Li3Sb3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(2), one O(3), and one O(8) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Sb(1)O5 square pyramid, corners with two equivalent Sb(2)O5 square pyramids,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(3), one O(4), and one O(9) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Sb(2)O5 square pyramid, corners with two equivalent Sb(1)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(4)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(10), one O(15), one O(16), and one O(6) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Sb(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(11), one O(14), one O(2), one O(5), and one O(9) atom to form SbO5 square pyramids that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. In the second Sb site, Sb(2) is bonded to one O(12), one O(16), one O(4), one O(7), and one O(8) atom to form SbO5 square pyramids that share corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. In the third Sb site, Sb(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(15), and one O(6) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(1)O5 square pyramid,  a cornercorner with one Sb(2)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. In the second P site, P(2) is bonded to one O(10), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one Sb(1)O5 square pyramid,  a cornercorner with one Sb(2)O5 square pyramid,  a cornercorner with one Li(3)O4 tetrahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(12), one O(13), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(1)O5 square pyramid, corners with two equivalent Sb(2)O5 square pyramids, and  an edgeedge with one Li(1)O5 square pyramid. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(16), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(2)O5 square pyramid, corners with two equivalent Sb(1)O5 square pyramids, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one Sb(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Sb(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Sb(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Sb(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Sb(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Sb(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Sb(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Sb(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one Sb(3), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(2), one Sb(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Sb(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Sb(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted single-bond geometry to one Sb(1), one Sb(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Sb(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(4) atom.
Li3Sb3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(2), one O(3), and one O(8) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Sb(1)O5 square pyramid, corners with two equivalent Sb(2)O5 square pyramids,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(12) bond length is 2.09 Å. The Li(1)-O(2) bond length is 2.43 Å. The Li(1)-O(3) bond length is 1.95 Å. The Li(1)-O(8) bond length is 2.40 Å. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(3), one O(4), and one O(9) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Sb(2)O5 square pyramid, corners with two equivalent Sb(1)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(4)O4 tetrahedra. The Li(2)-O(1) bond length is 2.03 Å. The Li(2)-O(11) bond length is 2.17 Å. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.24 Å. The Li(2)-O(9) bond length is 2.14 Å. In the third Li site, Li(3) is bonded to one O(10), one O(15), one O(16), and one O(6) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Sb(2)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Li(3)-O(10) bond length is 2.05 Å. The Li(3)-O(15) bond length is 2.05 Å. The Li(3)-O(16) bond length is 2.11 Å. The Li(3)-O(6) bond length is 2.12 Å. There are three inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(11), one O(14), one O(2), one O(5), and one O(9) atom to form SbO5 square pyramids that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The Sb(1)-O(11) bond length is 2.33 Å. The Sb(1)-O(14) bond length is 2.45 Å. The Sb(1)-O(2) bond length is 2.25 Å. The Sb(1)-O(5) bond length is 2.01 Å. The Sb(1)-O(9) bond length is 2.18 Å. In the second Sb site, Sb(2) is bonded to one O(12), one O(16), one O(4), one O(7), and one O(8) atom to form SbO5 square pyramids that share corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The Sb(2)-O(12) bond length is 2.39 Å. The Sb(2)-O(16) bond length is 2.29 Å. The Sb(2)-O(4) bond length is 2.34 Å. The Sb(2)-O(7) bond length is 2.08 Å. The Sb(2)-O(8) bond length is 2.12 Å. In the third Sb site, Sb(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(15), and one O(6) atom. The Sb(3)-O(1) bond length is 2.76 Å. The Sb(3)-O(10) bond length is 2.13 Å. The Sb(3)-O(13) bond length is 2.06 Å. The Sb(3)-O(14) bond length is 2.53 Å. The Sb(3)-O(15) bond length is 2.65 Å. The Sb(3)-O(6) bond length is 2.22 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(1)O5 square pyramid,  a cornercorner with one Sb(2)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one Li(3)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.58 Å. In the second P site, P(2) is bonded to one O(10), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one Sb(1)O5 square pyramid,  a cornercorner with one Sb(2)O5 square pyramid,  a cornercorner with one Li(3)O4 tetrahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The P(2)-O(10) bond length is 1.58 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(12), one O(13), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(1)O5 square pyramid, corners with two equivalent Sb(2)O5 square pyramids, and  an edgeedge with one Li(1)O5 square pyramid. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(13) bond length is 1.56 Å. The P(3)-O(14) bond length is 1.55 Å. The P(3)-O(8) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(16), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Sb(2)O5 square pyramid, corners with two equivalent Sb(1)O5 square pyramids, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The P(4)-O(11) bond length is 1.56 Å. The P(4)-O(15) bond length is 1.55 Å. The P(4)-O(16) bond length is 1.57 Å. The P(4)-O(9) bond length is 1.58 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), one Sb(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Sb(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Sb(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Sb(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Sb(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Sb(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Sb(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one Sb(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(3), one Sb(3), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(2), one Sb(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Sb(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Sb(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted single-bond geometry to one Sb(1), one Sb(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Sb(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(3), one Sb(2), and one P(4) atom.