LiSi2BiO6 is Esseneite structured and crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-60°. Bi(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Si(1), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing OLi2SiBi trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Si(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms.
LiSi2BiO6 is Esseneite structured and crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. Both Li(1)-O(2) bond lengths are 2.22 Å. There are two shorter (2.10 Å) and two longer (2.22 Å) Li(1)-O(1) bond lengths. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-60°. The Si(1)-O(1) bond length is 1.64 Å. The Si(1)-O(2) bond length is 1.61 Å. There is one shorter (1.67 Å) and one longer (1.69 Å) Si(1)-O(3) bond length. Bi(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Bi(1)-O(1) bond lengths are 2.19 Å. Both Bi(1)-O(2) bond lengths are 2.34 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Si(1), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing OLi2SiBi trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Si(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms.