LiSb(PO3)4 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Sb(1)O6 pentagonal pyramid. Sb(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form distorted SbO6 pentagonal pyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. There are two 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(5) atom to form PO4 tetrahedra that share corners with two equivalent Sb(1)O6 pentagonal pyramids,  a cornercorner with one Li(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(1)O6 pentagonal pyramid,  a cornercorner with one Li(1)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Sb(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Sb(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Sb(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom.
LiSb(PO3)4 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Sb(1)O6 pentagonal pyramid. Both Li(1)-O(5) bond lengths are 2.03 Å. Both Li(1)-O(6) bond lengths are 1.93 Å. Sb(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form distorted SbO6 pentagonal pyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. Both Sb(1)-O(1) bond lengths are 2.45 Å. Both Sb(1)-O(3) bond lengths are 2.29 Å. Both Sb(1)-O(5) bond lengths are 2.27 Å. There are two 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(5) atom to form PO4 tetrahedra that share corners with two equivalent Sb(1)O6 pentagonal pyramids,  a cornercorner with one Li(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The P(1)-O(2) bond length is 1.61 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(4) bond length is 1.59 Å. The P(1)-O(5) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(1)O6 pentagonal pyramid,  a cornercorner with one Li(1)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The P(2)-O(1) bond length is 1.50 Å. The P(2)-O(2) bond length is 1.62 Å. The P(2)-O(4) bond length is 1.63 Å. The P(2)-O(6) bond length is 1.50 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Sb(1) and one P(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Sb(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Sb(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(1) and one P(2) atom.