Li2Cu2TeO6 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, edges with two equivalent Te(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 20°. Cu(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Te(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TeO6 octahedra that share corners with four equivalent Li(1)O6 octahedra and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 20°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Cu(1), and one Te(1) atom to form a mixture of corner and edge-sharing OLi2Cu2Te trigonal bipyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cu(1), and one Te(1) atom.
Li2Cu2TeO6 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, edges with two equivalent Te(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 20°. Both Li(1)-O(1) bond lengths are 2.36 Å. There are two shorter (2.12 Å) and two longer (2.13 Å) Li(1)-O(2) bond lengths. Cu(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(1)-O(1) bond lengths are 1.99 Å. Both Cu(1)-O(2) bond lengths are 1.97 Å. Te(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TeO6 octahedra that share corners with four equivalent Li(1)O6 octahedra and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 20°. Both Te(1)-O(1) bond lengths are 2.00 Å. All Te(1)-O(2) bond lengths are 1.94 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Cu(1), and one Te(1) atom to form a mixture of corner and edge-sharing OLi2Cu2Te trigonal bipyramids. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cu(1), and one Te(1) atom.