Li4Sb(TeO4)3 crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and two equivalent O(6) atoms to form LiO4 tetrahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and corners with four equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-68°. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to two equivalent O(3) and two equivalent O(6) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(4) atoms. In the fourth Li site, Li(4) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and corners with four equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-80°. Sb(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form SbO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with four equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TeO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Te site, Te(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. In the third Te site, Te(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(2)O6 octahedra, corners with four equivalent Li(1)O4 tetrahedra, and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Sb(1), and one Te(1) atom to form distorted corner-sharing OLi2SbTe trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Te(1), and one Te(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Sb(1), and one Te(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(3), one Te(1), and one Te(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(4), one Sb(1), and one Te(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Te(2), and one Te(3) atom to form distorted corner-sharing OLi2Te2 trigonal pyramids.
Li4Sb(TeO4)3 crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and two equivalent O(6) atoms to form LiO4 tetrahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and corners with four equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-68°. Both Li(1)-O(2) bond lengths are 1.95 Å. Both Li(1)-O(6) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Li(2)-O(3) bond lengths are 2.04 Å. Both Li(2)-O(6) bond lengths are 2.21 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Li(3)-O(1) bond lengths are 2.24 Å. Both Li(3)-O(4) bond lengths are 1.95 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and corners with four equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-80°. Both Li(4)-O(1) bond lengths are 2.21 Å. Both Li(4)-O(5) bond lengths are 2.02 Å. Sb(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form SbO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with four equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Both Sb(1)-O(1) bond lengths are 1.99 Å. Both Sb(1)-O(3) bond lengths are 2.09 Å. Both Sb(1)-O(5) bond lengths are 2.03 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TeO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. Both Te(1)-O(1) bond lengths are 2.22 Å. Both Te(1)-O(2) bond lengths are 2.00 Å. Both Te(1)-O(4) bond lengths are 2.06 Å. In the second Te site, Te(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. Both Te(2)-O(3) bond lengths are 1.99 Å. Both Te(2)-O(5) bond lengths are 2.04 Å. Both Te(2)-O(6) bond lengths are 1.91 Å. In the third Te site, Te(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(2)O6 octahedra, corners with four equivalent Li(1)O4 tetrahedra, and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. Both Te(3)-O(2) bond lengths are 2.09 Å. Both Te(3)-O(4) bond lengths are 2.03 Å. Both Te(3)-O(6) bond lengths are 2.46 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(4), one Sb(1), and one Te(1) atom to form distorted corner-sharing OLi2SbTe trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Te(1), and one Te(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Sb(1), and one Te(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(3), one Te(1), and one Te(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(4), one Sb(1), and one Te(2) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Te(2), and one Te(3) atom to form distorted corner-sharing OLi2Te2 trigonal pyramids.