Na6MgCl8 crystallizes in the cubic Fm-3m space group. Na(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form NaCl6 octahedra that share corners with six equivalent Na(1)Cl6 octahedra, edges with two equivalent Mg(1)Cl6 octahedra, and edges with eight equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. Mg(1) is bonded to six equivalent Cl(2) atoms to form MgCl6 octahedra that share edges with twelve equivalent Na(1)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to six equivalent Na(1) atoms to form ClNa6 octahedra that share corners with six equivalent Cl(1)Na6 octahedra and edges with twelve equivalent Cl(2)Na4Mg square pyramids. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(2) is bonded to four equivalent Na(1) and one Mg(1) atom to form ClNa4Mg square pyramids that share corners with nine equivalent Cl(2)Na4Mg square pyramids, edges with four equivalent Cl(1)Na6 octahedra, and edges with four equivalent Cl(2)Na4Mg square pyramids.
Na6MgCl8 crystallizes in the cubic Fm-3m space group. Na(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form NaCl6 octahedra that share corners with six equivalent Na(1)Cl6 octahedra, edges with two equivalent Mg(1)Cl6 octahedra, and edges with eight equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. Both Na(1)-Cl(1) bond lengths are 2.78 Å. All Na(1)-Cl(2) bond lengths are 2.79 Å. Mg(1) is bonded to six equivalent Cl(2) atoms to form MgCl6 octahedra that share edges with twelve equivalent Na(1)Cl6 octahedra. All Mg(1)-Cl(2) bond lengths are 2.53 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to six equivalent Na(1) atoms to form ClNa6 octahedra that share corners with six equivalent Cl(1)Na6 octahedra and edges with twelve equivalent Cl(2)Na4Mg square pyramids. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(2) is bonded to four equivalent Na(1) and one Mg(1) atom to form ClNa4Mg square pyramids that share corners with nine equivalent Cl(2)Na4Mg square pyramids, edges with four equivalent Cl(1)Na6 octahedra, and edges with four equivalent Cl(2)Na4Mg square pyramids.