BaCaInBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form BaO12 cuboctahedra that share faces with four equivalent In(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 four equivalent O(1) and four equivalent O(3) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted square co-planar 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. In(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form InO6 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 range from 20-31°. 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 In(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 20-31°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ca(1), one In(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ca(1), one In(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ca(2), one In(1), and one Bi(1) atom.
BaCaInBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form BaO12 cuboctahedra that share faces with four equivalent In(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. All Ba(1)-O(1) bond lengths are 3.01 Å. All Ba(1)-O(2) bond lengths are 2.92 Å. All Ba(1)-O(3) bond lengths are 3.09 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(3) atoms. All Ba(2)-O(1) bond lengths are 2.62 Å. All Ba(2)-O(3) bond lengths are 2.99 Å. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted square co-planar geometry to four equivalent O(1) and four equivalent O(2) atoms. All Ca(1)-O(1) bond lengths are 3.00 Å. All Ca(1)-O(2) bond lengths are 2.42 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 2.40 Å. In(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form InO6 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 range from 20-31°. Both In(1)-O(1) bond lengths are 2.15 Å. Both In(1)-O(2) bond lengths are 2.22 Å. Both In(1)-O(3) bond lengths are 2.21 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 In(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 20-31°. Both Bi(1)-O(1) bond lengths are 2.13 Å. Both Bi(1)-O(2) bond lengths are 2.16 Å. Both Bi(1)-O(3) bond lengths are 2.16 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ca(1), one In(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ca(1), one In(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ca(2), one In(1), and one Bi(1) atom.