DOE OSTI2020
Ba12Sm4Al3(CoO6)5 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 12-coordinate geometry to twelve O2- atoms. There are a spread of Ba–O bond distances ranging from 2.78–3.39 Å. In the second Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form distorted BaO12 cuboctahedra that share faces with two equivalent CoO6 octahedra and faces with three AlO4 tetrahedra. There are a spread of Ba–O bond distances ranging from 2.66–3.27 Å. In the third Ba2+ site, Ba2+ is bonded to six O2- atoms to form BaO6 octahedra that share corners with three CoO4 tetrahedra, corners with three AlO4 tetrahedra, and faces with two equivalent BaO6 octahedra. There are a spread of Ba–O bond distances ranging from 2.57–2.82 Å. In the fourth Ba2+ site, Ba2+ is bonded to six O2- atoms to form BaO6 octahedra that share corners with three CoO4 tetrahedra, corners with three AlO4 tetrahedra, and faces with two equivalent BaO6 octahedra. There are a spread of Ba–O bond distances ranging from 2.60–2.77 Å. In the fifth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Ba–O bond distances ranging from 2.70–3.31 Å. In the sixth Ba2+ site, Ba2+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Ba–O bond distances ranging from 2.76–3.38 Å. In the seventh Ba2+ site, Ba2+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Ba–O bond distances ranging from 2.77–3.38 Å. In the eighth Ba2+ site, Ba2+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Ba–O bond distances ranging from 2.76–3.31 Å. In the ninth Ba2+ site, Ba2+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Ba–O bond distances ranging from 2.70–3.37 Å. In the tenth Ba2+ site, Ba2+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Ba–O bond distances ranging from 2.73–3.32 Å. In the eleventh Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Ba–O bond distances ranging from 2.59–2.86 Å. In the twelfth Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Ba–O bond distances ranging from 2.58–2.86 Å. There are four inequivalent Sm3+ sites. In the first Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Sm–O bond distances ranging from 2.41–2.77 Å. In the second Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Sm–O bond distances ranging from 2.37–2.68 Å. In the third Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Sm–O bond distances ranging from 2.36–2.68 Å. In the fourth Sm3+ site, Sm3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Sm–O bond distances ranging from 2.32–2.78 Å. There are five inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form corner-sharing CoO6 octahedra. There are a spread of Co–O bond distances ranging from 1.84–2.25 Å. In the second Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with three AlO4 tetrahedra and faces with two equivalent BaO12 cuboctahedra. There are a spread of Co–O bond distances ranging from 1.85–2.26 Å. In the third Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share a cornercorner with one CoO6 octahedra and corners with two BaO6 octahedra. The corner-sharing octahedra tilt angles range from 8–60°. There are a spread of Co–O bond distances ranging from 1.80–1.91 Å. In the fourth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share a cornercorner with one CoO6 octahedra and corners with two BaO6 octahedra. The corner-sharing octahedra tilt angles range from 10–69°. There are a spread of Co–O bond distances ranging from 1.80–1.98 Å. In the fifth Co3+ site, Co3+ is bonded to four O2- atoms to form CoO4 tetrahedra that share a cornercorner with one CoO6 octahedra and corners with two BaO6 octahedra. The corner-sharing octahedra tilt angles range from 8–66°. There are a spread of Co–O bond distances ranging from 1.82–1.92 Å. There are three inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share a cornercorner with one CoO6 octahedra, corners with two BaO6 octahedra, and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 10–65°. There are a spread of Al–O bond distances ranging from 1.76–1.84 Å. In the second Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share a cornercorner with one CoO6 octahedra, corners with two BaO6 octahedra, and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 10–60°. There are a spread of Al–O bond distances ranging from 1.76–1.80 Å. In the third Al3+ site, Al3+ is bonded to four O2- atoms to form AlO4 tetrahedra that share a cornercorner with one CoO6 octahedra, corners with two BaO6 octahedra, and a faceface with one BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 11–67°. There are a spread of Al–O bond distances ranging from 1.76–1.82 Å. There are thirty inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+, one Sm3+, and one Al3+ atom. In the second O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+, one Sm3+, and one Al3+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to three Ba2+, two Sm3+, and one Al3+ atom. In the fourth O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+, one Sm3+, and one Al3+ atom. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to three Ba2+, two Sm3+, and one Al3+ atom. In the sixth O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+, one Sm3+, and one Al3+ atom. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to four Ba2+, one Sm3+, and one Co3+ atom. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+, one Sm3+, and one Co3+ atom. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to three Ba2+, two Sm3+, and one Co3+ atom. In the tenth O2- site, O2- is bonded in a 2-coordinate geometry to four Ba2+, one Sm3+, and one Co3+ atom. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to three Ba2+, two Sm3+, and one Co3+ atom. In the twelfth O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+, one Sm3+, and one Co3+ atom. In the thirteenth O2- site, O2- is bonded to four Ba2+, one Sm3+, and one Co3+ atom to form distorted face-sharing OBa4SmCo octahedra. In the fourteenth O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+, one Sm3+, and one Co3+ atom. In the fifteenth O2- site, O2- is bonded to three Ba2+, two Sm3+, and one Co3+ atom to form distorted OBa3Sm2Co octahedra that share corners with two equivalent OBa3Sm2Co octahedra and a faceface with one OBa4SmCo octahedra. The corner-sharing octahedra tilt angles range from 31–33°. In the sixteenth O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+, one Sm3+, and one Co3+ atom. In the seventeenth O2- site, O2- is bonded to four Ba2+, one Sm3+, and one Co3+ atom to form distorted face-sharing OBa4SmCo octahedra. In the eighteenth O2- site, O2- is bonded to three Ba2+, two Sm3+, and one Co3+ atom to form distorted OBa3Sm2Co octahedra that share corners with two equivalent OBa3Sm2Co octahedra and a faceface with one OBa4SmCo octahedra. The corner-sharing octahedra tilt angles range from 31–33°. In the nineteenth O2- site, O2- is bonded in a 6-coordinate geometry to two Ba2+, two Sm3+, and two Co3+ atoms. In the twentieth O2- site, O2- is bonded in a 6-coordinate geometry to three Ba2+, one Sm3+, and two Co3+ atoms. In the twenty-first O2- site, O2- is bonded in a 6-coordinate geometry to three Ba2+, one Sm3+, and two Co3+ atoms. In the twenty-second O2- site, O2- is bonded in a 6-coordinate geometry to three Ba2+, one Sm3+, one Co3+, and one Al3+ atom. In the twenty-third O2- site, O2- is bonded in a 1-coordinate geometry to two Ba2+, two Sm3+, one Co3+, and one Al3+ atom. In the twenty-fourth O2- site, O2- is bonded in a 1-coordinate geometry to three Ba2+, one Sm3+, one Co3+, and one Al3+ atom. In the twenty-fifth O2- site, O2- is bonded in a 1-coordinate geometry to five Ba2+ and one Al3+ atom. In the twenty-sixth O2- site, O2- is bonded in a 1-coordinate geometry to five Ba2+ and one Al3+ atom. In the twenty-seventh O2- site, O2- is bonded in a 1-coordinate geometry to five Ba2+ and one Al3+ atom. In the twenty-eighth O2- site, O2- is bonded in a 1-coordinate geometry to four Ba2+ and one Co3+ atom. In the twenty-ninth O2- site, O2- is bonded in a 1-coordinate geometry to five Ba2+ and one Co3+ atom. In the thirtieth O2- site, O2- is bonded in a 1-coordinate geometry to five Ba2+ and one Co3+ atom.