DOE OSTI2020
Li2VO2F is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are ten 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 2.10 Å. There are a spread of Li–F bond distances ranging from 1.91–2.43 Å. In the second Li1+ site, Li1+ is bonded in a 6-coordinate geometry to five O2- and one F1- atom. There are a spread of Li–O bond distances ranging from 1.90–2.53 Å. The Li–F bond length is 2.40 Å. In the third Li1+ site, Li1+ is bonded to three O2- and three F1- atoms to form LiO3F3 octahedra that share corners with three LiO3F3 octahedra, corners with three VO6 octahedra, edges with three VO6 octahedra, and edges with nine LiO3F3 octahedra. The corner-sharing octahedra tilt angles range from 2–12°. There are two shorter (2.15 Å) and one longer (2.35 Å) Li–O bond lengths. There are one shorter (1.94 Å) and two longer (2.13 Å) Li–F bond lengths. In the fourth Li1+ site, Li1+ is bonded to three O2- and three F1- atoms to form LiO3F3 octahedra that share corners with two equivalent LiO3F3 octahedra, corners with three VO6 octahedra, edges with three VO4F2 octahedra, and edges with nine LiO3F3 octahedra. The corner-sharing octahedra tilt angles range from 7–9°. There are a spread of Li–O bond distances ranging from 2.14–2.26 Å. There are two shorter (2.02 Å) and one longer (2.18 Å) Li–F bond lengths. In the fifth Li1+ site, Li1+ is bonded to five O2- and one F1- atom to form distorted LiO5F octahedra that share a cornercorner with one LiO3F3 octahedra, corners with three VO6 octahedra, edges with three VO6 octahedra, and edges with six LiO5F octahedra. The corner-sharing octahedra tilt angles range from 11–14°. There are a spread of Li–O bond distances ranging from 1.93–2.47 Å. The Li–F bond length is 2.21 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- and two equivalent F1- atoms to form distorted LiO4F2 octahedra that share corners with two equivalent LiO3F3 octahedra, corners with three VO6 octahedra, edges with three VO6 octahedra, and edges with seven LiO3F3 octahedra. The corner-sharing octahedra tilt angles range from 2–14°. There are a spread of Li–O bond distances ranging from 1.89–2.46 Å. Both Li–F bond lengths are 2.16 Å. In the seventh Li1+ site, Li1+ is bonded to two equivalent O2- and four F1- atoms to form LiO2F4 octahedra that share corners with three LiO3F3 octahedra, corners with three VO5F octahedra, edges with three VO4F2 octahedra, and edges with seven LiO3F3 octahedra. The corner-sharing octahedra tilt angles range from 2–11°. There are one shorter (2.21 Å) and one longer (2.22 Å) Li–O bond lengths. There are a spread of Li–F bond distances ranging from 1.97–2.24 Å. In the eighth Li1+ site, Li1+ is bonded to three O2- and three F1- atoms to form LiO3F3 octahedra that share corners with two equivalent LiO2F4 octahedra, corners with three VO5F octahedra, edges with three VO5F octahedra, and edges with five LiO3F3 octahedra. The corner-sharing octahedra tilt angles range from 2–16°. There are a spread of Li–O bond distances ranging from 2.24–2.29 Å. There are one shorter (1.95 Å) and two longer (2.10 Å) Li–F bond lengths. In the ninth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to four O2- and two equivalent F1- atoms. There are a spread of Li–O bond distances ranging from 1.84–2.66 Å. Both Li–F bond lengths are 2.21 Å. In the tenth Li1+ site, Li1+ is bonded to three O2- and three F1- atoms to form LiO3F3 octahedra that share corners with three LiO4F2 octahedra, corners with three VO6 octahedra, edges with three VO6 octahedra, and edges with nine LiO3F3 octahedra. The corner-sharing octahedra tilt angles range from 2–14°. There are one shorter (2.13 Å) and two longer (2.29 Å) Li–O bond lengths. There are two shorter (1.99 Å) and one longer (2.25 Å) Li–F bond lengths. There are five inequivalent V3+ sites. In the first V3+ site, V3+ is bonded to five O2- and one F1- atom to form VO5F octahedra that share corners with four LiO5F octahedra, an edgeedge with one LiO3F3 octahedra, and edges with six VO5F octahedra. The corner-sharing octahedra tilt angles range from 5–16°. There are a spread of V–O bond distances ranging from 1.98–2.07 Å. The V–F bond length is 2.24 Å. In the second V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with five LiO3F3 octahedra, edges with six LiO3F3 octahedra, and edges with six VO6 octahedra. The corner-sharing octahedra tilt angles range from 8–11°. There are a spread of V–O bond distances ranging from 2.02–2.10 Å. In the third V3+ site, V3+ is bonded to four O2- and two equivalent F1- atoms to form VO4F2 octahedra that share corners with three LiO3F3 