DOE OSTI2020
LiBa4(IrO4)3 is (Cubic) Perovskite-derived structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six IrO6 octahedra and faces with eight BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 1–2°. There are a spread of Li–O bond distances ranging from 2.14–2.17 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six IrO6 octahedra and faces with eight BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–2°. There are two shorter (2.14 Å) and four longer (2.16 Å) Li–O bond lengths. There are six inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with twelve BaO12 cuboctahedra, faces with six BaO12 cuboctahedra, faces with two LiO6 octahedra, and faces with six IrO6 octahedra. There are a spread of Ba–O bond distances ranging from 2.93–3.03 Å. In the second Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with twelve BaO12 cuboctahedra, faces with six BaO12 cuboctahedra, a faceface with one LiO6 octahedra, and faces with seven IrO6 octahedra. There are a spread of Ba–O bond distances ranging from 2.89–3.02 Å. In the third Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three IrO6 octahedra, faces with seven BaO12 cuboctahedra, faces with three equivalent LiO6 octahedra, and faces with four IrO6 octahedra. The corner-sharing octahedra tilt angles range from 13–16°. There are a spread of Ba–O bond distances ranging from 2.86–3.17 Å. In the fourth Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three IrO6 octahedra, faces with seven BaO12 cuboctahedra, faces with three equivalent LiO6 octahedra, and faces with four IrO6 octahedra. The corner-sharing octahedra tilt angles range from 11–14°. There are a spread of Ba–O bond distances ranging from 2.87–3.06 Å. In the fifth Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three IrO6 octahedra, faces with seven BaO12 cuboctahedra, a faceface with one LiO6 octahedra, and faces with six IrO6 octahedra. The corner-sharing octahedra tilt angles range from 10–14°. There are a spread of Ba–O bond distances ranging from 2.81–3.04 Å. In the sixth Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three IrO6 octahedra, faces with seven BaO12 cuboctahedra, faces with two equivalent LiO6 octahedra, and faces with five IrO6 octahedra. The corner-sharing octahedra tilt angles range from 8–12°. There are a spread of Ba–O bond distances ranging from 2.87–3.04 Å. There are five inequivalent Ir5+ sites. In the first Ir5+ site, Ir5+ is bonded to six O2- atoms to form IrO6 octahedra that share corners with three BaO12 cuboctahedra, corners with three equivalent LiO6 octahedra, faces with seven BaO12 cuboctahedra, and a faceface with one IrO6 octahedra. The corner-sharing octahedra tilt angles range from 1–2°. There are a spread of Ir–O bond distances ranging from 1.93–2.08 Å. In the second Ir5+ site, Ir5+ is bonded to six O2- atoms to form IrO6 octahedra that share corners with three BaO12 cuboctahedra, corners with three equivalent LiO6 octahedra, faces with seven BaO12 cuboctahedra, and a faceface with one IrO6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are a spread of Ir–O bond distances ranging from 1.93–2.06 Å. In the third Ir5+ site, Ir5+ is bonded to six O2- atoms to form IrO6 octahedra that share corners with three BaO12 cuboctahedra, a cornercorner with one LiO6 octahedra, corners with two equivalent IrO6 octahedra, faces with seven BaO12 cuboctahedra, and a faceface with one IrO6 octahedra. The corner-sharing octahedra tilt angles range from 0–5°. There are a spread of Ir–O bond distances ranging from 1.93–2.06 Å. In the fourth Ir5+ site, Ir5+ is bonded to six O2- atoms to form IrO6 octahedra that share corners with three BaO12 cuboctahedra, a cornercorner with one IrO6 octahedra, corners with two equivalent LiO6 octahedra, faces with seven BaO12 cuboctahedra, and a faceface with one IrO6 octahedra. The corner-sharing octahedra tilt angles range from 2–5°. There are a spread of Ir–O bond distances ranging from 1.94–2.06 Å. In the fifth Ir5+ site, Ir5+ is bonded to six O2- atoms to form IrO6 octahedra that share corners with six IrO6 octahedra and faces with eight BaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. There are four shorter (2.00 Å) and two longer (2.02 Å) Ir–O bond lengths. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted linear geometry to one Li1+, four Ba2+, and one Ir5+ atom. In the second O2- site, O2- is bonded in a distorted linear geometry to one Li1+, four Ba2+, and one Ir5+ atom. In the third O2- site, O2- is bonded in a distorted linear geometry to one Li1+, four Ba2+, and one Ir5+ atom. In the fourth O2- site, O2- is bonded in a distorted linear geometry to one Li1+, four Ba2+, and one Ir5+ atom. In the fifth O2- site, O2- is bonded in a distorted linear geometry to four Ba2+ and two Ir5+ atoms. In the sixth O2- site, O2- is bonded in a distorted linear geometry to one Li1+, four Ba2+, and one Ir5+ atom. In the seventh O2- site, O2- is bonded in a distorted linear geometry to one Li1+, four Ba2+, and one Ir5+ atom. In the eighth O2- site, O2- is bonded in a distorted linear geometry to four Ba2+ and two Ir5+ atoms. In the ninth O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+ and two Ir5+ atoms. In the tenth O2- site, O2- is bonded in a 2-coordinate geometry to four Ba2+ and two Ir5+ atoms. In the eleventh O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+ and two Ir5+ atoms. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to four Ba2+ and two Ir5+ atoms.