CsMnVF6 crystallizes in the orthorhombic Imma space group. Cs(1) is bonded to one F(1), one F(2), and four equivalent F(3) atoms to form CsF6 octahedra that share corners with six equivalent V(1)F6 octahedra and corners with six equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 65-71°. V(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and corners with six equivalent Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-71°. Mn(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and corners with six equivalent Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-71°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Cs(1) and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Cs(1), one V(1), and one Mn(1) atom.
CsMnVF6 crystallizes in the orthorhombic Imma space group. Cs(1) is bonded to one F(1), one F(2), and four equivalent F(3) atoms to form CsF6 octahedra that share corners with six equivalent V(1)F6 octahedra and corners with six equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 65-71°. The Cs(1)-F(1) bond length is 3.31 Å. The Cs(1)-F(2) bond length is 3.10 Å. All Cs(1)-F(3) bond lengths are 3.24 Å. V(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra, and corners with six equivalent Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-71°. Both V(1)-F(1) bond lengths are 1.99 Å. All V(1)-F(3) bond lengths are 1.92 Å. Mn(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form MnF6 octahedra that share corners with two equivalent Mn(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and corners with six equivalent Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-71°. Both Mn(1)-F(2) bond lengths are 2.06 Å. All Mn(1)-F(3) bond lengths are 2.11 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Cs(1) and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a 2-coordinate geometry to one Cs(1), one V(1), and one Mn(1) atom.