CsSbF4 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to two equivalent F(2), two equivalent F(3), two equivalent F(4), two equivalent F(5), and four equivalent F(1) atoms. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), two equivalent F(4), and four equivalent F(5) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one F(2), two equivalent F(1), and two equivalent F(3) atoms to form distorted corner-sharing SbF5 square pyramids. In the second Sb site, Sb(2) is bonded to one F(4), two equivalent F(3), and two equivalent F(5) atoms to form distorted corner-sharing SbF5 square pyramids. There are five inequivalent F sites. In the first F site, F(4) is bonded in a single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Sb(2) atom. In the second F site, F(5) is bonded in a 4-coordinate geometry to one Cs(1), two equivalent Cs(2), and one Sb(2) atom. In the third F site, F(1) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one Sb(1) atom. In the fourth F site, F(2) is bonded in a single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Sb(1) atom. In the fifth F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cs(2), one Sb(1), and one Sb(2) atom.
CsSbF4 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to two equivalent F(2), two equivalent F(3), two equivalent F(4), two equivalent F(5), and four equivalent F(1) atoms. Both Cs(1)-F(2) bond lengths are 3.25 Å. Both Cs(1)-F(3) bond lengths are 3.19 Å. There is one shorter (3.25 Å) and one longer (3.27 Å) Cs(1)-F(4) bond length. Both Cs(1)-F(5) bond lengths are 3.15 Å. There are two shorter (3.15 Å) and two longer (3.18 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), two equivalent F(4), and four equivalent F(5) atoms. Both Cs(2)-F(1) bond lengths are 3.27 Å. There is one shorter (3.22 Å) and one longer (3.64 Å) Cs(2)-F(2) bond length. Both Cs(2)-F(3) bond lengths are 3.22 Å. Both Cs(2)-F(4) bond lengths are 3.24 Å. There are two shorter (3.01 Å) and two longer (3.08 Å) Cs(2)-F(5) bond lengths. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one F(2), two equivalent F(1), and two equivalent F(3) atoms to form distorted corner-sharing SbF5 square pyramids. The Sb(1)-F(2) bond length is 1.95 Å. Both Sb(1)-F(1) bond lengths are 2.00 Å. Both Sb(1)-F(3) bond lengths are 2.26 Å. In the second Sb site, Sb(2) is bonded to one F(4), two equivalent F(3), and two equivalent F(5) atoms to form distorted corner-sharing SbF5 square pyramids. The Sb(2)-F(4) bond length is 1.96 Å. Both Sb(2)-F(3) bond lengths are 2.23 Å. Both Sb(2)-F(5) bond lengths are 2.01 Å. There are five inequivalent F sites. In the first F site, F(4) is bonded in a single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Sb(2) atom. In the second F site, F(5) is bonded in a 4-coordinate geometry to one Cs(1), two equivalent Cs(2), and one Sb(2) atom. In the third F site, F(1) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one Sb(1) atom. In the fourth F site, F(2) is bonded in a single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Sb(1) atom. In the fifth F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cs(2), one Sb(1), and one Sb(2) atom.