Li2Ni3TeO8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Te(1)O6 octahedra and corners with nine equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-61°. Ni(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Te(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. Te(1) is bonded to six equivalent O(2) atoms to form TeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent Ni(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent Ni(1) atoms to form OLiNi3 tetrahedra that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with nine equivalent O(2)LiNi2Te trigonal pyramids, and edges with three equivalent O(2)LiNi2Te trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent Ni(1), and one Te(1) atom to form distorted OLiNi2Te trigonal pyramids that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with nine equivalent O(2)LiNi2Te trigonal pyramids,  an edgeedge with one O(1)LiNi3 tetrahedra, and edges with two equivalent O(2)LiNi2Te trigonal pyramids.
Li2Ni3TeO8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Te(1)O6 octahedra and corners with nine equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-61°. The Li(1)-O(1) bond length is 2.02 Å. All Li(1)-O(2) bond lengths are 1.99 Å. Ni(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Te(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. Both Ni(1)-O(1) bond lengths are 1.95 Å. All Ni(1)-O(2) bond lengths are 2.08 Å. Te(1) is bonded to six equivalent O(2) atoms to form TeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent Ni(1)O6 octahedra. All Te(1)-O(2) bond lengths are 1.96 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent Ni(1) atoms to form OLiNi3 tetrahedra that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with nine equivalent O(2)LiNi2Te trigonal pyramids, and edges with three equivalent O(2)LiNi2Te trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent Ni(1), and one Te(1) atom to form distorted OLiNi2Te trigonal pyramids that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with nine equivalent O(2)LiNi2Te trigonal pyramids,  an edgeedge with one O(1)LiNi3 tetrahedra, and edges with two equivalent O(2)LiNi2Te trigonal pyramids.