CaMnF5 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 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 17-46°. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) 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 35°. 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 Mn(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Mn(1) atoms.
CaMnF5 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 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 17-46°. The Ca(1)-F(3) bond length is 2.24 Å. The Ca(1)-F(4) bond length is 2.22 Å. The Ca(1)-F(5) bond length is 2.29 Å. There is one shorter (2.33 Å) and one longer (2.48 Å) Ca(1)-F(1) bond length. There is one shorter (2.33 Å) and one longer (2.45 Å) Ca(1)-F(2) bond length. Mn(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) 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 35°. The Mn(1)-F(1) bond length is 1.91 Å. The Mn(1)-F(2) bond length is 1.88 Å. The Mn(1)-F(3) bond length is 1.83 Å. The Mn(1)-F(4) bond length is 1.84 Å. Both Mn(1)-F(5) bond lengths are 2.08 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 Mn(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one Mn(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one Mn(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one Mn(1) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Mn(1) atoms.