Na6MnCl8 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 Mn(1)Cl6 octahedra, and edges with eight equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Mn(1) is bonded to six equivalent Cl(2) atoms to form MnCl6 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)Na4Mn 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 Mn(1) atom to form ClNa4Mn square pyramids that share corners with nine equivalent Cl(2)Na4Mn square pyramids, edges with four equivalent Cl(1)Na6 octahedra, and edges with four equivalent Cl(2)Na4Mn square pyramids.
Na6MnCl8 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 Mn(1)Cl6 octahedra, and edges with eight equivalent Na(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Na(1)-Cl(1) bond lengths are 2.78 Å. All Na(1)-Cl(2) bond lengths are 2.79 Å. Mn(1) is bonded to six equivalent Cl(2) atoms to form MnCl6 octahedra that share edges with twelve equivalent Na(1)Cl6 octahedra. All Mn(1)-Cl(2) bond lengths are 2.56 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)Na4Mn 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 Mn(1) atom to form ClNa4Mn square pyramids that share corners with nine equivalent Cl(2)Na4Mn square pyramids, edges with four equivalent Cl(1)Na6 octahedra, and edges with four equivalent Cl(2)Na4Mn square pyramids.