Na8Zr6BBr20 crystallizes in the cubic Fm-3m space group. Na(1) is bonded in a 4-coordinate geometry to one Br(3) and three equivalent Br(2) atoms. Zr(1) is bonded to one B(1), one Br(2), and four equivalent Br(1) atoms to form a mixture of corner and edge-sharing ZrBBr5 octahedra. The corner-sharing octahedra are not tilted. B(1) is bonded to six equivalent Zr(1) atoms to form BZr6 octahedra that share corners with six equivalent Br(2)Na4Zr square pyramids. There are three inequivalent Br sites. In the first Br site, Br(2) is bonded to four equivalent Na(1) and one Zr(1) atom to form BrNa4Zr square pyramids that share  a cornercorner with one B(1)Zr6 octahedra, corners with four equivalent Br(3)Na4 tetrahedra, and edges with four equivalent Br(2)Na4Zr square pyramids. The corner-sharing octahedra are not tilted. In the second Br site, Br(3) is bonded to four equivalent Na(1) atoms to form corner-sharing BrNa4 tetrahedra. In the third Br site, Br(1) is bonded in a 2-coordinate geometry to two equivalent Zr(1) atoms.
Na8Zr6BBr20 crystallizes in the cubic Fm-3m space group. Na(1) is bonded in a 4-coordinate geometry to one Br(3) and three equivalent Br(2) atoms. The Na(1)-Br(3) bond length is 3.04 Å. All Na(1)-Br(2) bond lengths are 3.18 Å. Zr(1) is bonded to one B(1), one Br(2), and four equivalent Br(1) atoms to form a mixture of corner and edge-sharing ZrBBr5 octahedra. The corner-sharing octahedra are not tilted. The Zr(1)-B(1) bond length is 2.32 Å. The Zr(1)-Br(2) bond length is 2.88 Å. All Zr(1)-Br(1) bond lengths are 2.73 Å. B(1) is bonded to six equivalent Zr(1) atoms to form BZr6 octahedra that share corners with six equivalent Br(2)Na4Zr square pyramids. There are three inequivalent Br sites. In the first Br site, Br(2) is bonded to four equivalent Na(1) and one Zr(1) atom to form BrNa4Zr square pyramids that share  a cornercorner with one B(1)Zr6 octahedra, corners with four equivalent Br(3)Na4 tetrahedra, and edges with four equivalent Br(2)Na4Zr square pyramids. The corner-sharing octahedra are not tilted. In the second Br site, Br(3) is bonded to four equivalent Na(1) atoms to form corner-sharing BrNa4 tetrahedra. In the third Br site, Br(1) is bonded in a 2-coordinate geometry to two equivalent Zr(1) atoms.