DOE OSTI2020
Li2VOF4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 6-coordinate geometry to one O2- and five F1- atoms. The Li–O bond length is 2.08 Å. There are a spread of Li–F bond distances ranging from 1.89–2.65 Å. In the second Li1+ site, Li1+ is bonded to one O2- and four F1- atoms to form distorted LiOF4 trigonal bipyramids that share a cornercorner with one VF5 square pyramid, corners with two VO2F3 trigonal bipyramids, a cornercorner with one LiF4 trigonal pyramid, and an edgeedge with one VF5 square pyramid. The Li–O bond length is 2.05 Å. There are a spread of Li–F bond distances ranging from 1.94–2.28 Å. In the third Li1+ site, Li1+ is bonded to one O2- and four F1- atoms to form LiOF4 trigonal bipyramids that share a cornercorner with one VF5 square pyramid, corners with two VOF4 trigonal bipyramids, a cornercorner with one LiF4 trigonal pyramid, and an edgeedge with one VOF4 trigonal bipyramid. The Li–O bond length is 2.09 Å. There are a spread of Li–F bond distances ranging from 1.93–2.09 Å. In the fourth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four F1- atoms. There are a spread of Li–F bond distances ranging from 1.88–2.23 Å. In the fifth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to six F1- atoms. There are a spread of Li–F bond distances ranging from 1.88–2.58 Å. In the sixth Li1+ site, Li1+ is bonded in a 5-coordinate geometry to one O2- and four F1- atoms. The Li–O bond length is 2.03 Å. There are a spread of Li–F bond distances ranging from 1.99–2.27 Å. In the seventh Li1+ site, Li1+ is bonded in a 5-coordinate geometry to one O2- and four F1- atoms. The Li–O bond length is 2.16 Å. There are a spread of Li–F bond distances ranging from 1.92–2.25 Å. In the eighth Li1+ site, Li1+ is bonded to four F1- atoms to form distorted LiF4 trigonal pyramids that share a cornercorner with one VF5 square pyramid, corners with two LiOF4 trigonal bipyramids, and corners with three VO2F3 trigonal bipyramids. There are a spread of Li–F bond distances ranging from 1.87–1.99 Å. There are four inequivalent V4+ sites. In the first V4+ site, V4+ is bonded to one O2- and four F1- atoms to form distorted VOF4 trigonal bipyramids that share a cornercorner with one LiOF4 trigonal bipyramid. The V–O bond length is 1.65 Å. There are a spread of V–F bond distances ranging from 1.92–1.97 Å. In the second V4+ site, V4+ is bonded to two O2- and three F1- atoms to form VO2F3 trigonal bipyramids that share a cornercorner with one LiOF4 trigonal bipyramid and corners with two equivalent LiF4 trigonal pyramids. There is one shorter (1.65 Å) and one longer (1.67 Å) V–O bond length. There are a spread of V–F bond distances ranging from 1.89–2.00 Å. In the third V4+ site, V4+ is bonded to five F1- atoms to form VF5 square pyramids that share corners with two LiOF4 trigonal bipyramids, a cornercorner with one LiF4 trigonal pyramid, and an edgeedge with one LiOF4 trigonal bipyramid. There are a spread of V–F bond distances ranging from 1.90–1.97 Å. In the fourth V4+ site, V4+ is bonded to one O2- and four F1- atoms to form distorted VOF4 trigonal bipyramids that share corners with two LiOF4 trigonal bipyramids, a cornercorner with one LiF4 trigonal pyramid, and an edgeedge with one LiOF4 trigonal bipyramid. The V–O bond length is 1.65 Å. There are a spread of V–F bond distances ranging from 1.92–1.96 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Li1+ and one V4+ atom. In the second O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to two Li1+ and one V4+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Li1+ and one V4+ atom. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to one Li1+ and one V4+ atom. There are sixteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to two Li1+ and one V4+ atom. In the second F1- site, F1- is bonded in a distorted trigonal planar geometry to two Li1+ and one V4+ atom. In the third F1- site, F1- is bonded in a bent 150 degrees geometry to one Li1+ and one V4+ atom. In the fourth F1- site, F1- is bonded in a trigonal non-coplanar geometry to two Li1+ and one V4+ atom. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to two Li1+ and one V4+ atom. In the sixth F1- site, F1- is bonded in a distorted trigonal planar geometry to two Li1+ and one V4+ atom. In the seventh F1- site, F1- is bonded in a 4-coordinate geometry to three Li1+ and one V4+ atom. In the eighth F1- site, F1- is bonded in a distorted trigonal pyramidal geometry to three Li1+ and one V4+ atom. In the ninth F1- site, F1- is bonded in a distorted trigonal planar geometry to two Li1+ and one V4+ atom. In the tenth F1- site, F1- is bonded in a distorted T-shaped geometry to two Li1+ and one V4+ atom. In the eleventh F1- site, F1- is bonded in a distorted trigonal planar geometry to two Li1+ and one V4+ atom. In the twelfth F1- site, F1- is bonded in a distorted trigonal planar geometry to two Li1+ and one V4+ atom. In the thirteenth F1- site, F1- is bonded in a 2-coordinate geometry to two Li1+ and one V4+ atom. In the fourteenth F1- site, F1- is bonded in a 2-coordinate geometry to two Li1+ and one V4+ atom. In the fifteenth F1- site, F1- is bonded to three Li1+ and one V4+ atom to form distorted edge-sharing FLi3V trigonal pyramids. In the sixteenth F1- site, F1- is bonded to three Li1+ and one V4+ atom to form distorted edge-sharing FLi3V trigonal pyramids.