LiBi(PO3)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Bi(1)O6 pentagonal pyramids. Bi(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form distorted BiO6 pentagonal pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Bi(1)O6 pentagonal pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-62°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Bi(1)O6 pentagonal pyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(6) is bonded in a distorted single-bond geometry to one Bi(1) and one P(2) atom. In the third O site, O(7) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the fourth O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one P(1) atom. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom.
LiBi(PO3)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Bi(1)O6 pentagonal pyramids. Both Li(1)-O(1) bond lengths are 2.38 Å. Both Li(1)-O(2) bond lengths are 1.94 Å. Both Li(1)-O(4) bond lengths are 2.40 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form distorted BiO6 pentagonal pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Bi(1)-O(1) bond lengths are 2.34 Å. Both Bi(1)-O(4) bond lengths are 2.48 Å. Both Bi(1)-O(6) bond lengths are 2.32 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra,  a cornercorner with one Bi(1)O6 pentagonal pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-62°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.48 Å. The P(1)-O(5) bond length is 1.60 Å. The P(1)-O(7) bond length is 1.61 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Bi(1)O6 pentagonal pyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The P(2)-O(3) bond length is 1.60 Å. The P(2)-O(4) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.51 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(6) is bonded in a distorted single-bond geometry to one Bi(1) and one P(2) atom. In the third O site, O(7) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the fourth O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one P(1) atom. In the sixth O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom.