LiBi2(SO4)3 crystallizes in the trigonal R-3c space group. Li(1) is bonded to six equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. Bi(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. S(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 42°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one S(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Bi(1) and one S(1) atom.
LiBi2(SO4)3 crystallizes in the trigonal R-3c space group. Li(1) is bonded to six equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. All Li(1)-O(1) bond lengths are 2.35 Å. Bi(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. All Bi(1)-O(1) bond lengths are 2.49 Å. All Bi(1)-O(2) bond lengths are 2.38 Å. S(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 42°. Both S(1)-O(1) bond lengths are 1.50 Å. Both S(1)-O(2) bond lengths are 1.49 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one S(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Bi(1) and one S(1) atom.