Ti3Se4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form a mixture of corner, face, and edge-sharing TiSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. In the second Ti site, Ti(2) is bonded to three equivalent Se(1) and three equivalent Se(2) atoms to form a mixture of distorted corner, face, and edge-sharing TiSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Ti(1) and three equivalent Ti(2) atoms. In the second Se site, Se(2) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1) and three equivalent Ti(2) atoms.
Ti3Se4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent Se(2) and four equivalent Se(1) atoms to form a mixture of corner, face, and edge-sharing TiSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. Both Ti(1)-Se(2) bond lengths are 2.60 Å. All Ti(1)-Se(1) bond lengths are 2.64 Å. In the second Ti site, Ti(2) is bonded to three equivalent Se(1) and three equivalent Se(2) atoms to form a mixture of distorted corner, face, and edge-sharing TiSe6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. There are two shorter (2.67 Å) and one longer (2.80 Å) Ti(2)-Se(1) bond length. There is one shorter (2.54 Å) and two longer (2.55 Å) Ti(2)-Se(2) bond lengths. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Ti(1) and three equivalent Ti(2) atoms. In the second Se site, Se(2) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1) and three equivalent Ti(2) atoms.