Na2ZrS3: Ein ternäres Sulfid des Zirconiums mit aufgefüllter AlCl3‐Struktur

Na₂ZrS₃: A Ternary Zirconium Sulfide with Stuffed AlCl₃‐type Structure Dark green, plate‐like single crystals of Na₂ZrS₃ (monoclinic, C2/m; a = 664.69(6), b = 1152.5(1), c = 695.48(7) pm, β = 108.78(1)°; Z = 4) are obtained along with pale yellow platelets of NaZr₂N₂SCl (trigonal, R3m; a = 363.56(3), c = 2951.2(4) pm; Z = 3) upon oxidation of zirconium metal with sulfur and sodium azide (NaN₃) in the presence of fluxing NaCl (molar ratio 7:6:2:3) in evacuated silica tubes at 850°C within three weeks. The crystal structure is best described as stuffed AlCl₃ type with all cations (Na⁺ and Zr⁴⁺) in octahedral coordination of the S^2– anions, which build up a cubic closest packed host lattice. The internuclear metal sulfur distances range from 276 to 296 pm for all three crystallographically different Na⁺ cations, and from 258 to 260 pm for Zr⁴⁺.