Na5BrCl4 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form NaCl6 octahedra that share corners with three equivalent Na(3)Br3Cl3 octahedra, corners with three equivalent Na(2)Cl6 octahedra, edges with three equivalent Na(3)Br3Cl3 octahedra, edges with three equivalent Na(2)Cl6 octahedra, and edges with six equivalent Na(1)Cl6 octahedra. The corner-sharing octahedra are not tilted. In the second Na site, Na(2) is bonded to six equivalent Cl(2) atoms to form a mixture of corner and edge-sharing NaCl6 octahedra. The corner-sharing octahedra are not tilted. In the third Na site, Na(3) is bonded to three equivalent Br(1) and three equivalent Cl(1) atoms to form NaBr3Cl3 octahedra that share corners with three equivalent Na(3)Br3Cl3 octahedra, corners with three equivalent Na(1)Cl6 octahedra, edges with three equivalent Na(1)Cl6 octahedra, and edges with nine equivalent Na(3)Br3Cl3 octahedra. The corner-sharing octahedra are not tilted. Br(1) is bonded to six equivalent Na(3) atoms to form BrNa6 octahedra that share corners with six equivalent Cl(1)Na6 octahedra, edges with six equivalent Br(1)Na6 octahedra, and edges with six equivalent Cl(1)Na6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to three equivalent Na(1) and three equivalent Na(3) atoms to form ClNa6 octahedra that share corners with three equivalent Br(1)Na6 octahedra, corners with three equivalent Cl(2)Na6 octahedra, edges with three equivalent Br(1)Na6 octahedra, edges with three equivalent Cl(2)Na6 octahedra, and edges with six equivalent Cl(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second Cl site, Cl(2) is bonded to three equivalent Na(1) and three equivalent Na(2) atoms to form a mixture of corner and edge-sharing ClNa6 octahedra. The corner-sharing octahedra are not tilted.
Na5BrCl4 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form NaCl6 octahedra that share corners with three equivalent Na(3)Br3Cl3 octahedra, corners with three equivalent Na(2)Cl6 octahedra, edges with three equivalent Na(3)Br3Cl3 octahedra, edges with three equivalent Na(2)Cl6 octahedra, and edges with six equivalent Na(1)Cl6 octahedra. The corner-sharing octahedra are not tilted. All Na(1)-Cl(1) bond lengths are 2.81 Å. All Na(1)-Cl(2) bond lengths are 2.81 Å. In the second Na site, Na(2) is bonded to six equivalent Cl(2) atoms to form a mixture of corner and edge-sharing NaCl6 octahedra. The corner-sharing octahedra are not tilted. All Na(2)-Cl(2) bond lengths are 2.82 Å. In the third Na site, Na(3) is bonded to three equivalent Br(1) and three equivalent Cl(1) atoms to form NaBr3Cl3 octahedra that share corners with three equivalent Na(3)Br3Cl3 octahedra, corners with three equivalent Na(1)Cl6 octahedra, edges with three equivalent Na(1)Cl6 octahedra, and edges with nine equivalent Na(3)Br3Cl3 octahedra. The corner-sharing octahedra are not tilted. All Na(3)-Br(1) bond lengths are 2.92 Å. All Na(3)-Cl(1) bond lengths are 2.81 Å. Br(1) is bonded to six equivalent Na(3) atoms to form BrNa6 octahedra that share corners with six equivalent Cl(1)Na6 octahedra, edges with six equivalent Br(1)Na6 octahedra, and edges with six equivalent Cl(1)Na6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to three equivalent Na(1) and three equivalent Na(3) atoms to form ClNa6 octahedra that share corners with three equivalent Br(1)Na6 octahedra, corners with three equivalent Cl(2)Na6 octahedra, edges with three equivalent Br(1)Na6 octahedra, edges with three equivalent Cl(2)Na6 octahedra, and edges with six equivalent Cl(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second Cl site, Cl(2) is bonded to three equivalent Na(1) and three equivalent Na(2) atoms to form a mixture of corner and edge-sharing ClNa6 octahedra. The corner-sharing octahedra are not tilted.