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Na3[BN2] and Na2K[BN2] were obtained as white polycrystalline powders from the reaction of the respective binary mixtures NaNH2:NaBH4 and NaNH2:KBH4 in molar ratio 2:1 at 873 K and 683 K, respectively, in an argon stream. According to the results of thermal analysis measurements, both compounds are thermally stable only up to 954 K (Na3[BN2]) and 712 K (Na2K[BN2]), respectively, decomposing under evolution of alkali metal and nitrogen to yield hexagonal BN as final residue, which was identified from powder patterns. The crystal structure of Na3[BN2] {β-Li3[BN2] type; P21/c (No. 14); Z = 4} was confirmed and the unit cell parameters redetermined: a = 5.724(1) Å, b = 7.944(1) Å, c = 7.893(1) Å, β = 111.31(1)°. According to X-ray powder data, Na2K[BN2] crystallizes isotypic to Na2KCuO2 in the tetragonal space group I4/mmm (No. 139) with a = 4.2359(1) Å, c = 10.3014(2) Å and Z = 2. The crystal structure of Na2K[BN2] is composed of linear [N–B–N]3– anions centering elongated M14 rhombic dodecahedra, which are formed by 8 sodium and 6 potassium atoms. The [BN2]@Na8/4K6/6 polyhedra are stacked along [001] and condensed via common tetragonal faces to generate a space-filling 3D arrangement. The B–N bond lengths for the strictly linear [N–B–N]3– units are 1.357(4) Å. Vibrational spectra of the title compounds were measured and analyzed based on D∞h symmetry of the relevant [N–B–N]3– groups taking into account the site symmetry effects for Na3[BN2]. Both the wavenumbers, as well as the calculated valence force constants f(B–N) = 7.29 N·cm–1 (Na3[BN2]) and 7.33 N·cm–1 (Na2K[BN2]), respectively, are in good agreement with those of the known alkali and alkaline earth dinitridoborates.
