Sn 6 [P 12 N 24 ] – A Sodalite‐Type Nitridophosphate

Sn 6 [P 12 N 24 ] was synthesized from Sn and HPN 2 at 820 °C in an evacuated silica glass ampoule. According to powder X‐ray diffraction investigations and Rietveld refinement [space group I $\bar {4}$ 3 m (no. 217), a = 8.2882(2) Å, R P = 0.03645, wR P = 0.04613], Sn 6 [P 12 N 24 ] crystallizes with a sodalite‐type structure with a reduced occupation factor of 3/4 for the Sn atom at Wyckoff site 8 c and an empty Wyckoff site 2 a at the center of the β‐cages. The structural results are further corroborated by energy‐dispersive X‐ray spectroscopy (EDX) analyses, solid‐state NMR spectroscopy, and theoretical investigations (DFT), including density of states (DOS), energy/volume, and electron localization (ELF) calculations. The 119 Sn Mössbauer spectrum shows a single, quadrupole‐split signal for Sn II at an isomer shift of 3.05 mm/s. In addition to SiPN 3 with a defective wurtzite type of structure, the nitridophosphate sodalite Sn 6 [P 12 N 24 ] represents the second ternary nitridophosphate containing only p‐block elements.