CaSbF5 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one F(10), one F(2), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form distorted CaF7 pentagonal bipyramids that share corners with two equivalent Sb(1)F6 octahedra, corners with two equivalent Sb(2)F6 octahedra,  an edgeedge with one Sb(1)F6 octahedra,  an edgeedge with one Sb(2)F6 octahedra, and edges with two equivalent Ca(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 3-36°. In the second Ca site, Ca(2) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form distorted CaF7 pentagonal bipyramids that share corners with two equivalent Sb(1)F6 octahedra, corners with two equivalent Sb(2)F6 octahedra,  an edgeedge with one Sb(1)F6 octahedra,  an edgeedge with one Sb(2)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-41°. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form SbF6 octahedra that share corners with two equivalent Sb(2)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 45-49°. In the second Sb site, Sb(2) is bonded to one F(1), one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form SbF6 octahedra that share corners with two equivalent Sb(1)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 45-49°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Ca(2), one Sb(1), and one Sb(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Ca(1), one Sb(1), and one Sb(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Ca(2) and one Sb(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(2) and one Sb(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sb(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Sb(2) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sb(1) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sb(2) atom. In the ninth F site, F(9) is bonded in a linear geometry to one Ca(1) and one Sb(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Ca(1) and one Sb(2) atom.
CaSbF5 crystallizes in the triclinic P1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one F(10), one F(2), one F(5), one F(6), one F(7), one F(8), and one F(9) atom to form distorted CaF7 pentagonal bipyramids that share corners with two equivalent Sb(1)F6 octahedra, corners with two equivalent Sb(2)F6 octahedra,  an edgeedge with one Sb(1)F6 octahedra,  an edgeedge with one Sb(2)F6 octahedra, and edges with two equivalent Ca(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 3-36°. The Ca(1)-F(10) bond length is 2.23 Å. The Ca(1)-F(2) bond length is 2.45 Å. The Ca(1)-F(5) bond length is 2.70 Å. The Ca(1)-F(6) bond length is 2.65 Å. The Ca(1)-F(7) bond length is 2.32 Å. The Ca(1)-F(8) bond length is 2.31 Å. The Ca(1)-F(9) bond length is 2.22 Å. In the second Ca site, Ca(2) is bonded to one F(1), one F(3), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form distorted CaF7 pentagonal bipyramids that share corners with two equivalent Sb(1)F6 octahedra, corners with two equivalent Sb(2)F6 octahedra,  an edgeedge with one Sb(1)F6 octahedra,  an edgeedge with one Sb(2)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-41°. The Ca(2)-F(1) bond length is 2.39 Å. The Ca(2)-F(3) bond length is 2.22 Å. The Ca(2)-F(4) bond length is 2.22 Å. The Ca(2)-F(5) bond length is 2.31 Å. The Ca(2)-F(6) bond length is 2.30 Å. The Ca(2)-F(7) bond length is 2.70 Å. The Ca(2)-F(8) bond length is 2.78 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one F(1), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form SbF6 octahedra that share corners with two equivalent Sb(2)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 45-49°. The Sb(1)-F(1) bond length is 2.20 Å. The Sb(1)-F(2) bond length is 2.32 Å. The Sb(1)-F(4) bond length is 2.16 Å. The Sb(1)-F(5) bond length is 2.24 Å. The Sb(1)-F(7) bond length is 2.19 Å. The Sb(1)-F(9) bond length is 2.14 Å. In the second Sb site, Sb(2) is bonded to one F(1), one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form SbF6 octahedra that share corners with two equivalent Sb(1)F6 octahedra, corners with two equivalent Ca(1)F7 pentagonal bipyramids, corners with two equivalent Ca(2)F7 pentagonal bipyramids,  an edgeedge with one Ca(1)F7 pentagonal bipyramid, and  an edgeedge with one Ca(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 45-49°. The Sb(2)-F(1) bond length is 2.33 Å. The Sb(2)-F(10) bond length is 2.15 Å. The Sb(2)-F(2) bond length is 2.19 Å. The Sb(2)-F(3) bond length is 2.15 Å. The Sb(2)-F(6) bond length is 2.23 Å. The Sb(2)-F(8) bond length is 2.19 Å. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Ca(2), one Sb(1), and one Sb(2) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Ca(1), one Sb(1), and one Sb(2) atom. In the third F site, F(3) is bonded in a linear geometry to one Ca(2) and one Sb(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(2) and one Sb(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sb(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Sb(2) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sb(1) atom. In the eighth F site, F(8) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one Sb(2) atom. In the ninth F site, F(9) is bonded in a linear geometry to one Ca(1) and one Sb(1) atom. In the tenth F site, F(10) is bonded in a linear geometry to one Ca(1) and one Sb(2) atom.