VPbOF5 crystallizes in the orthorhombic Pbcm space group. V(1) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted VOF5 octahedra that share corners with six equivalent Pb(1)F6 pentagonal pyramids. Pb(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted PbF6 pentagonal pyramids that share corners with six equivalent V(1)OF5 octahedra and corners with two equivalent Pb(1)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 35-71°. O(1) is bonded in a single-bond geometry to one V(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Pb(1) atoms. In the second F site, F(2) is bonded in a distorted single-bond geometry to one V(1) and one Pb(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Pb(1) atom.
VPbOF5 crystallizes in the orthorhombic Pbcm space group. V(1) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted VOF5 octahedra that share corners with six equivalent Pb(1)F6 pentagonal pyramids. The V(1)-O(1) bond length is 1.60 Å. The V(1)-F(1) bond length is 2.16 Å. Both V(1)-F(2) bond lengths are 1.87 Å. Both V(1)-F(3) bond lengths are 1.87 Å. Pb(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted PbF6 pentagonal pyramids that share corners with six equivalent V(1)OF5 octahedra and corners with two equivalent Pb(1)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 35-71°. Both Pb(1)-F(1) bond lengths are 2.52 Å. Both Pb(1)-F(2) bond lengths are 2.53 Å. Both Pb(1)-F(3) bond lengths are 2.53 Å. O(1) is bonded in a single-bond geometry to one V(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Pb(1) atoms. In the second F site, F(2) is bonded in a distorted single-bond geometry to one V(1) and one Pb(1) atom. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one Pb(1) atom.