TiSi is Parent of FeAs superconductors-derived structured and crystallizes in the orthorhombic Amm2 space group. The structure is three-dimensional. Ti4+ is bonded in a 8-coordinate geometry to eight equivalent Si4- atoms. There are a spread of Ti–Si bond distances ranging from 2.63–2.88 Å. Si4- is bonded to eight equivalent Ti4+ and four equivalent Si4- atoms to form a mixture of distorted corner, edge, and face-sharing SiTi8Si4 cuboctahedra. All Si–Si bond lengths are 2.79 Å.