Ge4Ti5 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent Ge(1), two equivalent Ge(2), and two equivalent Ge(3) atoms to form distorted TiGe6 octahedra that share corners with four equivalent Ti(1)Ge6 octahedra, corners with eight equivalent Ti(3)Ge7 pentagonal bipyramids, and faces with four equivalent Ti(3)Ge7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 44-56°. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one Ge(1), two equivalent Ge(2), and three equivalent Ge(3) atoms. In the third Ti site, Ti(3) is bonded to one Ge(2), two equivalent Ge(1), and four equivalent Ge(3) atoms to form distorted TiGe7 pentagonal bipyramids that share corners with four equivalent Ti(1)Ge6 octahedra, corners with six equivalent Ti(3)Ge7 pentagonal bipyramids, edges with two equivalent Ti(3)Ge7 pentagonal bipyramids, faces with two equivalent Ti(1)Ge6 octahedra, and faces with three equivalent Ti(3)Ge7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 47-52°. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 9-coordinate geometry to two equivalent Ti(1), two equivalent Ti(2), four equivalent Ti(3), and one Ge(2) atom. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to two equivalent Ti(1), two equivalent Ti(3), four equivalent Ti(2), and one Ge(1) atom. In the third Ge site, Ge(3) is bonded in a 8-coordinate geometry to one Ti(1), three equivalent Ti(2), and four equivalent Ti(3) atoms.
Ge4Ti5 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent Ge(1), two equivalent Ge(2), and two equivalent Ge(3) atoms to form distorted TiGe6 octahedra that share corners with four equivalent Ti(1)Ge6 octahedra, corners with eight equivalent Ti(3)Ge7 pentagonal bipyramids, and faces with four equivalent Ti(3)Ge7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 44-56°. There is one shorter (2.56 Å) and one longer (2.59 Å) Ti(1)-Ge(1) bond length. There is one shorter (2.59 Å) and one longer (2.74 Å) Ti(1)-Ge(2) bond length. Both Ti(1)-Ge(3) bond lengths are 2.70 Å. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one Ge(1), two equivalent Ge(2), and three equivalent Ge(3) atoms. The Ti(2)-Ge(1) bond length is 2.68 Å. There is one shorter (2.55 Å) and one longer (2.60 Å) Ti(2)-Ge(2) bond length. There are a spread of Ti(2)-Ge(3) bond distances ranging from 2.52-2.67 Å. In the third Ti site, Ti(3) is bonded to one Ge(2), two equivalent Ge(1), and four equivalent Ge(3) atoms to form distorted TiGe7 pentagonal bipyramids that share corners with four equivalent Ti(1)Ge6 octahedra, corners with six equivalent Ti(3)Ge7 pentagonal bipyramids, edges with two equivalent Ti(3)Ge7 pentagonal bipyramids, faces with two equivalent Ti(1)Ge6 octahedra, and faces with three equivalent Ti(3)Ge7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 47-52°. The Ti(3)-Ge(2) bond length is 2.80 Å. There is one shorter (2.65 Å) and one longer (2.85 Å) Ti(3)-Ge(1) bond length. There are a spread of Ti(3)-Ge(3) bond distances ranging from 2.68-2.92 Å. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 9-coordinate geometry to two equivalent Ti(1), two equivalent Ti(2), four equivalent Ti(3), and one Ge(2) atom. The Ge(1)-Ge(2) bond length is 2.53 Å. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to two equivalent Ti(1), two equivalent Ti(3), four equivalent Ti(2), and one Ge(1) atom. In the third Ge site, Ge(3) is bonded in a 8-coordinate geometry to one Ti(1), three equivalent Ti(2), and four equivalent Ti(3) atoms.