Li3B4BiO9 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and one O(6) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(4) atoms. There are three inequivalent B sites. In the first B site, B(1) is bonded to one O(2), one O(5), and two equivalent O(1) atoms to form BO4 tetrahedra that share  a cornercorner with one B(2)O4 tetrahedra and  a cornercorner with one Bi(1)O4 trigonal pyramid. In the second B site, B(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form BO4 tetrahedra that share  a cornercorner with one B(1)O4 tetrahedra and  a cornercorner with one Bi(1)O4 trigonal pyramid. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. Bi(1) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form BiO4 trigonal pyramids that share  a cornercorner with one B(1)O4 tetrahedra and  a cornercorner with one B(2)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one B(1), and one B(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one B(1), and one B(2) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to two equivalent Li(1), one B(2), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one B(2), and one B(3) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one B(1), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one B(3), and one Bi(1) atom.
Li3B4BiO9 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.23 Å. The Li(1)-O(3) bond length is 2.14 Å. The Li(1)-O(4) bond length is 2.01 Å. The Li(1)-O(5) bond length is 2.47 Å. The Li(1)-O(6) bond length is 1.98 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(4) atoms. The Li(2)-O(2) bond length is 1.90 Å. The Li(2)-O(5) bond length is 2.05 Å. Both Li(2)-O(4) bond lengths are 2.08 Å. There are three inequivalent B sites. In the first B site, B(1) is bonded to one O(2), one O(5), and two equivalent O(1) atoms to form BO4 tetrahedra that share  a cornercorner with one B(2)O4 tetrahedra and  a cornercorner with one Bi(1)O4 trigonal pyramid. The B(1)-O(2) bond length is 1.48 Å. The B(1)-O(5) bond length is 1.43 Å. Both B(1)-O(1) bond lengths are 1.52 Å. In the second B site, B(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form BO4 tetrahedra that share  a cornercorner with one B(1)O4 tetrahedra and  a cornercorner with one Bi(1)O4 trigonal pyramid. The B(2)-O(2) bond length is 1.42 Å. The B(2)-O(3) bond length is 1.47 Å. Both B(2)-O(4) bond lengths are 1.53 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. The B(3)-O(1) bond length is 1.39 Å. The B(3)-O(4) bond length is 1.39 Å. The B(3)-O(6) bond length is 1.37 Å. Bi(1) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form BiO4 trigonal pyramids that share  a cornercorner with one B(1)O4 tetrahedra and  a cornercorner with one B(2)O4 tetrahedra. The Bi(1)-O(3) bond length is 2.18 Å. The Bi(1)-O(5) bond length is 2.32 Å. Both Bi(1)-O(6) bond lengths are 2.27 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one B(1), and one B(3) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one B(1), and one B(2) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to two equivalent Li(1), one B(2), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one B(2), and one B(3) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one B(1), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one B(3), and one Bi(1) atom.