MnCdF5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Mn(2)F6 octahedra, corners with four equivalent Cd(1)F7 pentagonal bipyramids, and edges with two equivalent Cd(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 37°. In the second Mn site, Mn(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(5) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent Cd(1)F7 pentagonal bipyramids, and edges with two equivalent Cd(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 37°. Cd(1) is bonded to one F(2), one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form distorted CdF7 pentagonal bipyramids that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Cd(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-38°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Mn(1) and two equivalent Cd(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Cd(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(2) and two equivalent Cd(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one Mn(1) and one Cd(1) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Mn(2) and one Cd(1) atom.
MnCdF5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Mn(2)F6 octahedra, corners with four equivalent Cd(1)F7 pentagonal bipyramids, and edges with two equivalent Cd(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 37°. Both Mn(1)-F(1) bond lengths are 1.93 Å. Both Mn(1)-F(2) bond lengths are 2.12 Å. Both Mn(1)-F(4) bond lengths are 1.87 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(5) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent Cd(1)F7 pentagonal bipyramids, and edges with two equivalent Cd(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 37°. Both Mn(2)-F(2) bond lengths are 2.12 Å. Both Mn(2)-F(3) bond lengths are 1.94 Å. Both Mn(2)-F(5) bond lengths are 1.86 Å. Cd(1) is bonded to one F(2), one F(4), one F(5), two equivalent F(1), and two equivalent F(3) atoms to form distorted CdF7 pentagonal bipyramids that share corners with two equivalent Mn(1)F6 octahedra, corners with two equivalent Mn(2)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra,  an edgeedge with one Mn(2)F6 octahedra, and edges with two equivalent Cd(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-38°. The Cd(1)-F(2) bond length is 2.27 Å. The Cd(1)-F(4) bond length is 2.22 Å. The Cd(1)-F(5) bond length is 2.22 Å. There is one shorter (2.31 Å) and one longer (2.56 Å) Cd(1)-F(1) bond length. There is one shorter (2.30 Å) and one longer (2.57 Å) Cd(1)-F(3) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Mn(1) and two equivalent Cd(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Cd(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(2) and two equivalent Cd(1) atoms. In the fourth F site, F(4) is bonded in a linear geometry to one Mn(1) and one Cd(1) atom. In the fifth F site, F(5) is bonded in a linear geometry to one Mn(2) and one Cd(1) atom.