Li3Bi3(PO4)4 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. 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  a cornercorner with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Bi(1), one Bi(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to 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(1), one Bi(1), one Bi(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Bi(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one P(2) atom.
Li3Bi3(PO4)4 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(3) bond length is 2.31 Å. The Li(1)-O(5) bond length is 2.51 Å. The Li(1)-O(6) bond length is 1.97 Å. The Li(1)-O(7) bond length is 2.58 Å. The Li(1)-O(8) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Li(2)-O(4) bond lengths are 2.35 Å. Both Li(2)-O(7) bond lengths are 2.35 Å. Both Li(2)-O(8) bond lengths are 2.01 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Bi(1)-O(1) bond length is 2.37 Å. The Bi(1)-O(3) bond length is 2.71 Å. The Bi(1)-O(4) bond length is 2.23 Å. The Bi(1)-O(5) bond length is 2.46 Å. The Bi(1)-O(6) bond length is 2.32 Å. The Bi(1)-O(7) bond length is 2.46 Å. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Bi(2)-O(1) bond lengths are 2.58 Å. Both Bi(2)-O(2) bond lengths are 2.33 Å. Both Bi(2)-O(3) bond lengths are 2.49 Å. Both Bi(2)-O(5) bond lengths are 2.54 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  a cornercorner with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. 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 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.58 Å. The P(2)-O(8) bond length is 1.53 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Bi(1), one Bi(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Bi(1), one Bi(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to 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(1), one Bi(1), one Bi(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Bi(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one P(2) atom.