CaMnF5 crystallizes in the monoclinic C2/c space group. Ca(1) is bonded to one F(1), two equivalent F(2), and four equivalent F(3) atoms to form CaF7 pentagonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-38°. Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with two equivalent Mn(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 34°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Mn(1) atom.
CaMnF5 crystallizes in the monoclinic C2/c space group. Ca(1) is bonded to one F(1), two equivalent F(2), and four equivalent F(3) atoms to form CaF7 pentagonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-38°. The Ca(1)-F(1) bond length is 2.32 Å. Both Ca(1)-F(2) bond lengths are 2.24 Å. There are two shorter (2.30 Å) and two longer (2.45 Å) Ca(1)-F(3) bond lengths. Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with two equivalent Mn(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 34°. Both Mn(1)-F(1) bond lengths are 2.04 Å. Both Mn(1)-F(2) bond lengths are 1.82 Å. Both Mn(1)-F(3) bond lengths are 1.94 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Mn(1) atom.