Li3Bi(BO3)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with three equivalent Bi(1)O5 trigonal bipyramids and corners with two equivalent Li(2)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Bi(1)O5 trigonal bipyramid, and  an edgeedge with one Bi(1)O5 trigonal bipyramid. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(3) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. Bi(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form BiO5 trigonal bipyramids that share corners with three equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(2)O4 trigonal pyramid. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one B(2), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one B(2), and one Bi(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one B(2), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Li(1), one B(1), and one Bi(1) atom.
Li3Bi(BO3)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with three equivalent Bi(1)O5 trigonal bipyramids and corners with two equivalent Li(2)O4 trigonal pyramids. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.20 Å. The Li(1)-O(4) bond length is 1.88 Å. The Li(1)-O(6) bond length is 2.00 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Bi(1)O5 trigonal bipyramid, and  an edgeedge with one Bi(1)O5 trigonal bipyramid. The Li(2)-O(1) bond length is 2.10 Å. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(3) bond length is 2.15 Å. The Li(2)-O(5) bond length is 2.13 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(3) atoms. The Li(3)-O(2) bond length is 1.90 Å. The Li(3)-O(5) bond length is 1.89 Å. There is one shorter (1.93 Å) and one longer (2.42 Å) Li(3)-O(3) bond length. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. The B(1)-O(2) bond length is 1.40 Å. The B(1)-O(3) bond length is 1.39 Å. The B(1)-O(6) bond length is 1.40 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(2)-O(1) bond length is 1.40 Å. The B(2)-O(4) bond length is 1.38 Å. The B(2)-O(5) bond length is 1.40 Å. Bi(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form BiO5 trigonal bipyramids that share corners with three equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(2)O4 trigonal pyramid. The Bi(1)-O(1) bond length is 2.44 Å. The Bi(1)-O(2) bond length is 2.31 Å. The Bi(1)-O(4) bond length is 2.25 Å. The Bi(1)-O(5) bond length is 2.37 Å. The Bi(1)-O(6) bond length is 2.37 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one B(2), and one Bi(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), two equivalent Li(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one B(2), and one Bi(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one B(2), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Li(1), one B(1), and one Bi(1) atom.