Abstract: | On Tripraseodymium Hexanitridotriborate Pr3B3N6: New Synthesis and Crystal Structure Refinement Single‐crystalline Pr3B3N6 was obtained by the reaction of praseodymium and BNx(NH)y(NH2)z in a NaCl melt under N2 atmosphere in a high‐frequency furnace at 1250 °C. Contrary to literature data, Pr3B3N6 crystallizes in the centrosymmetric space group R 3 c as revealed by single‐crystal X‐ray diffraction (a = 1211.95(9), c = 701.53(7) pm, Z = 6, R1 = 0.0258, wR2 = 0.0658). In the solid, Pr3B3N6 contains Pr3+ and planar cyclotrinitridoborate units B3N69–. The anions represent motifs from the structure of hexagonal boron nitride (h‐BN) and they are stacked analogously along 001]. Both the bond lengths B–N (average value 147.8 pm) and the interionic distances between the anions (350.8 pm) are comparable with the values in h‐BN. |