LiBi2(PO4)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-65°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(10), one O(11), one O(3), one O(4), one O(6), and one O(7) atom to form BiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. In the second Bi site, Bi(2) is bonded to one O(1), one O(12), one O(2), one O(5), one O(8), and one O(9) atom to form BiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, and  an edgeedge with one Li(1)O4 trigonal pyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(8) 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 two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 17-52°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 29-58°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 29-49°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Bi(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one Bi(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(2), and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Bi(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(3) atom.
LiBi2(PO4)3 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-65°. The Li(1)-O(11) bond length is 1.93 Å. The Li(1)-O(2) bond length is 2.07 Å. The Li(1)-O(5) bond length is 2.00 Å. The Li(1)-O(8) bond length is 2.13 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(10), one O(11), one O(3), one O(4), one O(6), and one O(7) atom to form BiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The Bi(1)-O(10) bond length is 2.33 Å. The Bi(1)-O(11) bond length is 2.42 Å. The Bi(1)-O(3) bond length is 2.32 Å. The Bi(1)-O(4) bond length is 2.36 Å. The Bi(1)-O(6) bond length is 2.36 Å. The Bi(1)-O(7) bond length is 2.32 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(12), one O(2), one O(5), one O(8), and one O(9) atom to form BiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Bi(2)-O(1) bond length is 2.16 Å. The Bi(2)-O(12) bond length is 2.15 Å. The Bi(2)-O(2) bond length is 2.24 Å. The Bi(2)-O(5) bond length is 2.23 Å. The Bi(2)-O(8) bond length is 2.24 Å. The Bi(2)-O(9) bond length is 2.17 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(8) 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 two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 17-52°. The P(1)-O(2) bond length is 1.60 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(8) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 29-58°. The P(2)-O(1) bond length is 1.58 Å. The P(2)-O(11) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 octahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 29-49°. The P(3)-O(10) bond length is 1.52 Å. The P(3)-O(12) bond length is 1.57 Å. The P(3)-O(5) bond length is 1.60 Å. The P(3)-O(6) bond length is 1.53 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Bi(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one Bi(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(2), and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Bi(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Bi(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Bi(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Bi(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Bi(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Bi(2) and one P(3) atom.