LiBiP2O7 crystallizes in the monoclinic C2 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with three equivalent Bi(1)O6 octahedra. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with three equivalent Li(1)O6 octahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Bi(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-60°. There are four inequivalent O sites. In the first 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 second O site, O(2) is bonded in a distorted single-bond geometry to one Li(1), one Bi(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent P(1) atoms.
LiBiP2O7 crystallizes in the monoclinic C2 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with three equivalent Bi(1)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.28 Å. Both Li(1)-O(2) bond lengths are 2.58 Å. Both Li(1)-O(3) bond lengths are 2.27 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with three equivalent Li(1)O6 octahedra. Both Bi(1)-O(1) bond lengths are 2.32 Å. Both Bi(1)-O(2) bond lengths are 2.33 Å. Both Bi(1)-O(3) bond lengths are 2.43 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Bi(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-60°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.58 Å. There are four inequivalent O sites. In the first 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 second O site, O(2) is bonded in a distorted single-bond geometry to one Li(1), one Bi(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent P(1) atoms.