Na2ZrS3: A ternary zirconium sulfide with stuffed AlCl3-type structure

Dark green, plate-like single crystals of Na2ZrS3 (monoclinic, C2/m; a = 66 4.69(6), b = 1152.5(1), c = 695.48(7) pm, beta = 108.78(1)degrees; Z = 4) a re obtained along with pale yellow platelets of NaZr2N2SCl (trigonal, R (3) over bar m; a = 363.56(3), c = 2951.2(4) pm; Z = 3) upon oxidation of zirc onium conium metal with sulfur and sodium azide (NaN3) in the presence of f luxing NaCl (molar ratio 7:6:2:3) in evacuated silica tubes at 850 degrees C within three weeks. The crystal structure is best described as stuffed Al Cl3 type with all cations (Na+ and Zr4+) in octahedral coordination of the S2- anions, which build up a cubic closest packed host lattice. The internu clear metal sulfur distances range from 276 to 296 m for all three crystall ographically different Na+ cations, and from 258 to 260 pm for Zr4+.