NaTlO2 is Caswellsilverite-like structured and crystallizes in the tetragonal P4/mmm space group. Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with six equivalent Na(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with eight equivalent Tl(1)O6 octahedra. The corner-sharing octahedra are not tilted. Tl(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TlO6 octahedra that share corners with six equivalent Tl(1)O6 octahedra, edges with four equivalent Tl(1)O6 octahedra, and edges with eight equivalent Na(1)O6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and four equivalent Tl(1) atoms to form ONa2Tl4 octahedra that share corners with six equivalent O(1)Na2Tl4 octahedra, edges with four equivalent O(1)Na2Tl4 octahedra, and edges with eight equivalent O(2)Na4Tl2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to four equivalent Na(1) and two equivalent Tl(1) atoms to form ONa4Tl2 octahedra that share corners with six equivalent O(2)Na4Tl2 octahedra, edges with four equivalent O(2)Na4Tl2 octahedra, and edges with eight equivalent O(1)Na2Tl4 octahedra. The corner-sharing octahedra are not tilted.
NaTlO2 is Caswellsilverite-like structured and crystallizes in the tetragonal P4/mmm space group. Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with six equivalent Na(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with eight equivalent Tl(1)O6 octahedra. The corner-sharing octahedra are not tilted. Both Na(1)-O(1) bond lengths are 2.26 Å. All Na(1)-O(2) bond lengths are 2.44 Å. Tl(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TlO6 octahedra that share corners with six equivalent Tl(1)O6 octahedra, edges with four equivalent Tl(1)O6 octahedra, and edges with eight equivalent Na(1)O6 octahedra. The corner-sharing octahedra are not tilted. Both Tl(1)-O(2) bond lengths are 2.26 Å. All Tl(1)-O(1) bond lengths are 2.44 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and four equivalent Tl(1) atoms to form ONa2Tl4 octahedra that share corners with six equivalent O(1)Na2Tl4 octahedra, edges with four equivalent O(1)Na2Tl4 octahedra, and edges with eight equivalent O(2)Na4Tl2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to four equivalent Na(1) and two equivalent Tl(1) atoms to form ONa4Tl2 octahedra that share corners with six equivalent O(2)Na4Tl2 octahedra, edges with four equivalent O(2)Na4Tl2 octahedra, and edges with eight equivalent O(1)Na2Tl4 octahedra. The corner-sharing octahedra are not tilted.