Ca(BiO3)2 crystallizes in the orthorhombic Pmn2_1 space group. Ca(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), two equivalent O(1), and four equivalent O(2) atoms. Bi(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 29-42°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a T-shaped geometry to one Ca(1) and two equivalent Bi(1) atoms.
Ca(BiO3)2 crystallizes in the orthorhombic Pmn2_1 space group. Ca(1) is bonded in a 8-coordinate geometry to one O(3), one O(4), two equivalent O(1), and four equivalent O(2) atoms. The Ca(1)-O(3) bond length is 2.33 Å. The Ca(1)-O(4) bond length is 2.35 Å. Both Ca(1)-O(1) bond lengths are 2.35 Å. There are two shorter (2.56 Å) and two longer (2.90 Å) Ca(1)-O(2) bond lengths. Bi(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 29-42°. The Bi(1)-O(3) bond length is 2.16 Å. The Bi(1)-O(4) bond length is 2.15 Å. There is one shorter (2.13 Å) and one longer (2.15 Å) Bi(1)-O(1) bond length. There is one shorter (2.17 Å) and one longer (2.18 Å) Bi(1)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ca(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Ca(1) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a T-shaped geometry to one Ca(1) and two equivalent Bi(1) atoms.