Cs2SbF5 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to four equivalent F(2) and eight equivalent F(1) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one F(2) and eight equivalent F(1) atoms. Sb(1) is bonded in a square pyramidal geometry to one F(2) and four equivalent F(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Sb(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Cs(2), four equivalent Cs(1), and one Sb(1) atom.
Cs2SbF5 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to four equivalent F(2) and eight equivalent F(1) atoms. There are two shorter (3.35 Å) and two longer (3.58 Å) Cs(1)-F(2) bond lengths. There are four shorter (3.11 Å) and four longer (3.16 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one F(2) and eight equivalent F(1) atoms. The Cs(2)-F(2) bond length is 3.05 Å. There are four shorter (2.95 Å) and four longer (3.39 Å) Cs(2)-F(1) bond lengths. Sb(1) is bonded in a square pyramidal geometry to one F(2) and four equivalent F(1) atoms. The Sb(1)-F(2) bond length is 1.97 Å. All Sb(1)-F(1) bond lengths are 2.09 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Sb(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Cs(2), four equivalent Cs(1), and one Sb(1) atom.