octahedra, edges with five LiO3F3 octahedra, and edges with six VO5F octahedra. The corner-sharing octahedra tilt angles range from 2–8°. There are a spread of V–O bond distances ranging from 1.97–2.00 Å. Both V–F bond lengths are 2.19 Å. In the fourth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO3F3 octahedra, edges with three LiO5F octahedra, and edges with six VO5F octahedra. The corner-sharing octahedra tilt angles range from 11–12°. There are a spread of V–O bond distances ranging from 2.02–2.15 Å. In the fifth V3+ site, V3+ is bonded to six O2- atoms to form VO6 octahedra that share corners with six LiO3F3 octahedra, edges with six LiO3F3 octahedra, and edges with six VO6 octahedra. The corner-sharing octahedra tilt angles range from 2–11°. There are a spread of V–O bond distances ranging from 2.00–2.10 Å. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded in a 6-coordinate geometry to three Li1+ and three V3+ atoms. In the second O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share corners with three OLi3V3 octahedra, corners with three FLi6 octahedra, edges with three FLi6 octahedra, and edges with nine OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 1–10°. In the third O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share corners with two equivalent OLi3V3 octahedra, corners with two FLi6 octahedra, and edges with nine OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 2–19°. In the fourth O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share corners with two equivalent FLi6 octahedra, corners with three OLi3V3 octahedra, an edgeedge with one FLi6 octahedra, and edges with eleven OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 1–16°. In the fifth O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share corners with two equivalent OLi3V3 octahedra, corners with three FLi6 octahedra, edges with five FLi6 octahedra, and edges with seven OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 1–10°. In the sixth O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share a cornercorner with one FLi6 octahedra, corners with five OLi6 octahedra, edges with two equivalent FLi6 octahedra, and edges with ten OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 2–14°. In the seventh O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share a cornercorner with one OLi3V3 octahedra, corners with four FLi3V3 octahedra, edges with four FLi6 octahedra, and edges with six OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 1–7°. In the eighth O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form OLi3V3 octahedra that share corners with two equivalent FLi6 octahedra, corners with four OLi6 octahedra, edges with three FLi6 octahedra, and edges with nine OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 1–9°. In the ninth O2- site, O2- is bonded to three Li1+ and three V3+ atoms to form distorted OLi3V3 octahedra that share a cornercorner with one FLi6 octahedra, corners with three OLi6 octahedra, edges with two equivalent FLi3V3 octahedra, and edges with seven OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 2–22°. In the tenth O2- site, O2- is bonded to six Li1+ atoms to form OLi6 octahedra that share corners with five OLi3V3 octahedra, edges with two equivalent FLi6 octahedra, and edges with eight OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 4–17°. There are five inequivalent F1- sites. In the first F1- site, F1- is bonded in a 6-coordinate geometry to six Li1+ atoms. In the second F1- site, F1- is bonded to six Li1+ atoms to form FLi6 octahedra that share corners with six OLi3V3 octahedra, edges with four FLi6 octahedra, and edges with eight OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 1–19°. In the third F1- site, F1- is bonded to six Li1+ atoms to form FLi6 octahedra that share corners with four OLi3V3 octahedra, edges with three OLi3V3 octahedra, and edges with six FLi6 octahedra. The corner-sharing octahedra tilt angles range from 10–22°. In the fourth F1- site, F1- is bonded to three Li1+ and three V3+ atoms to form FLi3V3 octahedra that share a cornercorner with one FLi6 octahedra, corners with three OLi3V3 octahedra, edges with four FLi6 octahedra, and edges with five OLi3V3 octahedra. The corner-sharing octahedra tilt angles range from 2–6°. In the fifth F1- site, F1- is bonded to six Li1+ atoms to form FLi6 octahedra that share a cornercorner with one FLi3V3 octahedra, corners with five OLi3V3 octahedra, edges with six OLi3V3 octahedra, and edges with six FLi6 octahedra. The corner-sharing octahedra tilt angles range from 4–11°.