KCaCeBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form KO12 cuboctahedra that share faces with four equivalent Ce(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. In the second K site, K(2) is bonded in a 8-coordinate geometry to four equivalent O(2) and four equivalent O(3) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted body-centered cubic geometry to four equivalent O(1) and four equivalent O(2) atoms. In the second Ca site, Ca(2) is bonded in a square co-planar geometry to four equivalent O(3) atoms. Ce(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CeO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra and faces with two equivalent K(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 20-32°. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent Ce(1)O6 octahedra and faces with two equivalent K(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 20-32°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one K(1), one Ca(1), one Ce(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ca(1), one Ce(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one K(2), one Ca(2), one Ce(1), and one Bi(1) atom.
KCaCeBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form KO12 cuboctahedra that share faces with four equivalent Ce(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. All K(1)-O(1) bond lengths are 3.00 Å. All K(1)-O(2) bond lengths are 3.10 Å. All K(1)-O(3) bond lengths are 3.11 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to four equivalent O(2) and four equivalent O(3) atoms. All K(2)-O(2) bond lengths are 2.65 Å. All K(2)-O(3) bond lengths are 3.05 Å. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted body-centered cubic geometry to four equivalent O(1) and four equivalent O(2) atoms. All Ca(1)-O(1) bond lengths are 2.42 Å. All Ca(1)-O(2) bond lengths are 2.96 Å. In the second Ca site, Ca(2) is bonded in a square co-planar geometry to four equivalent O(3) atoms. All Ca(2)-O(3) bond lengths are 2.41 Å. Ce(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CeO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra and faces with two equivalent K(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 20-32°. Both Ce(1)-O(1) bond lengths are 2.27 Å. Both Ce(1)-O(2) bond lengths are 2.19 Å. Both Ce(1)-O(3) bond lengths are 2.25 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent Ce(1)O6 octahedra and faces with two equivalent K(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 20-32°. Both Bi(1)-O(1) bond lengths are 2.16 Å. Both Bi(1)-O(2) bond lengths are 2.13 Å. Both Bi(1)-O(3) bond lengths are 2.15 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one K(1), one Ca(1), one Ce(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one K(1), one K(2), one Ca(1), one Ce(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one K(2), one Ca(2), one Ce(1), and one Bi(1) atom.