DOE OSTI2020
Li11V6O5F19 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eleven 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 2.00 Å. There are a spread of Li–F bond distances ranging from 1.92–2.54 Å. In the second Li1+ site, Li1+ is bonded in a 4-coordinate geometry to two O2- and four F1- atoms. There are one shorter (2.47 Å) and one longer (2.70 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.93–2.17 Å. In the third Li1+ site, Li1+ is bonded in a 3-coordinate geometry to four F1- atoms. There are a spread of Li–F bond distances ranging from 1.86–2.47 Å. In the fourth Li1+ site, Li1+ is bonded in a 3-coordinate geometry to two O2- and four F1- atoms. There are one shorter (2.00 Å) and one longer (2.60 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.93–2.57 Å. In the fifth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to two O2- and four F1- atoms. There are one shorter (2.35 Å) and one longer (2.49 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.98–2.15 Å. In the sixth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to two O2- and four F1- atoms. There are one shorter (1.98 Å) and one longer (2.32 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.96–2.50 Å. In the seventh Li1+ site, Li1+ is bonded in a 6-coordinate geometry to one O2- and five F1- atoms. The Li–O bond length is 2.42 Å. There are a spread of Li–F bond distances ranging from 1.87–2.49 Å. In the eighth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to one O2- and four F1- atoms. The Li–O bond length is 2.49 Å. There are a spread of Li–F bond distances ranging from 1.86–2.08 Å. In the ninth Li1+ site, Li1+ is bonded in a 4-coordinate geometry to one O2- and five F1- atoms. The Li–O bond length is 2.01 Å. There are a spread of Li–F bond distances ranging from 1.88–2.66 Å. In the tenth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to one O2- and five F1- atoms. The Li–O bond length is 1.99 Å. There are a spread of Li–F bond distances ranging from 1.93–2.49 Å. In the eleventh Li1+ site, Li1+ is bonded in a 6-coordinate geometry to one O2- and five F1- atoms. The Li–O bond length is 2.33 Å. There are a spread of Li–F bond distances ranging from 1.93–2.69 Å. There are six inequivalent V3+ sites. In the first V3+ site, V3+ is bonded to two O2- and four F1- atoms to form corner-sharing VO2F4 octahedra. The corner-sharing octahedra tilt angles range from 40–47°. There is one shorter (1.89 Å) and one longer (1.93 Å) V–O bond length. There are a spread of V–F bond distances ranging from 2.00–2.15 Å. In the second V3+ site, V3+ is bonded to one O2- and five F1- atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedra tilt angles range from 39–49°. The V–O bond length is 1.90 Å. There are a spread of V–F bond distances ranging from 1.96–2.10 Å. In the third V3+ site, V3+ is bonded to two O2- and four F1- atoms to form corner-sharing VO2F4 octahedra. The corner-sharing octahedra tilt angles range from 34–50°. Both V–O bond lengths are 1.95 Å. There are a spread of V–F bond distances ranging from 2.02–2.07 Å. In the fourth V3+ site, V3+ is bonded to one O2- and five F1- atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedra tilt angles range from 39–49°. The V–O bond length is 1.91 Å. There are a spread of V–F bond distances ranging from 1.90–2.16 Å. In the fifth V3+ site, V3+ is bonded to two O2- and four F1- atoms to form corner-sharing VO2F4 octahedra. The corner-sharing octahedra tilt angles range from 40–47°. There is one shorter (1.89 Å) and one longer (1.93 Å) V–O bond length. There are a spread of V–F bond distances ranging from 2.04–2.13 Å. In the sixth V3+ site, V3+ is bonded to two O2- and four F1- atoms to form corner-sharing VO2F4 octahedra. The corner-sharing octahedra tilt angles range from 34–50°. There is one shorter (1.95 Å) and one longer (1.96 Å) V–O bond length. There are a spread of V–F bond distances ranging from 2.00–2.08 Å. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to three Li1+ and two V3+ atoms. In the second O2- site, O2- is bonded in a 5-coordinate geometry to three Li1+ and two V3+ atoms. In the third O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+ and two V3+ atoms. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to three Li1+ and two V3+ atoms. In the fifth O2- site, O2- is bonded in a 5-coordinate geometry to three Li1+ and two V3+ atoms. There are nineteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a 4-coordinate geometry to two Li1+ and two V3+ atoms. In the second F1- site, F1- is bonded in a 4-coordinate geometry to two Li1+ and two V3+ atoms. In the third F1- site, F1- is bonded to three Li1+ and one V3+ atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the fourth F1- site, F1- is bonded to three Li1+ and one V3+ atom to form distorted corner-sharing FLi3V trigonal pyramids. In the fifth F1- site, F1- is bonded in a distorted trigonal planar geometry to two Li1+ and one V3+ atom. In the sixth F1- site, F1- is bonded to three Li1+ and one V3+ atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the seventh F1- site, F1- is bonded to three Li1+ and one V3+ atom to form distorted corner-sharing FLi3V tetrahedra. In the eighth F1- site, F1- is bonded to three Li1+ and one V3+ atom to form distorted corner-sharing FLi3V trigonal pyramids. In the ninth F1- site, F1- is bonded in a 5-coordinate geometry to three Li1+ and two V3+ atoms. In the tenth F1- site, F1- is bonded in a 4-coordinate geometry to two Li1+ and two V3+ atoms. In the eleventh F1- site, F1- is bonded in a 2-coordinate geometry to one Li1+ and two V3+ atoms. In the twelfth F1- site, F1- is bonded in a 3-coordinate geometry to three Li1+ and one V3+ atom. In the thirteenth F1- site, F1- is bonded in a 3-coordinate geometry to three Li1+ and one V3+ atom. In the fourteenth F1- site, F1- is bonded to three Li1+ and one V3+ atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the fifteenth F1- site, F1- is bonded in a distorted T-shaped geometry to two Li1+ and one V3+ atom. In the sixteenth F1- site, F1- is bonded in a distorted T-shaped geometry to two Li1+ and one V3+ atom. In the seventeenth F1- site, F1- is bonded to three Li1+ and one V3+ atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids. In the eighteenth F1- site, F1- is bonded in a 3-coordinate geometry to three Li1+ and two V3+ atoms. In the nineteenth F1- site, F1- is bonded in a 5-coordinate geometry to three Li1+ and two V3+ atoms.