Ti3V3Ge5 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(5), two equivalent Ge(3), and three equivalent Ge(4) atoms. In the second Ti site, Ti(2) is bonded in a 7-coordinate geometry to one Ge(2), one Ge(4), two equivalent Ge(3), and three equivalent Ge(5) atoms. In the third Ti site, Ti(3) is bonded in a 7-coordinate geometry to one Ge(4), two equivalent Ge(1), two equivalent Ge(2), and two equivalent Ge(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one Ge(1), one Ge(2), two equivalent Ge(4), and two equivalent Ge(5) atoms. In the second V site, V(2) is bonded in a 7-coordinate geometry to one Ge(5), two equivalent Ge(1), two equivalent Ge(2), and two equivalent Ge(3) atoms. There are five inequivalent Ge sites. In the first Ge site, Ge(5) is bonded in a 9-coordinate geometry to one Ti(1), three equivalent Ti(2), one V(2), and four equivalent V(1) atoms. In the second Ge site, Ge(1) is bonded in a 7-coordinate geometry to one Ti(1), two equivalent Ti(3), two equivalent V(1), and two equivalent V(2) atoms. In the third Ge site, Ge(2) is bonded in a 7-coordinate geometry to one Ti(2), two equivalent Ti(3), two equivalent V(1), and two equivalent V(2) atoms. In the fourth Ge site, Ge(3) is bonded in a 10-coordinate geometry to two equivalent Ti(1), two equivalent Ti(2), two equivalent Ti(3), two equivalent V(2), and two equivalent Ge(3) atoms. In the fifth Ge site, Ge(4) is bonded in a 9-coordinate geometry to one Ti(2), one Ti(3), three equivalent Ti(1), and four equivalent V(1) atoms.
Ti3V3Ge5 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 7-coordinate geometry to one Ge(1), one Ge(5), two equivalent Ge(3), and three equivalent Ge(4) atoms. The Ti(1)-Ge(1) bond length is 2.64 Å. The Ti(1)-Ge(5) bond length is 2.70 Å. Both Ti(1)-Ge(3) bond lengths are 2.80 Å. There is one shorter (2.77 Å) and two longer (2.88 Å) Ti(1)-Ge(4) bond lengths. In the second Ti site, Ti(2) is bonded in a 7-coordinate geometry to one Ge(2), one Ge(4), two equivalent Ge(3), and three equivalent Ge(5) atoms. The Ti(2)-Ge(2) bond length is 2.59 Å. The Ti(2)-Ge(4) bond length is 2.69 Å. Both Ti(2)-Ge(3) bond lengths are 2.82 Å. There is one shorter (2.80 Å) and two longer (2.87 Å) Ti(2)-Ge(5) bond lengths. In the third Ti site, Ti(3) is bonded in a 7-coordinate geometry to one Ge(4), two equivalent Ge(1), two equivalent Ge(2), and two equivalent Ge(3) atoms. The Ti(3)-Ge(4) bond length is 2.50 Å. Both Ti(3)-Ge(1) bond lengths are 2.79 Å. There is one shorter (2.48 Å) and one longer (2.64 Å) Ti(3)-Ge(2) bond length. Both Ti(3)-Ge(3) bond lengths are 2.61 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one Ge(1), one Ge(2), two equivalent Ge(4), and two equivalent Ge(5) atoms. The V(1)-Ge(1) bond length is 2.51 Å. The V(1)-Ge(2) bond length is 2.50 Å. There is one shorter (2.55 Å) and one longer (2.66 Å) V(1)-Ge(4) bond length. There is one shorter (2.57 Å) and one longer (2.66 Å) V(1)-Ge(5) bond length. In the second V site, V(2) is bonded in a 7-coordinate geometry to one Ge(5), two equivalent Ge(1), two equivalent Ge(2), and two equivalent Ge(3) atoms. The V(2)-Ge(5) bond length is 2.47 Å. There is one shorter (2.47 Å) and one longer (2.60 Å) V(2)-Ge(1) bond length. Both V(2)-Ge(2) bond lengths are 2.77 Å. Both V(2)-Ge(3) bond lengths are 2.58 Å. There are five inequivalent Ge sites. In the first Ge site, Ge(5) is bonded in a 9-coordinate geometry to one Ti(1), three equivalent Ti(2), one V(2), and four equivalent V(1) atoms. In the second Ge site, Ge(1) is bonded in a 7-coordinate geometry to one Ti(1), two equivalent Ti(3), two equivalent V(1), and two equivalent V(2) atoms. In the third Ge site, Ge(2) is bonded in a 7-coordinate geometry to one Ti(2), two equivalent Ti(3), two equivalent V(1), and two equivalent V(2) atoms. In the fourth Ge site, Ge(3) is bonded in a 10-coordinate geometry to two equivalent Ti(1), two equivalent Ti(2), two equivalent Ti(3), two equivalent V(2), and two equivalent Ge(3) atoms. There is one shorter (2.49 Å) and one longer (2.56 Å) Ge(3)-Ge(3) bond length. In the fifth Ge site, Ge(4) is bonded in a 9-coordinate geometry to one Ti(2), one Ti(3), three equivalent Ti(1), and four equivalent V(1) atoms.