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(6), one F(7), one F(8), and one F(9) atom to form distorted CaF6 octahedra that share corners with two equivalent Ca(2)F6 octahedra, corners with two equivalent Sb(1)F5 square pyramids, corners with two equivalent Sb(2)F5 square pyramids, and  an edgeedge with one Sb(2)F5 square pyramid. The corner-sharing octahedral tilt angles range from 43-44°. 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), and one F(7) atom to form distorted CaF6 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Sb(1)F5 square pyramids, corners with two equivalent Sb(2)F5 square pyramids, and  an edgeedge with one Sb(1)F5 square pyramid. The corner-sharing octahedral tilt angles range from 43-44°. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one F(1), one F(4), one F(5), one F(7), and one F(9) atom to form distorted SbF5 square pyramids that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Ca(2)F6 octahedra, and  an edgeedge with one Ca(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-62°. In the second Sb site, Sb(2) is bonded to one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form distorted SbF5 square pyramids that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Ca(2)F6 octahedra, and  an edgeedge with one Ca(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-63°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one Ca(2) and one Sb(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ca(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 bent 150 degrees geometry to one Ca(2) and one Sb(1) atom. In the fifth F site, F(5) is bonded in a linear geometry to 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 distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Sb(1) atom. In the eighth F site, F(8) is bonded in a linear geometry to one Ca(1) and one Sb(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Ca(1) and one Sb(1) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees 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(6), one F(7), one F(8), and one F(9) atom to form distorted CaF6 octahedra that share corners with two equivalent Ca(2)F6 octahedra, corners with two equivalent Sb(1)F5 square pyramids, corners with two equivalent Sb(2)F5 square pyramids, and  an edgeedge with one Sb(2)F5 square pyramid. The corner-sharing octahedral tilt angles range from 43-44°. The Ca(1)-F(10) bond length is 2.23 Å. The Ca(1)-F(2) bond length is 2.38 Å. The Ca(1)-F(6) bond length is 2.33 Å. The Ca(1)-F(7) bond length is 2.29 Å. The Ca(1)-F(8) bond length is 2.28 Å. The Ca(1)-F(9) bond length is 2.24 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), and one F(7) atom to form distorted CaF6 octahedra that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Sb(1)F5 square pyramids, corners with two equivalent Sb(2)F5 square pyramids, and  an edgeedge with one Sb(1)F5 square pyramid. The corner-sharing octahedral tilt angles range from 43-44°. The Ca(2)-F(1) bond length is 2.39 Å. The Ca(2)-F(3) bond length is 2.25 Å. The Ca(2)-F(4) bond length is 2.24 Å. The Ca(2)-F(5) bond length is 2.28 Å. The Ca(2)-F(6) bond length is 2.30 Å. The Ca(2)-F(7) bond length is 2.30 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one F(1), one F(4), one F(5), one F(7), and one F(9) atom to form distorted SbF5 square pyramids that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Ca(2)F6 octahedra, and  an edgeedge with one Ca(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 6-62°. The Sb(1)-F(1) bond length is 2.03 Å. The Sb(1)-F(4) bond length is 2.13 Å. The Sb(1)-F(5) bond length is 2.06 Å. The Sb(1)-F(7) bond length is 2.35 Å. The Sb(1)-F(9) bond length is 2.11 Å. In the second Sb site, Sb(2) is bonded to one F(10), one F(2), one F(3), one F(6), and one F(8) atom to form distorted SbF5 square pyramids that share corners with two equivalent Ca(1)F6 octahedra, corners with two equivalent Ca(2)F6 octahedra, and  an edgeedge with one Ca(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 10-63°. The Sb(2)-F(10) bond length is 2.13 Å. The Sb(2)-F(2) bond length is 2.03 Å. The Sb(2)-F(3) bond length is 2.11 Å. The Sb(2)-F(6) bond length is 2.36 Å. The Sb(2)-F(8) bond length is 2.06 Å. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one Ca(2) and one Sb(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ca(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 bent 150 degrees geometry to one Ca(2) and one Sb(1) atom. In the fifth F site, F(5) is bonded in a linear geometry to 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 distorted trigonal planar geometry to one Ca(1), one Ca(2), and one Sb(1) atom. In the eighth F site, F(8) is bonded in a linear geometry to one Ca(1) and one Sb(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Ca(1) and one Sb(1) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one Ca(1) and one Sb(2) atom.