Li3Bi2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-74°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form BiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. In the second Bi site, Bi(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form BiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. 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 two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-60°. 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 trigonal planar geometry to one Li(1), one Bi(2), and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one Bi(1), and one P(1) atom to form distorted corner-sharing OLi2BiP tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(1) atom.
Li3Bi2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-74°. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 1.94 Å. There is one shorter (1.99 Å) and one longer (2.12 Å) Li(1)-O(3) bond length. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form BiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. All Bi(1)-O(1) bond lengths are 2.31 Å. All Bi(1)-O(3) bond lengths are 2.45 Å. In the second Bi site, Bi(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form BiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All Bi(2)-O(2) bond lengths are 2.51 Å. All Bi(2)-O(4) bond lengths are 2.26 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 two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-60°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.53 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 trigonal planar geometry to one Li(1), one Bi(2), and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one Bi(1), and one P(1) atom to form distorted corner-sharing OLi2BiP tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(1) atom.