Li3Sb2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, and  an edgeedge with one Sb(3)O6 octahedra. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(6), one O(9), and two equivalent O(3) atoms. In the third Li site, Li(3) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 71-83°. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form SbO6 octahedra that share corners with six equivalent P(3)O4 tetrahedra and edges with two equivalent Sb(2)O6 octahedra. In the second Sb site, Sb(2) is bonded to one O(7), one O(8), two equivalent O(1), and two equivalent O(2) atoms to form SbO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Sb(1)O6 octahedra. In the third Sb site, Sb(3) is bonded to two equivalent O(9) and four equivalent O(3) atoms to form SbO6 octahedra that share corners with six equivalent P(2)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(6), one O(8), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the second P site, P(2) is bonded to one O(5), one O(9), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Sb(3)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Sb(1)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-56°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(2), and one P(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Sb(2), and one P(1) atom to form distorted edge-sharing OLi2SbP tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Sb(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Sb(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Sb(2) and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Sb(3), and one P(2) atom.
Li3Sb2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, and  an edgeedge with one Sb(3)O6 octahedra. The Li(1)-O(5) bond length is 2.14 Å. The Li(1)-O(6) bond length is 2.19 Å. Both Li(1)-O(2) bond lengths are 2.30 Å. Both Li(1)-O(3) bond lengths are 2.24 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(6), one O(9), and two equivalent O(3) atoms. The Li(2)-O(6) bond length is 1.92 Å. The Li(2)-O(9) bond length is 2.30 Å. Both Li(2)-O(3) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to one O(5), one O(7), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 71-83°. The Li(3)-O(5) bond length is 2.06 Å. The Li(3)-O(7) bond length is 2.12 Å. Both Li(3)-O(2) bond lengths are 2.08 Å. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form SbO6 octahedra that share corners with six equivalent P(3)O4 tetrahedra and edges with two equivalent Sb(2)O6 octahedra. Both Sb(1)-O(4) bond lengths are 2.22 Å. All Sb(1)-O(1) bond lengths are 2.35 Å. In the second Sb site, Sb(2) is bonded to one O(7), one O(8), two equivalent O(1), and two equivalent O(2) atoms to form SbO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Sb(1)O6 octahedra. The Sb(2)-O(7) bond length is 2.46 Å. The Sb(2)-O(8) bond length is 2.13 Å. Both Sb(2)-O(1) bond lengths are 2.38 Å. Both Sb(2)-O(2) bond lengths are 2.31 Å. In the third Sb site, Sb(3) is bonded to two equivalent O(9) and four equivalent O(3) atoms to form SbO6 octahedra that share corners with six equivalent P(2)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. Both Sb(3)-O(9) bond lengths are 2.29 Å. All Sb(3)-O(3) bond lengths are 2.35 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(6), one O(8), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-53°. The P(1)-O(6) bond length is 1.51 Å. The P(1)-O(8) bond length is 1.55 Å. Both P(1)-O(2) bond lengths are 1.59 Å. In the second P site, P(2) is bonded to one O(5), one O(9), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Sb(3)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-53°. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.57 Å. Both P(2)-O(3) bond lengths are 1.59 Å. In the third P site, P(3) is bonded to one O(4), one O(7), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Sb(1)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-56°. The P(3)-O(4) bond length is 1.53 Å. The P(3)-O(7) bond length is 1.54 Å. Both P(3)-O(1) bond lengths are 1.58 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(2), and one P(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Sb(2), and one P(1) atom to form distorted edge-sharing OLi2SbP tetrahedra. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Sb(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Sb(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Sb(2) and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Sb(3), and one P(2) atom.