LiSb3(PO5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 5-coordinate geometry to one O(10), one O(3), one O(4), one O(6), and one O(7) atom. In the second Sb site, Sb(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(9) atom. In the third Sb site, Sb(3) is bonded to one O(1), one O(2), one O(6), one O(7), and one O(8) atom to form distorted SbO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(3)O5 square pyramid. In the second P site, P(2) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Sb(3)O5 square pyramids. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Sb(2), one Sb(3), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Sb(2), one Sb(3), 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 bent 120 degrees geometry to one Sb(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one P(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Sb(1), one Sb(2), and one Sb(3) atom to form edge-sharing OLiSb3 tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Sb(1), one Sb(2), and one Sb(3) atom to form distorted edge-sharing OLiSb3 tetrahedra. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Sb(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Sb(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(2), and one P(1) atom.
LiSb3(PO5)2 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. The Li(1)-O(5) bond length is 2.40 Å. The Li(1)-O(6) bond length is 2.14 Å. The Li(1)-O(7) bond length is 2.05 Å. The Li(1)-O(8) bond length is 1.96 Å. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 5-coordinate geometry to one O(10), one O(3), one O(4), one O(6), and one O(7) atom. The Sb(1)-O(10) bond length is 2.59 Å. The Sb(1)-O(3) bond length is 2.11 Å. The Sb(1)-O(4) bond length is 2.17 Å. The Sb(1)-O(6) bond length is 2.12 Å. The Sb(1)-O(7) bond length is 2.36 Å. In the second Sb site, Sb(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(9) atom. The Sb(2)-O(1) bond length is 2.67 Å. The Sb(2)-O(10) bond length is 2.21 Å. The Sb(2)-O(2) bond length is 2.55 Å. The Sb(2)-O(6) bond length is 2.14 Å. The Sb(2)-O(7) bond length is 2.14 Å. The Sb(2)-O(9) bond length is 2.42 Å. In the third Sb site, Sb(3) is bonded to one O(1), one O(2), one O(6), one O(7), and one O(8) atom to form distorted SbO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Sb(3)-O(1) bond length is 2.30 Å. The Sb(3)-O(2) bond length is 2.28 Å. The Sb(3)-O(6) bond length is 2.30 Å. The Sb(3)-O(7) bond length is 2.05 Å. The Sb(3)-O(8) bond length is 2.31 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(3)O5 square pyramid. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(10) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Sb(3)O5 square pyramids. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(4) bond length is 1.58 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.57 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Sb(2), one Sb(3), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Sb(2), one Sb(3), 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 bent 120 degrees geometry to one Sb(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one P(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Sb(1), one Sb(2), and one Sb(3) atom to form edge-sharing OLiSb3 tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), one Sb(1), one Sb(2), and one Sb(3) atom to form distorted edge-sharing OLiSb3 tetrahedra. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Sb(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Sb(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Sb(1), one Sb(2), and one P(1) atom.