CaVF5 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 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 16-45°. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) 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 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 V(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one V(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 V(1) atoms.
CaVF5 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 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 16-45°. The Ca(1)-F(3) bond length is 2.22 Å. The Ca(1)-F(4) bond length is 2.23 Å. The Ca(1)-F(5) bond length is 2.40 Å. There is one shorter (2.32 Å) and one longer (2.41 Å) Ca(1)-F(1) bond length. There is one shorter (2.31 Å) and one longer (2.40 Å) Ca(1)-F(2) bond length. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), and two equivalent F(5) 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 35°. The V(1)-F(1) bond length is 1.97 Å. The V(1)-F(2) bond length is 1.94 Å. The V(1)-F(3) bond length is 1.88 Å. The V(1)-F(4) bond length is 1.88 Å. Both V(1)-F(5) bond lengths are 2.00 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 V(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Ca(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a linear geometry to one Ca(1) and one V(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 V(1) atoms.