Na5Br4Cl is Caswellsilverite-like structured and crystallizes in the tetragonal I4/mmm space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to one Br(1) and five equivalent Br(2) atoms to form NaBr6 octahedra that share  a cornercorner with one Na(3)Br2Cl4 octahedra;  a cornercorner with one Na(2)Br5Cl octahedra; corners with four equivalent Na(1)Br6 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with eight Na(1,1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Na site, Na(1) is bonded to one Br(1) and five equivalent Br(2) atoms to form NaBr6 octahedra that share  a cornercorner with one Na(3)Br2Cl4 octahedra;  a cornercorner with one Na(2)Br5Cl octahedra; corners with four equivalent Na(1)Br6 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with eight Na(1,1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third Na site, Na(2) is bonded to one Br(2), four equivalent Br(1), and one Cl(1) atom to form NaBr5Cl octahedra that share  a cornercorner with one Na(1)Br6 octahedra; corners with five Na(2,2)Br5Cl octahedra; edges with four equivalent Na(3)Br2Cl4 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with four equivalent Na(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth Na site, Na(3) is bonded to two equivalent Br(1) and four equivalent Cl(1) atoms to form NaBr2Cl4 octahedra that share corners with two equivalent Na(1)Br6 octahedra; corners with four equivalent Na(3)Br2Cl4 octahedra; edges with four equivalent Na(3)Br2Cl4 octahedra; and edges with eight Na(2,2)Br5Cl octahedra. The corner-sharing octahedra are not tilted. In the fifth Na site, Na(2) is bonded to one Br(2), four equivalent Br(1), and one Cl(1) atom to form NaBr5Cl octahedra that share  a cornercorner with one Na(1)Br6 octahedra; corners with five Na(2,2)Br5Cl octahedra; edges with four equivalent Na(3)Br2Cl4 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with four equivalent Na(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to one Na(1), one Na(3), and four equivalent Na(2) atoms to form BrNa6 octahedra that share  a cornercorner with one Br(2)Na6 octahedra, corners with five equivalent Br(1)Na6 octahedra, edges with four equivalent Br(1)Na6 octahedra, edges with four equivalent Br(2)Na6 octahedra, and edges with four equivalent Cl(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Br site, Br(2) is bonded to one Na(2) and five Na(1,1) atoms to form BrNa6 octahedra that share  a cornercorner with one Br(1)Na6 octahedra,  a cornercorner with one Cl(1)Na6 octahedra, corners with four equivalent Br(2)Na6 octahedra, edges with four equivalent Br(1)Na6 octahedra, and edges with eight equivalent Br(2)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Cl(1) is bonded to two Na(2,2) and four equivalent Na(3) atoms to form ClNa6 octahedra that share corners with two equivalent Br(2)Na6 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with four equivalent Cl(1)Na6 octahedra, and edges with eight equivalent Br(1)Na6 octahedra. The corner-sharing octahedra are not tilted.
Na5Br4Cl is Caswellsilverite-like structured and crystallizes in the tetragonal I4/mmm space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded to one Br(1) and five equivalent Br(2) atoms to form NaBr6 octahedra that share  a cornercorner with one Na(3)Br2Cl4 octahedra;  a cornercorner with one Na(2)Br5Cl octahedra; corners with four equivalent Na(1)Br6 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with eight Na(1,1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Na(1)-Br(1) bond length is 2.97 Å. There are four shorter (2.94 Å) and one longer (2.96 Å) Na(1)-Br(2) bond length. In the second Na site, Na(1) is bonded to one Br(1) and five equivalent Br(2) atoms to form NaBr6 octahedra that share  a cornercorner with one Na(3)Br2Cl4 octahedra;  a cornercorner with one Na(2)Br5Cl octahedra; corners with four equivalent Na(1)Br6 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with eight Na(1,1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Na(1)-Br(1) bond length is 2.97 Å. There are four shorter (2.94 Å) and one longer (2.96 Å) Na(1)-Br(2) bond length. In the third Na site, Na(2) is bonded to one Br(2), four equivalent Br(1), and one Cl(1) atom to form NaBr5Cl octahedra that share  a cornercorner with one Na(1)Br6 octahedra; corners with five Na(2,2)Br5Cl octahedra; edges with four equivalent Na(3)Br2Cl4 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with four equivalent Na(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Na(2)-Br(2) bond length is 3.00 Å. All Na(2)-Br(1) bond lengths are 2.94 Å. The Na(2)-Cl(1) bond length is 2.84 Å. In the fourth Na site, Na(3) is bonded to two equivalent Br(1) and four equivalent Cl(1) atoms to form NaBr2Cl4 octahedra that share corners with two equivalent Na(1)Br6 octahedra; corners with four equivalent Na(3)Br2Cl4 octahedra; edges with four equivalent Na(3)Br2Cl4 octahedra; and edges with eight Na(2,2)Br5Cl octahedra. The corner-sharing octahedra are not tilted. Both Na(3)-Br(1) bond lengths are 2.90 Å. All Na(3)-Cl(1) bond lengths are 2.94 Å. In the fifth Na site, Na(2) is bonded to one Br(2), four equivalent Br(1), and one Cl(1) atom to form NaBr5Cl octahedra that share  a cornercorner with one Na(1)Br6 octahedra; corners with five Na(2,2)Br5Cl octahedra; edges with four equivalent Na(3)Br2Cl4 octahedra; edges with four equivalent Na(2)Br5Cl octahedra; and edges with four equivalent Na(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The Na(2)-Br(2) bond length is 3.00 Å. All Na(2)-Br(1) bond lengths are 2.94 Å. The Na(2)-Cl(1) bond length is 2.84 Å. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to one Na(1), one Na(3), and four equivalent Na(2) atoms to form BrNa6 octahedra that share  a cornercorner with one Br(2)Na6 octahedra, corners with five equivalent Br(1)Na6 octahedra, edges with four equivalent Br(1)Na6 octahedra, edges with four equivalent Br(2)Na6 octahedra, and edges with four equivalent Cl(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second Br site, Br(2) is bonded to one Na(2) and five Na(1,1) atoms to form BrNa6 octahedra that share  a cornercorner with one Br(1)Na6 octahedra,  a cornercorner with one Cl(1)Na6 octahedra, corners with four equivalent Br(2)Na6 octahedra, edges with four equivalent Br(1)Na6 octahedra, and edges with eight equivalent Br(2)Na6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Cl(1) is bonded to two Na(2,2) and four equivalent Na(3) atoms to form ClNa6 octahedra that share corners with two equivalent Br(2)Na6 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with four equivalent Cl(1)Na6 octahedra, and edges with eight equivalent Br(1)Na6 octahedra. The corner-sharing octahedra are not tilted.