NaSbSe2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six Se(1,1,1) atoms to form NaSe6 octahedra that share corners with two equivalent Sb(1)Se6 octahedra, corners with four equivalent Na(1)Se6 octahedra, edges with four equivalent Na(1)Se6 octahedra, and edges with eight equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Sb(1) is bonded to six Se(1,1,1) atoms to form SbSe6 octahedra that share corners with two equivalent Na(1)Se6 octahedra, corners with four equivalent Sb(1)Se6 octahedra, edges with four equivalent Sb(1)Se6 octahedra, and edges with eight equivalent Na(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SeNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Se site, Se(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SeNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third Se site, Se(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SeNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
NaSbSe2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six Se(1,1,1) atoms to form NaSe6 octahedra that share corners with two equivalent Sb(1)Se6 octahedra, corners with four equivalent Na(1)Se6 octahedra, edges with four equivalent Na(1)Se6 octahedra, and edges with eight equivalent Sb(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are four shorter (2.92 Å) and two longer (3.14 Å) Na(1)-Se(1,1,1) bond lengths. Sb(1) is bonded to six Se(1,1,1) atoms to form SbSe6 octahedra that share corners with two equivalent Na(1)Se6 octahedra, corners with four equivalent Sb(1)Se6 octahedra, edges with four equivalent Sb(1)Se6 octahedra, and edges with eight equivalent Na(1)Se6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are two shorter (2.88 Å) and four longer (2.92 Å) Sb(1)-Se(1,1,1) bond lengths. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SeNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Se site, Se(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SeNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third Se site, Se(1) is bonded to three equivalent Na(1) and three equivalent Sb(1) atoms to form a mixture of corner and edge-sharing SeNa3Sb3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.