Li4VO3F2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form LiO3F2 trigonal bipyramids that share  a cornercorner with one V(1)O3F2 trigonal bipyramid, corners with three equivalent Li(1)O3F2 trigonal bipyramids, corners with four equivalent Li(2)O3F2 trigonal bipyramids,  an edgeedge with one Li(1)O3F2 trigonal bipyramid, edges with two equivalent V(1)O3F2 trigonal bipyramids, and edges with three equivalent Li(2)O3F2 trigonal bipyramids. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form LiO3F2 trigonal bipyramids that share  a cornercorner with one Li(2)O3F2 trigonal bipyramid, corners with three equivalent V(1)O3F2 trigonal bipyramids, corners with four equivalent Li(1)O3F2 trigonal bipyramids,  an edgeedge with one V(1)O3F2 trigonal bipyramid, edges with two equivalent Li(2)O3F2 trigonal bipyramids, and edges with three equivalent Li(1)O3F2 trigonal bipyramids. V(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form VO3F2 trigonal bipyramids that share corners with two equivalent Li(1)O3F2 trigonal bipyramids, corners with six equivalent Li(2)O3F2 trigonal bipyramids, edges with two equivalent Li(2)O3F2 trigonal bipyramids, and edges with four equivalent Li(1)O3F2 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form OLi4V trigonal bipyramids that share  a cornercorner with one O(1)Li4V trigonal bipyramid, corners with three equivalent O(2)Li4V trigonal bipyramids, corners with four equivalent F(1)Li4V trigonal bipyramids,  an edgeedge with one O(2)Li4V trigonal bipyramid, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with three equivalent F(1)Li4V trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form OLi4V trigonal bipyramids that share corners with two equivalent F(1)Li4V trigonal bipyramids, corners with six equivalent O(1)Li4V trigonal bipyramids, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with four equivalent F(1)Li4V trigonal bipyramids. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form FLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li4V trigonal bipyramid, corners with three equivalent F(1)Li4V trigonal bipyramids, corners with four equivalent O(1)Li4V trigonal bipyramids,  an edgeedge with one F(1)Li4V trigonal bipyramid, edges with two equivalent O(2)Li4V trigonal bipyramids, and edges with three equivalent O(1)Li4V trigonal bipyramids.
Li4VO3F2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form LiO3F2 trigonal bipyramids that share  a cornercorner with one V(1)O3F2 trigonal bipyramid, corners with three equivalent Li(1)O3F2 trigonal bipyramids, corners with four equivalent Li(2)O3F2 trigonal bipyramids,  an edgeedge with one Li(1)O3F2 trigonal bipyramid, edges with two equivalent V(1)O3F2 trigonal bipyramids, and edges with three equivalent Li(2)O3F2 trigonal bipyramids. The Li(1)-O(2) bond length is 2.13 Å. There is one shorter (1.94 Å) and one longer (2.00 Å) Li(1)-O(1) bond length. There is one shorter (1.97 Å) and one longer (1.99 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form LiO3F2 trigonal bipyramids that share  a cornercorner with one Li(2)O3F2 trigonal bipyramid, corners with three equivalent V(1)O3F2 trigonal bipyramids, corners with four equivalent Li(1)O3F2 trigonal bipyramids,  an edgeedge with one V(1)O3F2 trigonal bipyramid, edges with two equivalent Li(2)O3F2 trigonal bipyramids, and edges with three equivalent Li(1)O3F2 trigonal bipyramids. The Li(2)-O(2) bond length is 1.97 Å. There is one shorter (1.92 Å) and one longer (2.03 Å) Li(2)-O(1) bond length. There is one shorter (1.99 Å) and one longer (2.17 Å) Li(2)-F(1) bond length. V(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form VO3F2 trigonal bipyramids that share corners with two equivalent Li(1)O3F2 trigonal bipyramids, corners with six equivalent Li(2)O3F2 trigonal bipyramids, edges with two equivalent Li(2)O3F2 trigonal bipyramids, and edges with four equivalent Li(1)O3F2 trigonal bipyramids. The V(1)-O(2) bond length is 1.73 Å. Both V(1)-O(1) bond lengths are 1.79 Å. Both V(1)-F(1) bond lengths are 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form OLi4V trigonal bipyramids that share  a cornercorner with one O(1)Li4V trigonal bipyramid, corners with three equivalent O(2)Li4V trigonal bipyramids, corners with four equivalent F(1)Li4V trigonal bipyramids,  an edgeedge with one O(2)Li4V trigonal bipyramid, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with three equivalent F(1)Li4V trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form OLi4V trigonal bipyramids that share corners with two equivalent F(1)Li4V trigonal bipyramids, corners with six equivalent O(1)Li4V trigonal bipyramids, edges with two equivalent O(1)Li4V trigonal bipyramids, and edges with four equivalent F(1)Li4V trigonal bipyramids. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form FLi4V trigonal bipyramids that share  a cornercorner with one O(2)Li4V trigonal bipyramid, corners with three equivalent F(1)Li4V trigonal bipyramids, corners with four equivalent O(1)Li4V trigonal bipyramids,  an edgeedge with one F(1)Li4V trigonal bipyramid, edges with two equivalent O(2)Li4V trigonal bipyramids, and edges with three equivalent O(1)Li4V trigonal bipyramids.