NaTlO2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six O(1,1,1) atoms to form NaO6 octahedra that share corners with two equivalent Tl(1)O6 octahedra, corners with four 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 octahedral tilt angles range from 0-8°. Tl(1) is bonded to six O(1,1) atoms to form TlO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four 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 octahedral tilt angles range from 0-8°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Na(1) and three equivalent Tl(1) atoms to form a mixture of corner and edge-sharing ONa3Tl3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(1) is bonded to three equivalent Na(1) and three equivalent Tl(1) atoms to form a mixture of corner and edge-sharing ONa3Tl3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(1) is bonded to three equivalent Na(1) and three equivalent Tl(1) atoms to form a mixture of corner and edge-sharing ONa3Tl3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°.
NaTlO2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six O(1,1,1) atoms to form NaO6 octahedra that share corners with two equivalent Tl(1)O6 octahedra, corners with four 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 octahedral tilt angles range from 0-8°. There are four shorter (2.40 Å) and two longer (2.51 Å) Na(1)-O(1,1,1) bond lengths. Tl(1) is bonded to six O(1,1) atoms to form TlO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four 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 octahedral tilt angles range from 0-8°. There are two shorter (2.16 Å) and four longer (2.40 Å) Tl(1)-O(1,1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Na(1) and three equivalent Tl(1) atoms to form a mixture of corner and edge-sharing ONa3Tl3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(1) is bonded to three equivalent Na(1) and three equivalent Tl(1) atoms to form a mixture of corner and edge-sharing ONa3Tl3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(1) is bonded to three equivalent Na(1) and three equivalent Tl(1) atoms to form a mixture of corner and edge-sharing ONa3Tl3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. There is one shorter (2.16 Å) and two longer (2.40 Å) O(1)-Tl(1) bond lengths.