RbAlF4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to eight equivalent F(1) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to two equivalent F(3) and eight equivalent F(1) atoms. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles range from 20-23°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Al(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Rb(2) and two equivalent Al(1) atoms.
RbAlF4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to eight equivalent F(1) atoms. There are four shorter (2.88 Å) and four longer (2.93 Å) Rb(1)-F(1) bond lengths. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to two equivalent F(3) and eight equivalent F(1) atoms. Both Rb(2)-F(3) bond lengths are 3.18 Å. There are four shorter (2.88 Å) and four longer (2.92 Å) Rb(2)-F(1) bond lengths. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles range from 20-23°. Both Al(1)-F(1) bond lengths are 1.76 Å. Both Al(1)-F(2) bond lengths are 1.83 Å. Both Al(1)-F(3) bond lengths are 1.84 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Al(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Rb(2) and two equivalent Al(1) atoms.