LiSiBiO4 is Chalcostibite-derived structured and crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 trigonal pyramids that share corners with three equivalent Bi(1)O5 square pyramids, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with two equivalent Bi(1)O5 square pyramids, corners with two equivalent Si(1)O4 tetrahedra, and corners with four equivalent Li(1)O4 trigonal pyramids. Bi(1) is bonded to one O(2), one O(3), and three equivalent O(4) atoms to form BiO5 square pyramids that share corners with two equivalent Bi(1)O5 square pyramids, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids, edges with two equivalent Bi(1)O5 square pyramids, and  an edgeedge with one Li(1)O4 trigonal pyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Si(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Si(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Si(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1) and three equivalent Bi(1) atoms.
LiSiBiO4 is Chalcostibite-derived structured and crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form LiO4 trigonal pyramids that share corners with three equivalent Bi(1)O5 square pyramids, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O5 square pyramid. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.08 Å. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with two equivalent Bi(1)O5 square pyramids, corners with two equivalent Si(1)O4 tetrahedra, and corners with four equivalent Li(1)O4 trigonal pyramids. The Si(1)-O(2) bond length is 1.62 Å. The Si(1)-O(3) bond length is 1.62 Å. There is one shorter (1.68 Å) and one longer (1.69 Å) Si(1)-O(1) bond length. Bi(1) is bonded to one O(2), one O(3), and three equivalent O(4) atoms to form BiO5 square pyramids that share corners with two equivalent Bi(1)O5 square pyramids, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids, edges with two equivalent Bi(1)O5 square pyramids, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Bi(1)-O(2) bond length is 2.31 Å. The Bi(1)-O(3) bond length is 2.30 Å. There are a spread of Bi(1)-O(4) bond distances ranging from 2.12-2.46 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Si(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Si(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Si(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1) and three equivalent Bi(1) atoms.