Ba2CeBiO6 crystallizes in the cubic Pn-3 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to twelve equivalent O(1) atoms to form BaO12 cuboctahedra that share faces with four equivalent Ce(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to eight equivalent O(1) atoms. Ce(1) is bonded to six equivalent O(1) atoms to form CeO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 17°. Bi(1) is bonded to six equivalent O(1) atoms to form BiO6 octahedra that share corners with six equivalent Ce(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 17°. O(1) is bonded in a 5-coordinate geometry to one Ba(1), two equivalent Ba(2), one Ce(1), and one Bi(1) atom.
Ba2CeBiO6 crystallizes in the cubic Pn-3 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to twelve equivalent O(1) atoms to form BaO12 cuboctahedra that share faces with four equivalent Ce(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. All Ba(1)-O(1) bond lengths are 3.14 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to eight equivalent O(1) atoms. There are four shorter (2.81 Å) and four longer (3.18 Å) Ba(2)-O(1) bond lengths. Ce(1) is bonded to six equivalent O(1) atoms to form CeO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 17°. All Ce(1)-O(1) bond lengths are 2.23 Å. Bi(1) is bonded to six equivalent O(1) atoms to form BiO6 octahedra that share corners with six equivalent Ce(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 17°. All Bi(1)-O(1) bond lengths are 2.26 Å. O(1) is bonded in a 5-coordinate geometry to one Ba(1), two equivalent Ba(2), one Ce(1), and one Bi(1) atom.