Li2V(OF)2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom. In the second Li site, Li(2) is bonded to one O(1), one O(4), one F(1), one F(2), one F(3), and one F(4) atom to form distorted LiO2F4 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent Li(4)O3F3 octahedra, and edges with three equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one F(1), one F(2), one F(3), and one F(4) atom. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent Li(2)O2F4 octahedra, and edges with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(4), two equivalent O(1), one F(1), and two equivalent F(4) atoms to form distorted VO3F3 octahedra that share corners with two equivalent Li(4)O3F3 octahedra, edges with two equivalent V(1)O3F3 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, edges with two equivalent V(2)O4F2 octahedra, and edges with three equivalent Li(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with two equivalent O(1)Li2V2 trigonal pyramids, corners with two equivalent F(4)Li2V2 trigonal pyramids, and edges with two equivalent F(4)Li2V2 trigonal pyramids. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom. In the fourth F site, F(4) is bonded to one Li(2), one Li(3), and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent O(1)Li2V2 trigonal pyramids, corners with two equivalent F(4)Li2V2 trigonal pyramids, and edges with two equivalent O(1)Li2V2 trigonal pyramids.
Li2V(OF)2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.95 Å. The Li(1)-O(4) bond length is 2.43 Å. The Li(1)-F(1) bond length is 2.33 Å. The Li(1)-F(2) bond length is 2.39 Å. The Li(1)-F(3) bond length is 2.37 Å. In the second Li site, Li(2) is bonded to one O(1), one O(4), one F(1), one F(2), one F(3), and one F(4) atom to form distorted LiO2F4 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent Li(4)O3F3 octahedra, and edges with three equivalent V(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Li(2)-O(1) bond length is 2.22 Å. The Li(2)-O(4) bond length is 2.15 Å. The Li(2)-F(1) bond length is 2.15 Å. The Li(2)-F(2) bond length is 1.94 Å. The Li(2)-F(3) bond length is 1.94 Å. The Li(2)-F(4) bond length is 2.20 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one F(1), one F(2), one F(3), and one F(4) atom. The Li(3)-O(1) bond length is 1.98 Å. The Li(3)-O(4) bond length is 2.23 Å. The Li(3)-F(1) bond length is 2.38 Å. The Li(3)-F(2) bond length is 2.25 Å. The Li(3)-F(3) bond length is 2.40 Å. The Li(3)-F(4) bond length is 1.99 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form distorted LiO3F3 octahedra that share corners with two equivalent V(1)O3F3 octahedra, corners with four equivalent Li(2)O2F4 octahedra, and edges with three equivalent V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. The Li(4)-O(2) bond length is 2.31 Å. The Li(4)-O(3) bond length is 2.25 Å. The Li(4)-O(4) bond length is 1.99 Å. The Li(4)-F(1) bond length is 1.97 Å. The Li(4)-F(2) bond length is 2.08 Å. The Li(4)-F(3) bond length is 2.05 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(4), two equivalent O(1), one F(1), and two equivalent F(4) atoms to form distorted VO3F3 octahedra that share corners with two equivalent Li(4)O3F3 octahedra, edges with two equivalent V(1)O3F3 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 43-57°. The V(1)-O(4) bond length is 1.75 Å. There is one shorter (1.86 Å) and one longer (1.96 Å) V(1)-O(1) bond length. The V(1)-F(1) bond length is 2.00 Å. There is one shorter (2.04 Å) and one longer (2.20 Å) V(1)-F(4) bond length. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, edges with two equivalent V(2)O4F2 octahedra, and edges with three equivalent Li(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. There is one shorter (1.83 Å) and one longer (1.98 Å) V(2)-O(2) bond length. There is one shorter (1.83 Å) and one longer (1.98 Å) V(2)-O(3) bond length. The V(2)-F(2) bond length is 2.09 Å. The V(2)-F(3) bond length is 2.08 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with two equivalent O(1)Li2V2 trigonal pyramids, corners with two equivalent F(4)Li2V2 trigonal pyramids, and edges with two equivalent F(4)Li2V2 trigonal pyramids. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(2) atom. In the fourth F site, F(4) is bonded to one Li(2), one Li(3), and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with two equivalent O(1)Li2V2 trigonal pyramids, corners with two equivalent F(4)Li2V2 trigonal pyramids, and edges with two equivalent O(1)Li2V2 trigonal pyramids.