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

Li₄₇B₃P₁₄N₄₂, the first lithium nitridoborophosphate, is synthesized by two different routes using a Li₃N flux enabling a complete structure determination by single‐crystal X‐ray diffraction data. Li₄₇B₃P₁₄N₄₂ comprises three different complex anions: a cyclic [P₃N₉]¹²⁻, an adamantane‐like [P₄N₁₀]¹⁰⁻, and the novel anion [P₃B₃N₁₃]¹⁵⁻. [P₃B₃N₁₃]¹⁵⁻ is the first species with condensed B/N and P/N substructures. Rietveld refinement, ⁶Li, ⁷Li, ¹¹B, and ³¹P 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 Li₃N 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.