CaBi2O4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ca(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CaO6 octahedra that share corners with six equivalent Bi(1)O4 tetrahedra, edges with two equivalent Ca(1)O6 octahedra, and edges with four equivalent Bi(2)O6 octahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form BiO4 tetrahedra that share corners with six equivalent Ca(1)O6 octahedra and corners with six equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. In the second Bi site, Bi(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form BiO6 octahedra that share corners with six equivalent Bi(1)O4 tetrahedra, edges with two equivalent Bi(2)O6 octahedra, and edges with four equivalent Ca(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ca(1), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Bi(1), and two equivalent Bi(2) atoms.
CaBi2O4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ca(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CaO6 octahedra that share corners with six equivalent Bi(1)O4 tetrahedra, edges with two equivalent Ca(1)O6 octahedra, and edges with four equivalent Bi(2)O6 octahedra. Both Ca(1)-O(2) bond lengths are 2.39 Å. All Ca(1)-O(1) bond lengths are 2.42 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form BiO4 tetrahedra that share corners with six equivalent Ca(1)O6 octahedra and corners with six equivalent Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. Both Bi(1)-O(1) bond lengths are 2.25 Å. Both Bi(1)-O(2) bond lengths are 2.32 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form BiO6 octahedra that share corners with six equivalent Bi(1)O4 tetrahedra, edges with two equivalent Bi(2)O6 octahedra, and edges with four equivalent Ca(1)O6 octahedra. Both Bi(2)-O(1) bond lengths are 2.40 Å. All Bi(2)-O(2) bond lengths are 2.40 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ca(1), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Bi(1), and two equivalent Bi(2) atoms.