RbNiAlF6 crystallizes in the orthorhombic Imma space group. Rb(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), and four equivalent F(3) atoms. Ni(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra and corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. Al(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Rb(1) and two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Rb(1) and two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Rb(1), one Ni(1), and one Al(1) atom.
RbNiAlF6 crystallizes in the orthorhombic Imma space group. Rb(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), and four equivalent F(3) atoms. The Rb(1)-F(1) bond length is 3.25 Å. The Rb(1)-F(2) bond length is 2.87 Å. All Rb(1)-F(3) bond lengths are 3.03 Å. Ni(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form NiF6 octahedra that share corners with two equivalent Ni(1)F6 octahedra and corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. Both Ni(1)-F(2) bond lengths are 1.97 Å. All Ni(1)-F(3) bond lengths are 2.01 Å. Al(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with four equivalent Ni(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 29-45°. Both Al(1)-F(1) bond lengths are 1.81 Å. All Al(1)-F(3) bond lengths are 1.79 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Rb(1) and two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Rb(1) and two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Rb(1), one Ni(1), and one Al(1) atom.