Li2TiCuO4 crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to four equivalent O(2) atoms. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. Cu(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted CuO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Cu(1) atoms to form distorted OLi2TiCu2 square pyramids that share corners with four equivalent O(2)Li3Ti2Cu octahedra, corners with five equivalent O(1)Li2TiCu2 square pyramids, edges with four equivalent O(2)Li3Ti2Cu octahedra, and edges with four equivalent O(1)Li2TiCu2 square pyramids. The corner-sharing octahedral tilt angles are 80°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Ti(1), and one Cu(1) atom to form distorted OLi3Ti2Cu octahedra that share corners with six equivalent O(2)Li3Ti2Cu octahedra, corners with four equivalent O(1)Li2TiCu2 square pyramids, edges with four equivalent O(2)Li3Ti2Cu octahedra, and edges with four equivalent O(1)Li2TiCu2 square pyramids. The corner-sharing octahedra are not tilted.
Li2TiCuO4 crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. Both Li(1)-O(2) bond lengths are 2.16 Å. All Li(1)-O(1) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to four equivalent O(2) atoms. All Li(2)-O(2) bond lengths are 2.10 Å. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cu(1)O6 octahedra. Both Ti(1)-O(1) bond lengths are 2.02 Å. All Ti(1)-O(2) bond lengths are 1.99 Å. Cu(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted CuO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. Both Cu(1)-O(2) bond lengths are 2.47 Å. All Cu(1)-O(1) bond lengths are 1.99 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Cu(1) atoms to form distorted OLi2TiCu2 square pyramids that share corners with four equivalent O(2)Li3Ti2Cu octahedra, corners with five equivalent O(1)Li2TiCu2 square pyramids, edges with four equivalent O(2)Li3Ti2Cu octahedra, and edges with four equivalent O(1)Li2TiCu2 square pyramids. The corner-sharing octahedral tilt angles are 80°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Ti(1), and one Cu(1) atom to form distorted OLi3Ti2Cu octahedra that share corners with six equivalent O(2)Li3Ti2Cu octahedra, corners with four equivalent O(1)Li2TiCu2 square pyramids, edges with four equivalent O(2)Li3Ti2Cu octahedra, and edges with four equivalent O(1)Li2TiCu2 square pyramids. The corner-sharing octahedra are not tilted.