LiV3(O2F)2 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), and two equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form a mixture of corner and edge-sharing OLiV3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OLiV3 tetrahedra. F(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms.
LiV3(O2F)2 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-O(3) bond length is 1.82 Å. Both Li(1)-O(2) bond lengths are 1.97 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(3) bond length is 2.01 Å. Both V(1)-O(2) bond lengths are 2.05 Å. Both V(1)-F(1) bond lengths are 2.16 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The V(2)-O(1) bond length is 2.05 Å. The V(2)-O(3) bond length is 2.00 Å. There is one shorter (1.98 Å) and one longer (2.00 Å) V(2)-O(2) bond length. There is one shorter (2.11 Å) and one longer (2.16 Å) V(2)-F(1) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form a mixture of corner and edge-sharing OLiV3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OLiV3 tetrahedra. F(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(2) atoms.