Li3Bi2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent Bi(1)O6 octahedra. In the second Li site, Li(2) 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. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted BiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one 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(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra and corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-57°. In the second P site, P(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra and corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-45°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Bi(1) and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Bi(1), and one P(1) atom to form distorted corner-sharing OLi2BiP trigonal pyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Li(2), one Bi(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Bi(1), and one P(2) atom.
Li3Bi2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent Bi(1)O6 octahedra. Both Li(1)-O(3) bond lengths are 2.40 Å. Both Li(1)-O(4) bond lengths are 2.17 Å. Both Li(1)-O(6) bond lengths are 2.41 Å. In the second Li site, Li(2) 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(2)-O(1) bond length is 1.92 Å. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-O(4) bond length is 2.25 Å. The Li(2)-O(5) bond length is 2.53 Å. The Li(2)-O(6) bond length is 2.44 Å. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted BiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Li(1)O6 octahedra. The Bi(1)-O(1) bond length is 2.46 Å. The Bi(1)-O(2) bond length is 2.37 Å. The Bi(1)-O(3) bond length is 2.33 Å. The Bi(1)-O(4) bond length is 2.32 Å. The Bi(1)-O(5) bond length is 2.36 Å. The Bi(1)-O(6) bond length is 2.31 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(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra and corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-57°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.58 Å. In the second P site, P(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra and corners with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-45°. Both P(2)-O(5) bond lengths are 1.55 Å. Both P(2)-O(6) bond lengths are 1.57 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted linear geometry to one Bi(1) and one P(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Bi(1), and one P(1) atom to form distorted corner-sharing OLi2BiP trigonal pyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Bi(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Li(2), one Bi(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Bi(1), and one P(2) atom.