CaAlF5 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to one F(2), one F(3), one F(4), two equivalent F(1), and two equivalent F(5) atoms to form distorted CaF7 pentagonal bipyramids that share corners with four equivalent Al(1)F6 octahedra, edges with two equivalent Al(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 15-44°. Al(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 25°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Al(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Al(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Al(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Al(1) atom.
CaAlF5 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to one F(2), one F(3), one F(4), two equivalent F(1), and two equivalent F(5) atoms to form distorted CaF7 pentagonal bipyramids that share corners with four equivalent Al(1)F6 octahedra, edges with two equivalent Al(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 15-44°. The Ca(1)-F(2) bond length is 2.52 Å. The Ca(1)-F(3) bond length is 2.22 Å. The Ca(1)-F(4) bond length is 2.21 Å. There is one shorter (2.29 Å) and one longer (2.32 Å) Ca(1)-F(1) bond length. There is one shorter (2.31 Å) and one longer (2.34 Å) Ca(1)-F(5) bond length. Al(1) is bonded to one F(1), one F(3), one F(4), one F(5), and two equivalent F(2) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra, corners with four equivalent Ca(1)F7 pentagonal bipyramids, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 25°. The Al(1)-F(1) bond length is 1.81 Å. The Al(1)-F(3) bond length is 1.75 Å. The Al(1)-F(4) bond length is 1.75 Å. The Al(1)-F(5) bond length is 1.83 Å. Both Al(1)-F(2) bond lengths are 1.87 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Al(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Ca(1) and two equivalent Al(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Al(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Al(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Al(1) atom.