LiB2BiO5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(4), one O(5), and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with three equivalent Bi(1)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-62°. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. Bi(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form distorted BiO6 octahedra that share corners with three equivalent Li(1)O4 trigonal pyramids, edges with two equivalent Bi(1)O6 octahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one B(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one B(1) and one B(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one B(2), and two equivalent Bi(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one B(2), and one Bi(1) atom.
LiB2BiO5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(4), one O(5), and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with three equivalent Bi(1)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-62°. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(5) bond length is 2.07 Å. There is one shorter (1.98 Å) and one longer (2.08 Å) Li(1)-O(2) 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(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.38 Å. The B(1)-O(2) bond length is 1.39 Å. The B(1)-O(3) bond length is 1.39 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. The B(2)-O(3) bond length is 1.39 Å. The B(2)-O(4) bond length is 1.39 Å. The B(2)-O(5) bond length is 1.37 Å. Bi(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form distorted BiO6 octahedra that share corners with three equivalent Li(1)O4 trigonal pyramids, edges with two equivalent Bi(1)O6 octahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Bi(1)-O(2) bond length is 2.40 Å. The Bi(1)-O(5) bond length is 2.28 Å. There is one shorter (2.30 Å) and one longer (2.51 Å) Bi(1)-O(1) bond length. There is one shorter (2.37 Å) and one longer (2.48 Å) Bi(1)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one B(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one B(1) and one B(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one B(2), and two equivalent Bi(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one B(2), and one Bi(1) atom.