SrCaSmBiO6 crystallizes in the tetragonal P42_12 space group. Sr(1) is bonded in a distorted body-centered cubic geometry to four equivalent O(2) and four equivalent O(3) atoms. Ca(1) is bonded in a distorted body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. Sm(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form SmO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-36°. Bi(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent Sm(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-36°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to four equivalent Ca(1), one Sm(1), and one Bi(1) atom. In the second O site, O(2) is bonded to four equivalent Sr(1), one Sm(1), and one Bi(1) atom to form distorted OSr4SmBi octahedra that share corners with four equivalent O(2)Sr4SmBi octahedra, corners with eight equivalent O(3)SrCaSmBi tetrahedra, edges with four equivalent O(2)Sr4SmBi octahedra, and edges with eight equivalent O(3)SrCaSmBi tetrahedra. The corner-sharing octahedral tilt angles are 3°. In the third O site, O(3) is bonded to one Sr(1), one Ca(1), one Sm(1), and one Bi(1) atom to form distorted OSrCaSmBi tetrahedra that share corners with two equivalent O(2)Sr4SmBi octahedra, corners with ten equivalent O(3)SrCaSmBi tetrahedra, edges with two equivalent O(2)Sr4SmBi octahedra, and  an edgeedge with one O(3)SrCaSmBi tetrahedra. The corner-sharing octahedral tilt angles range from 67-68°.
SrCaSmBiO6 crystallizes in the tetragonal P42_12 space group. Sr(1) is bonded in a distorted body-centered cubic geometry to four equivalent O(2) and four equivalent O(3) atoms. All Sr(1)-O(2) bond lengths are 2.99 Å. All Sr(1)-O(3) bond lengths are 2.66 Å. Ca(1) is bonded in a distorted body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. All Ca(1)-O(1) bond lengths are 2.99 Å. All Ca(1)-O(3) bond lengths are 2.56 Å. Sm(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form SmO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-36°. The Sm(1)-O(1) bond length is 2.21 Å. The Sm(1)-O(2) bond length is 2.28 Å. All Sm(1)-O(3) bond lengths are 2.31 Å. Bi(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent Sm(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-36°. The Bi(1)-O(1) bond length is 2.09 Å. The Bi(1)-O(2) bond length is 2.14 Å. All Bi(1)-O(3) bond lengths are 2.14 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to four equivalent Ca(1), one Sm(1), and one Bi(1) atom. In the second O site, O(2) is bonded to four equivalent Sr(1), one Sm(1), and one Bi(1) atom to form distorted OSr4SmBi octahedra that share corners with four equivalent O(2)Sr4SmBi octahedra, corners with eight equivalent O(3)SrCaSmBi tetrahedra, edges with four equivalent O(2)Sr4SmBi octahedra, and edges with eight equivalent O(3)SrCaSmBi tetrahedra. The corner-sharing octahedral tilt angles are 3°. In the third O site, O(3) is bonded to one Sr(1), one Ca(1), one Sm(1), and one Bi(1) atom to form distorted OSrCaSmBi tetrahedra that share corners with two equivalent O(2)Sr4SmBi octahedra, corners with ten equivalent O(3)SrCaSmBi tetrahedra, edges with two equivalent O(2)Sr4SmBi octahedra, and  an edgeedge with one O(3)SrCaSmBi tetrahedra. The corner-sharing octahedral tilt angles range from 67-68°.