NaBiSe2 is Caswellsilverite-like structured and crystallizes in the tetragonal P4/mmm space group. Na(1) is bonded to two equivalent Se(1) and four equivalent Se(2) atoms to form NaSe6 octahedra that share corners with six equivalent Na(1)Se6 octahedra, edges with four equivalent Na(1)Se6 octahedra, and edges with eight equivalent Bi(1)Se6 octahedra. The corner-sharing octahedra are not tilted. Bi(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form BiSe6 octahedra that share corners with six equivalent Bi(1)Se6 octahedra, edges with four equivalent Bi(1)Se6 octahedra, and edges with eight equivalent Na(1)Se6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Na(1) and four equivalent Bi(1) atoms to form SeNa2Bi4 octahedra that share corners with six equivalent Se(1)Na2Bi4 octahedra, edges with four equivalent Se(1)Na2Bi4 octahedra, and edges with eight equivalent Se(2)Na4Bi2 octahedra. The corner-sharing octahedra are not tilted. In the second Se site, Se(2) is bonded to four equivalent Na(1) and two equivalent Bi(1) atoms to form SeNa4Bi2 octahedra that share corners with six equivalent Se(2)Na4Bi2 octahedra, edges with four equivalent Se(2)Na4Bi2 octahedra, and edges with eight equivalent Se(1)Na2Bi4 octahedra. The corner-sharing octahedra are not tilted.
NaBiSe2 is Caswellsilverite-like structured and crystallizes in the tetragonal P4/mmm space group. Na(1) is bonded to two equivalent Se(1) and four equivalent Se(2) atoms to form NaSe6 octahedra that share corners with six equivalent Na(1)Se6 octahedra, edges with four equivalent Na(1)Se6 octahedra, and edges with eight equivalent Bi(1)Se6 octahedra. The corner-sharing octahedra are not tilted. Both Na(1)-Se(1) bond lengths are 2.92 Å. All Na(1)-Se(2) bond lengths are 3.01 Å. Bi(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form BiSe6 octahedra that share corners with six equivalent Bi(1)Se6 octahedra, edges with four equivalent Bi(1)Se6 octahedra, and edges with eight equivalent Na(1)Se6 octahedra. The corner-sharing octahedra are not tilted. Both Bi(1)-Se(2) bond lengths are 2.92 Å. All Bi(1)-Se(1) bond lengths are 3.01 Å. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Na(1) and four equivalent Bi(1) atoms to form SeNa2Bi4 octahedra that share corners with six equivalent Se(1)Na2Bi4 octahedra, edges with four equivalent Se(1)Na2Bi4 octahedra, and edges with eight equivalent Se(2)Na4Bi2 octahedra. The corner-sharing octahedra are not tilted. In the second Se site, Se(2) is bonded to four equivalent Na(1) and two equivalent Bi(1) atoms to form SeNa4Bi2 octahedra that share corners with six equivalent Se(2)Na4Bi2 octahedra, edges with four equivalent Se(2)Na4Bi2 octahedra, and edges with eight equivalent Se(1)Na2Bi4 octahedra. The corner-sharing octahedra are not tilted.