LiV2H4(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(2), one F(3), one F(4), one F(8), and one F(9) atom to form distorted LiF5 trigonal bipyramids that share  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-51°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(2), one F(5), one F(7), and one F(8) atom to form VOF5 octahedra that share corners with two equivalent Li(1)F5 trigonal bipyramids. In the second V site, V(2) is bonded to one O(1), one F(10), one F(3), one F(4), one F(6), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F5 trigonal bipyramid and  an edgeedge with one Li(1)F5 trigonal bipyramid. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. In the third H site, H(3) is bonded in a linear geometry to one O(2) and one F(6) atom. In the fourth H site, H(4) is bonded in a linear geometry to one O(2) and one F(9) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one V(2), one H(1), and one H(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one H(3), and one H(4) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the fourth F site, F(4) is bonded in an L-shaped geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(1) atom. In the sixth F site, F(6) is bonded in a bent 120 degrees geometry to one V(2) and one H(3) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one V(1) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one H(4) atom. In the tenth F site, F(10) is bonded in a single-bond geometry to one V(2) atom.
LiV2H4(OF5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(2), one F(3), one F(4), one F(8), and one F(9) atom to form distorted LiF5 trigonal bipyramids that share  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-51°. The Li(1)-F(2) bond length is 2.31 Å. The Li(1)-F(3) bond length is 1.94 Å. The Li(1)-F(4) bond length is 2.28 Å. The Li(1)-F(8) bond length is 2.11 Å. The Li(1)-F(9) bond length is 1.97 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(2), one F(5), one F(7), and one F(8) atom to form VOF5 octahedra that share corners with two equivalent Li(1)F5 trigonal bipyramids. The V(1)-O(2) bond length is 1.98 Å. The V(1)-F(1) bond length is 1.77 Å. The V(1)-F(2) bond length is 1.85 Å. The V(1)-F(5) bond length is 1.80 Å. The V(1)-F(7) bond length is 1.76 Å. The V(1)-F(8) bond length is 1.83 Å. In the second V site, V(2) is bonded to one O(1), one F(10), one F(3), one F(4), one F(6), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F5 trigonal bipyramid and  an edgeedge with one Li(1)F5 trigonal bipyramid. The V(2)-O(1) bond length is 2.08 Å. The V(2)-F(10) bond length is 1.79 Å. The V(2)-F(3) bond length is 1.85 Å. The V(2)-F(4) bond length is 1.85 Å. The V(2)-F(6) bond length is 1.87 Å. The V(2)-F(9) bond length is 1.98 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. The H(2)-O(1) bond length is 0.98 Å. In the third H site, H(3) is bonded in a linear geometry to one O(2) and one F(6) atom. The H(3)-O(2) bond length is 1.01 Å. The H(3)-F(6) bond length is 1.51 Å. In the fourth H site, H(4) is bonded in a linear geometry to one O(2) and one F(9) atom. The H(4)-O(2) bond length is 1.02 Å. The H(4)-F(9) bond length is 1.49 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to one V(2), one H(1), and one H(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one H(3), and one H(4) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the fourth F site, F(4) is bonded in an L-shaped geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(1) atom. In the sixth F site, F(6) is bonded in a bent 120 degrees geometry to one V(2) and one H(3) atom. In the seventh F site, F(7) is bonded in a single-bond geometry to one V(1) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the ninth F site, F(9) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one H(4) atom. In the tenth F site, F(10) is bonded in a single-bond geometry to one V(2) atom.