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, Li-6, Li-7, B-11, and P-31 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.