could have a great potential for unprecedented anion topologies with interesting properties.