Li4C4Bi2SO16 crystallizes in the orthorhombic Fddd space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share edges with two equivalent Bi(1)O6 octahedra and  an edgeedge with one S(1)O4 tetrahedra. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. Bi(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form BiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra. S(1) is bonded to four equivalent O(2) atoms to form SO4 tetrahedra that share edges with two equivalent Li(1)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one C(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one C(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Li(1), one C(1), and one Bi(1) atom.
Li4C4Bi2SO16 crystallizes in the orthorhombic Fddd space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share edges with two equivalent Bi(1)O6 octahedra and  an edgeedge with one S(1)O4 tetrahedra. Both Li(1)-O(1) bond lengths are 2.31 Å. Both Li(1)-O(2) bond lengths are 2.13 Å. Both Li(1)-O(4) bond lengths are 2.43 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(2)-O(2) bond lengths are 2.10 Å. Both Li(2)-O(3) bond lengths are 2.19 Å. C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.29 Å. The C(1)-O(4) bond length is 1.30 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form BiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra. Both Bi(1)-O(1) bond lengths are 2.40 Å. Both Bi(1)-O(3) bond lengths are 2.40 Å. Both Bi(1)-O(4) bond lengths are 2.38 Å. S(1) is bonded to four equivalent O(2) atoms to form SO4 tetrahedra that share edges with two equivalent Li(1)O6 octahedra. All S(1)-O(2) bond lengths are 1.50 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one C(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one C(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Li(1), one C(1), and one Bi(1) atom.