V3F10 crystallizes in the monoclinic Pc space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(10), one F(4), one F(5), one F(9), and two equivalent F(8) atoms to form VF7 pentagonal bipyramids that share  a cornercorner with one V(3)F7 pentagonal bipyramid, corners with two equivalent V(1)F7 pentagonal bipyramids,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one V(3)F7 pentagonal bipyramid. In the second V site, V(2) is bonded to one F(10), one F(2), one F(3), one F(4), and two equivalent F(6) atoms to form distorted VF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(3)F7 pentagonal bipyramids, and  an edgeedge with one V(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 8°. In the third V site, V(3) is bonded to one F(1), one F(2), one F(3), one F(5), one F(9), and two equivalent F(7) atoms to form VF7 pentagonal bipyramids that share corners with two equivalent V(2)F6 octahedra,  a cornercorner with one V(1)F7 pentagonal bipyramid, corners with two equivalent V(3)F7 pentagonal bipyramids, and  an edgeedge with one V(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 4-48°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(1) and one V(3) atom. In the second F site, F(2) is bonded in a linear geometry to one V(2) and one V(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one V(2) and one V(3) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to two equivalent V(2) atoms. In the seventh F site, F(7) is bonded in a linear geometry to two equivalent V(3) atoms. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(1) atoms. In the ninth F site, F(9) is bonded in a distorted water-like geometry to one V(1) and one V(3) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one V(1) and one V(2) atom.
V3F10 crystallizes in the monoclinic Pc space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(10), one F(4), one F(5), one F(9), and two equivalent F(8) atoms to form VF7 pentagonal bipyramids that share  a cornercorner with one V(3)F7 pentagonal bipyramid, corners with two equivalent V(1)F7 pentagonal bipyramids,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one V(3)F7 pentagonal bipyramid. The V(1)-F(1) bond length is 1.96 Å. The V(1)-F(10) bond length is 2.00 Å. The V(1)-F(4) bond length is 2.05 Å. The V(1)-F(5) bond length is 2.02 Å. The V(1)-F(9) bond length is 2.08 Å. Both V(1)-F(8) bond lengths are 1.97 Å. In the second V site, V(2) is bonded to one F(10), one F(2), one F(3), one F(4), and two equivalent F(6) atoms to form distorted VF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent V(3)F7 pentagonal bipyramids, and  an edgeedge with one V(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 8°. The V(2)-F(10) bond length is 2.00 Å. The V(2)-F(2) bond length is 1.96 Å. The V(2)-F(3) bond length is 2.06 Å. The V(2)-F(4) bond length is 1.96 Å. There is one shorter (1.96 Å) and one longer (2.00 Å) V(2)-F(6) bond length. In the third V site, V(3) is bonded to one F(1), one F(2), one F(3), one F(5), one F(9), and two equivalent F(7) atoms to form VF7 pentagonal bipyramids that share corners with two equivalent V(2)F6 octahedra,  a cornercorner with one V(1)F7 pentagonal bipyramid, corners with two equivalent V(3)F7 pentagonal bipyramids, and  an edgeedge with one V(1)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 4-48°. The V(3)-F(1) bond length is 1.99 Å. The V(3)-F(2) bond length is 2.01 Å. The V(3)-F(3) bond length is 1.92 Å. The V(3)-F(5) bond length is 1.97 Å. The V(3)-F(9) bond length is 2.05 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) V(3)-F(7) bond length. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(1) and one V(3) atom. In the second F site, F(2) is bonded in a linear geometry to one V(2) and one V(3) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one V(2) and one V(3) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to two equivalent V(2) atoms. In the seventh F site, F(7) is bonded in a linear geometry to two equivalent V(3) atoms. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(1) atoms. In the ninth F site, F(9) is bonded in a distorted water-like geometry to one V(1) and one V(3) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one V(1) and one V(2) atom.