Ba 6 P 12 N 17 O 9 Br 3 – A Column‐Type Phosphate Structure Solved from Single‐Nanocrystal Data Obtained by Automated Electron Diffraction Tomography

Oxonitridophosphate Ba 6 P 12 N 17 O 9 Br 3 was synthesized by heating a multicomponent mixture of BaBr 2 , BaS, phosphoryl triamide and thiophosphoryl triamide in an evacuated and sealed silica‐glass ampoule to 750 °C. Ba 6 P 12 N 17 O 9 Br 3 was obtained as the main product as a nanocrystalline powder. The crystal structure was determined ab initio on the basis of electron diffraction data acquired from a single needle‐shaped nanocrystal by automated diffraction tomography. Ba 6 P 12 N 17 O 9 Br 3 crystallizes in the hexagonal space group P 6 3 / m (no. 176) with unit cell parameters a = 14.654(19), c = 8.255(9) Å and Z = 2. Its structure includes triangular, column‐shaped anions of ∞ 1 {(P 12 N 17 O 9 ) 9– }, which are built from vertex‐sharing P(O,N) 4 tetrahedra with 3‐rings and three‐coordinate nitrogen atoms. The 1D anions are separated by Ba 2+ and Br – ions, which are arranged in channels parallel to the phosphate anions along [001]. The Ba 2+ ions are eight‐ and nine‐coordinated by Br – and O/N atoms, respectively.