LiBiO3 is Ilmenite-like structured and crystallizes in the orthorhombic Pccn space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms. Bi(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles are 52°. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent Bi(1) atoms. In the second O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Bi(1) atoms. In the third O site, O(2) is bonded to two equivalent Li(1) and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids. In the fourth O site, O(3) is bonded to two equivalent Li(1) and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids.
LiBiO3 is Ilmenite-like structured and crystallizes in the orthorhombic Pccn space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms. The Li(1)-O(1) bond length is 2.34 Å. The Li(1)-O(2) bond length is 2.04 Å. There is one shorter (1.93 Å) and one longer (2.04 Å) Li(1)-O(3) bond length. There is one shorter (1.94 Å) and one longer (2.52 Å) Li(1)-O(4) bond length. Bi(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles are 52°. The Bi(1)-O(1) bond length is 2.11 Å. The Bi(1)-O(2) bond length is 2.13 Å. Both Bi(1)-O(3) bond lengths are 2.14 Å. There is one shorter (2.10 Å) and one longer (2.14 Å) Bi(1)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent Bi(1) atoms. In the second O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Bi(1) atoms. In the third O site, O(2) is bonded to two equivalent Li(1) and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids. In the fourth O site, O(3) is bonded to two equivalent Li(1) and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OLi2Bi2 trigonal pyramids.