DOE OSTI2020
Na5LiBaCo5F18 is Orthorhombic Perovskite-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are ten inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a distorted square co-planar geometry to four F1- atoms. There are one shorter (2.28 Å) and three longer (2.30 Å) Na–F bond lengths. In the second Na1+ site, Na1+ is bonded in a 4-coordinate geometry to five F1- atoms. There are a spread of Na–F bond distances ranging from 2.26–2.79 Å. In the third Na1+ site, Na1+ is bonded in a distorted rectangular see-saw-like geometry to four F1- atoms. There are a spread of Na–F bond distances ranging from 2.28–2.32 Å. In the fourth Na1+ site, Na1+ is bonded in a distorted square co-planar geometry to five F1- atoms. There are a spread of Na–F bond distances ranging from 2.30–2.86 Å. In the fifth Na1+ site, Na1+ is bonded to twelve F1- atoms to form NaF12 cuboctahedra that share faces with eight CoF6 octahedra. There are a spread of Na–F bond distances ranging from 2.73–2.89 Å. In the sixth Na1+ site, Na1+ is bonded in a distorted square co-planar geometry to four F1- atoms. There are a spread of Na–F bond distances ranging from 2.27–2.32 Å. In the seventh Na1+ site, Na1+ is bonded in a distorted rectangular see-saw-like geometry to four F1- atoms. There are a spread of Na–F bond distances ranging from 2.29–2.34 Å. In the eighth Na1+ site, Na1+ is bonded in a 4-coordinate geometry to five F1- atoms. There are a spread of Na–F bond distances ranging from 2.28–2.76 Å. In the ninth Na1+ site, Na1+ is bonded in a distorted square co-planar geometry to five F1- atoms. There are a spread of Na–F bond distances ranging from 2.29–2.85 Å. In the tenth Na1+ site, Na1+ is bonded in a distorted square co-planar geometry to five F1- atoms. There are a spread of Na–F bond distances ranging from 2.29–2.87 Å. There are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with six CoF6 octahedra and faces with two equivalent BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 27–30°. There are a spread of Li–F bond distances ranging from 2.10–2.13 Å. In the second Li1+ site, Li1+ is bonded to six F1- atoms to form LiF6 octahedra that share corners with six CoF6 octahedra and faces with two equivalent BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 27–29°. There are a spread of Li–F bond distances ranging from 2.10–2.15 Å. There are two inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded to twelve F1- atoms to form BaF12 cuboctahedra that share faces with two equivalent LiF6 octahedra and faces with six CoF6 octahedra. There are a spread of Ba–F bond distances ranging from 2.79–2.84 Å. In the second Ba2+ site, Ba2+ is bonded to twelve F1- atoms to form BaF12 cuboctahedra that share faces with two equivalent LiF6 octahedra and faces with six CoF6 octahedra. There are a spread of Ba–F bond distances ranging from 2.79–2.83 Å. There are ten inequivalent Co2+ sites. In the first Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share corners with six CoF6 octahedra and faces with two equivalent NaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 29–31°. There are a spread of Co–F bond distances ranging from 2.03–2.08 Å. In the second Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share a cornercorner with one LiF6 octahedra, corners with five CoF6 octahedra, a faceface with one NaF12 cuboctahedra, and a faceface with one BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 29–30°. There are a spread of Co–F bond distances ranging from 2.02–2.09 Å. In the third Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share corners with two LiF6 octahedra, corners with four CoF6 octahedra, and faces with two BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 27–31°. There are a spread of Co–F bond distances ranging from 2.01–2.10 Å. In the fourth Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share corners with two equivalent LiF6 octahedra, corners with four CoF6 octahedra, and faces with two equivalent BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 28–31°. There are a spread of Co–F bond distances ranging from 2.02–2.08 Å. In the fifth Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share a cornercorner with one LiF6 octahedra, corners with five CoF6 octahedra, a faceface with one NaF12 cuboctahedra, and a faceface with one BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 27–31°. There are a spread of Co–F bond distances ranging from 2.03–2.09 Å. In the sixth Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share a cornercorner with one LiF6 octahedra, corners with five CoF6 octahedra, a faceface with one NaF12 cuboctahedra, and a faceface with one BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 27–31°. There are a spread of Co–F bond distances ranging from 2.03–2.10 Å. In the seventh Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share corners with six CoF6 octahedra and faces with two equivalent NaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 29–31°. There are a spread of Co–F bond distances ranging from 2.05–2.07 Å. In the eighth Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share a cornercorner with one LiF6 octahedra, corners with five CoF6 octahedra, a faceface with one NaF12 cuboctahedra, and a faceface with one BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 28–31°. There are a spread of Co–F bond distances ranging from 2.04–2.09 Å. In the ninth Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share corners with two LiF6 octahedra, corners with four CoF6 octahedra, and faces with two BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 28–31°. There are a spread of Co–F bond distances ranging from 2.00–2.08 Å. In the tenth Co2+ site, Co2+ is bonded to six F1- atoms to form CoF6 octahedra that share corners with two equivalent LiF6 octahedra, corners with four CoF6 octahedra, and faces with two equivalent BaF12 cuboctahedra. The corner-sharing octahedra tilt angles range from 28–31°. There are a spread of Co–F bond distances ranging from 2.02–2.09 Å. There are thirty-six inequivalent F1- sites. In the first F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the second F1- site, F1- is bonded in a 4-coordinate geometry to two Na1+ and two Co2+ atoms. In the third F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+ and two Co2+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the fifth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the sixth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+ and two Co2+ atoms. In the seventh F1- site, F1- is bonded in a 4-coordinate geometry to two Na1+ and two Co2+ atoms. In the eighth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the ninth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the tenth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the eleventh F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+ and two Co2+ atoms. In the twelfth F1- site, F1- is bonded in a 3-coordinate geometry to two Na1+ and two Co2+ atoms. In the thirteenth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+ and two Co2+ atoms. In the fourteenth F1- site, F1- is bonded in a 3-coordinate geometry to two Na1+ and two Co2+ atoms. In the fifteenth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the sixteenth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the seventeenth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the eighteenth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the nineteenth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the twentieth F1- site, F1- is bonded in a 3-coordinate geometry to two Na1+ and two Co2+ atoms. In the twenty-first F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the twenty-second F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the twenty-third F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+ and two Co2+ atoms. In the twenty-fourth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the twenty-fifth F1- site, F1- is bonded in a 5-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the twenty-sixth F1- site, F1- is bonded in a 4-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the twenty-seventh F1- site, F1- is bonded in a 4-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the twenty-eighth F1- site, F1- is bonded in a 4-coordinate geometry to two Na1+ and two Co2+ atoms. In the twenty-ninth F1- site, F1- is bonded in a 4-coordinate geometry to two Na1+ and two Co2+ atoms. In the thirtieth F1- site, F1- is bonded in a 5-coordinate geometry to two Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the thirty-first F1- site, F1- is bonded in a 4-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the thirty-second F1- site, F1- is bonded in a 3-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the thirty-third F1- site, F1- is bonded in a 3-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the thirty-fourth F1- site, F1- is bonded in a 3-coordinate geometry to one Na1+, one Ba2+, and two Co2+ atoms. In the thirty-fifth F1- site, F1- is bonded in a 3-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom. In the thirty-sixth F1- site, F1- is bonded in a 3-coordinate geometry to one Na1+, one Li1+, one Ba2+, and one Co2+ atom.