CaFeF5 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted CaF7 pentagonal bipyramids that share corners with four equivalent Fe(1)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 16-46°. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(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 33°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Fe(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ca(1) and two equivalent Fe(1) atoms.
CaFeF5 crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to one F(3), one F(4), one F(5), two equivalent F(1), and two equivalent F(2) atoms to form distorted CaF7 pentagonal bipyramids that share corners with four equivalent Fe(1)F6 octahedra, edges with two equivalent Fe(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 16-46°. The Ca(1)-F(3) bond length is 2.23 Å. The Ca(1)-F(4) bond length is 2.23 Å. The Ca(1)-F(5) bond length is 2.43 Å. There is one shorter (2.31 Å) and one longer (2.40 Å) Ca(1)-F(1) bond length. There is one shorter (2.29 Å) and one longer (2.39 Å) Ca(1)-F(2) bond length. Fe(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(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 33°. The Fe(1)-F(1) bond length is 1.98 Å. The Fe(1)-F(2) bond length is 1.95 Å. The Fe(1)-F(3) bond length is 1.87 Å. The Fe(1)-F(4) bond length is 1.87 Å. Both Fe(1)-F(5) bond lengths are 1.98 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Fe(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ca(1) and one Fe(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Fe(1) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Ca(1) and two equivalent Fe(1) atoms.