Ti5Te4 is Titanium telluride structured and crystallizes in the tetragonal I4/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to eight equivalent Ti(2) and four equivalent Te(1) atoms to form distorted TiTi8Te4 cuboctahedra that share corners with four equivalent Ti(2)Ti2Te5 square pyramids, edges with eight equivalent Ti(2)Ti2Te5 square pyramids, and faces with two equivalent Ti(1)Ti8Te4 cuboctahedra. In the second Ti site, Ti(2) is bonded to two equivalent Ti(1) and five equivalent Te(1) atoms to form distorted TiTi2Te5 square pyramids that share  a cornercorner with one Ti(1)Ti8Te4 cuboctahedra, corners with six equivalent Ti(2)Ti2Te5 square pyramids, edges with two equivalent Ti(1)Ti8Te4 cuboctahedra, edges with seven equivalent Ti(2)Ti2Te5 square pyramids, and faces with four equivalent Ti(2)Ti2Te5 square pyramids. Te(1) is bonded in a 6-coordinate geometry to one Ti(1) and five equivalent Ti(2) atoms.
Ti5Te4 is Titanium telluride structured and crystallizes in the tetragonal I4/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to eight equivalent Ti(2) and four equivalent Te(1) atoms to form distorted TiTi8Te4 cuboctahedra that share corners with four equivalent Ti(2)Ti2Te5 square pyramids, edges with eight equivalent Ti(2)Ti2Te5 square pyramids, and faces with two equivalent Ti(1)Ti8Te4 cuboctahedra. All Ti(1)-Ti(2) bond lengths are 2.94 Å. All Ti(1)-Te(1) bond lengths are 2.90 Å. In the second Ti site, Ti(2) is bonded to two equivalent Ti(1) and five equivalent Te(1) atoms to form distorted TiTi2Te5 square pyramids that share  a cornercorner with one Ti(1)Ti8Te4 cuboctahedra, corners with six equivalent Ti(2)Ti2Te5 square pyramids, edges with two equivalent Ti(1)Ti8Te4 cuboctahedra, edges with seven equivalent Ti(2)Ti2Te5 square pyramids, and faces with four equivalent Ti(2)Ti2Te5 square pyramids. There are a spread of Ti(2)-Te(1) bond distances ranging from 2.78-2.80 Å. Te(1) is bonded in a 6-coordinate geometry to one Ti(1) and five equivalent Ti(2) atoms.