RbSF5 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 8-coordinate geometry to four equivalent F(2) and four equivalent F(3) atoms. S(1) is bonded in a square pyramidal geometry to one F(1), two equivalent F(2), and two equivalent F(3) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one S(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one S(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one S(1) atom.
RbSF5 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 8-coordinate geometry to four equivalent F(2) and four equivalent F(3) atoms. There are two shorter (2.89 Å) and two longer (2.98 Å) Rb(1)-F(2) bond lengths. There are two shorter (2.87 Å) and two longer (2.93 Å) Rb(1)-F(3) bond lengths. S(1) is bonded in a square pyramidal geometry to one F(1), two equivalent F(2), and two equivalent F(3) atoms. The S(1)-F(1) bond length is 1.61 Å. Both S(1)-F(2) bond lengths are 1.77 Å. Both S(1)-F(3) bond lengths are 1.74 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one S(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one S(1) atom. In the third F site, F(3) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one S(1) atom.