Cu4(TiS4) crystallizes in the tetragonal I-42m space group. Ti(1) is bonded to four equivalent S(1) atoms to form distorted TiS4 tetrahedra that share corners with four equivalent Cu(2)S4 tetrahedra, edges with two equivalent Cu(2)S4 tetrahedra, and edges with four equivalent Cu(1)S4 tetrahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to four equivalent S(1) atoms to form distorted CuS4 tetrahedra that share corners with four equivalent Cu(1)S4 tetrahedra, corners with eight equivalent Cu(2)S4 tetrahedra, and edges with two equivalent Ti(1)S4 tetrahedra. In the second Cu site, Cu(2) is bonded to four equivalent S(1) atoms to form distorted CuS4 tetrahedra that share corners with two equivalent Ti(1)S4 tetrahedra, corners with four equivalent Cu(2)S4 tetrahedra, corners with eight equivalent Cu(1)S4 tetrahedra, and  an edgeedge with one Ti(1)S4 tetrahedra. S(1) is bonded to one Ti(1), two equivalent Cu(1), and two equivalent Cu(2) atoms to form a mixture of distorted corner and edge-sharing STiCu4 trigonal bipyramids.
Cu4(TiS4) crystallizes in the tetragonal I-42m space group. Ti(1) is bonded to four equivalent S(1) atoms to form distorted TiS4 tetrahedra that share corners with four equivalent Cu(2)S4 tetrahedra, edges with two equivalent Cu(2)S4 tetrahedra, and edges with four equivalent Cu(1)S4 tetrahedra. All Ti(1)-S(1) bond lengths are 2.29 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to four equivalent S(1) atoms to form distorted CuS4 tetrahedra that share corners with four equivalent Cu(1)S4 tetrahedra, corners with eight equivalent Cu(2)S4 tetrahedra, and edges with two equivalent Ti(1)S4 tetrahedra. All Cu(1)-S(1) bond lengths are 2.33 Å. In the second Cu site, Cu(2) is bonded to four equivalent S(1) atoms to form distorted CuS4 tetrahedra that share corners with two equivalent Ti(1)S4 tetrahedra, corners with four equivalent Cu(2)S4 tetrahedra, corners with eight equivalent Cu(1)S4 tetrahedra, and  an edgeedge with one Ti(1)S4 tetrahedra. There are two shorter (2.31 Å) and two longer (2.34 Å) Cu(2)-S(1) bond lengths. S(1) is bonded to one Ti(1), two equivalent Cu(1), and two equivalent Cu(2) atoms to form a mixture of distorted corner and edge-sharing STiCu4 trigonal bipyramids.