Li3Sb2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Sb(1)O6 octahedra,  a cornercorner with one Sb(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Sb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 69-70°. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form distorted SbO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. In the second Sb site, Sb(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form SbO6 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. 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 Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-58°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Sb(2), and one P(1) atom to form distorted corner-sharing OLi2SbP tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Sb(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Sb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Sb(1) and one P(1) atom.
Li3Sb2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Sb(1)O6 octahedra,  a cornercorner with one Sb(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Sb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 69-70°. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.92 Å. There is one shorter (1.99 Å) and one longer (2.19 Å) Li(1)-O(1) bond length. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form distorted SbO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All Sb(1)-O(3) bond lengths are 2.61 Å. All Sb(1)-O(4) bond lengths are 2.10 Å. In the second Sb site, Sb(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form SbO6 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 Sb(2)-O(1) bond lengths are 2.42 Å. All Sb(2)-O(2) bond lengths are 2.25 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 Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-58°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Sb(2), and one P(1) atom to form distorted corner-sharing OLi2SbP tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Sb(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Sb(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Sb(1) and one P(1) atom.