CaVF5 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 V(1)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 3-37°. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(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 three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Ca(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one V(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one V(1) atom.
CaVF5 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 V(1)F6 octahedra, edges with two equivalent V(1)F6 octahedra, and edges with two equivalent Ca(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 3-37°. The Ca(1)-F(1) bond length is 2.36 Å. Both Ca(1)-F(2) bond lengths are 2.22 Å. There are two shorter (2.31 Å) and two longer (2.43 Å) Ca(1)-F(3) bond lengths. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(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°. Both V(1)-F(1) bond lengths are 2.00 Å. Both V(1)-F(2) bond lengths are 1.89 Å. Both V(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 3-coordinate geometry to one Ca(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Ca(1) and one V(1) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one V(1) atom.