Na4AgCl5 is Caswellsilverite-like structured and crystallizes in the orthorhombic Immm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with two equivalent Na(2)Cl6 octahedra, corners with four equivalent Na(1)Cl6 octahedra, edges with three equivalent Na(1)Cl6 octahedra, edges with four equivalent Ag(1)Cl6 octahedra, and edges with five equivalent Na(2)Cl6 octahedra. The corner-sharing octahedra are not tilted. In the second Na site, Na(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with two equivalent Na(1)Cl6 octahedra, corners with two equivalent Na(2)Cl6 octahedra, corners with two equivalent Ag(1)Cl6 octahedra,  an edgeedge with one Ag(1)Cl6 octahedra, edges with five equivalent Na(1)Cl6 octahedra, and edges with six equivalent Na(2)Cl6 octahedra. The corner-sharing octahedra are not tilted. Ag(1) is bonded to two equivalent Cl(3) and four equivalent Cl(2) atoms to form AgCl6 octahedra that share corners with two equivalent Ag(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra, edges with two equivalent Na(2)Cl6 octahedra, edges with two equivalent Ag(1)Cl6 octahedra, and edges with eight equivalent Na(1)Cl6 octahedra. The corner-sharing octahedra are not tilted. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form ClNa6 octahedra that share corners with two equivalent Cl(2)Na4Ag2 octahedra, corners with two equivalent Cl(3)Na4Ag2 octahedra, corners with two equivalent Cl(1)Na6 octahedra,  an edgeedge with one Cl(3)Na4Ag2 octahedra, edges with five equivalent Cl(2)Na4Ag2 octahedra, and edges with six equivalent Cl(1)Na6 octahedra. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Ag(1) atoms to form ClNa4Ag2 octahedra that share corners with two equivalent Cl(1)Na6 octahedra, corners with four equivalent Cl(2)Na4Ag2 octahedra, edges with three equivalent Cl(2)Na4Ag2 octahedra, edges with four equivalent Cl(3)Na4Ag2 octahedra, and edges with five equivalent Cl(1)Na6 octahedra. The corner-sharing octahedra are not tilted. In the third Cl site, Cl(3) is bonded to four equivalent Na(1) and two equivalent Ag(1) atoms to form ClNa4Ag2 octahedra that share corners with two equivalent Cl(3)Na4Ag2 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with two equivalent Cl(3)Na4Ag2 octahedra, edges with two equivalent Cl(1)Na6 octahedra, and edges with eight equivalent Cl(2)Na4Ag2 octahedra. The corner-sharing octahedra are not tilted.
Na4AgCl5 is Caswellsilverite-like structured and crystallizes in the orthorhombic Immm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with two equivalent Na(2)Cl6 octahedra, corners with four equivalent Na(1)Cl6 octahedra, edges with three equivalent Na(1)Cl6 octahedra, edges with four equivalent Ag(1)Cl6 octahedra, and edges with five equivalent Na(2)Cl6 octahedra. The corner-sharing octahedra are not tilted. Both Na(1)-Cl(1) bond lengths are 2.79 Å. Both Na(1)-Cl(2) bond lengths are 2.78 Å. Both Na(1)-Cl(3) bond lengths are 2.78 Å. In the second Na site, Na(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with two equivalent Na(1)Cl6 octahedra, corners with two equivalent Na(2)Cl6 octahedra, corners with two equivalent Ag(1)Cl6 octahedra,  an edgeedge with one Ag(1)Cl6 octahedra, edges with five equivalent Na(1)Cl6 octahedra, and edges with six equivalent Na(2)Cl6 octahedra. The corner-sharing octahedra are not tilted. Both Na(2)-Cl(2) bond lengths are 2.79 Å. There are two shorter (2.78 Å) and two longer (2.79 Å) Na(2)-Cl(1) bond lengths. Ag(1) is bonded to two equivalent Cl(3) and four equivalent Cl(2) atoms to form AgCl6 octahedra that share corners with two equivalent Ag(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra, edges with two equivalent Na(2)Cl6 octahedra, edges with two equivalent Ag(1)Cl6 octahedra, and edges with eight equivalent Na(1)Cl6 octahedra. The corner-sharing octahedra are not tilted. Both Ag(1)-Cl(3) bond lengths are 2.78 Å. All Ag(1)-Cl(2) bond lengths are 2.79 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form ClNa6 octahedra that share corners with two equivalent Cl(2)Na4Ag2 octahedra, corners with two equivalent Cl(3)Na4Ag2 octahedra, corners with two equivalent Cl(1)Na6 octahedra,  an edgeedge with one Cl(3)Na4Ag2 octahedra, edges with five equivalent Cl(2)Na4Ag2 octahedra, and edges with six equivalent Cl(1)Na6 octahedra. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Ag(1) atoms to form ClNa4Ag2 octahedra that share corners with two equivalent Cl(1)Na6 octahedra, corners with four equivalent Cl(2)Na4Ag2 octahedra, edges with three equivalent Cl(2)Na4Ag2 octahedra, edges with four equivalent Cl(3)Na4Ag2 octahedra, and edges with five equivalent Cl(1)Na6 octahedra. The corner-sharing octahedra are not tilted. In the third Cl site, Cl(3) is bonded to four equivalent Na(1) and two equivalent Ag(1) atoms to form ClNa4Ag2 octahedra that share corners with two equivalent Cl(3)Na4Ag2 octahedra, corners with four equivalent Cl(1)Na6 octahedra, edges with two equivalent Cl(3)Na4Ag2 octahedra, edges with two equivalent Cl(1)Na6 octahedra, and edges with eight equivalent Cl(2)Na4Ag2 octahedra. The corner-sharing octahedra are not tilted.