Li4Ce3Ge4 crystallizes in the orthorhombic Immm space group. Li(1) is bonded to three equivalent Ce(2), one Ge(1), and three equivalent Ge(2) atoms to form distorted LiCe3Ge4 tetrahedra that share  a cornercorner with one Ce(1)Ge6 octahedra, corners with five equivalent Li(1)Ce3Ge4 tetrahedra, edges with two equivalent Ce(1)Ge6 octahedra, edges with six equivalent Li(1)Ce3Ge4 tetrahedra, and faces with four equivalent Li(1)Ce3Ge4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to two equivalent Ge(2) and four equivalent Ge(1) atoms to form CeGe6 octahedra that share corners with four equivalent Li(1)Ce3Ge4 tetrahedra, edges with two equivalent Ce(1)Ge6 octahedra, and edges with eight equivalent Li(1)Ce3Ge4 tetrahedra. In the second Ce site, Ce(2) is bonded in a 12-coordinate geometry to six equivalent Li(1), two equivalent Ge(2), and four equivalent Ge(1) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 9-coordinate geometry to two equivalent Li(1), two equivalent Ce(1), four equivalent Ce(2), and one Ge(1) atom. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to six equivalent Li(1), one Ce(1), and two equivalent Ce(2) atoms.
Li4Ce3Ge4 crystallizes in the orthorhombic Immm space group. Li(1) is bonded to three equivalent Ce(2), one Ge(1), and three equivalent Ge(2) atoms to form distorted LiCe3Ge4 tetrahedra that share  a cornercorner with one Ce(1)Ge6 octahedra, corners with five equivalent Li(1)Ce3Ge4 tetrahedra, edges with two equivalent Ce(1)Ge6 octahedra, edges with six equivalent Li(1)Ce3Ge4 tetrahedra, and faces with four equivalent Li(1)Ce3Ge4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are two shorter (3.14 Å) and one longer (3.17 Å) Li(1)-Ce(2) bond length. The Li(1)-Ge(1) bond length is 2.62 Å. There are two shorter (2.66 Å) and one longer (2.70 Å) Li(1)-Ge(2) bond length. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to two equivalent Ge(2) and four equivalent Ge(1) atoms to form CeGe6 octahedra that share corners with four equivalent Li(1)Ce3Ge4 tetrahedra, edges with two equivalent Ce(1)Ge6 octahedra, and edges with eight equivalent Li(1)Ce3Ge4 tetrahedra. Both Ce(1)-Ge(2) bond lengths are 3.11 Å. All Ce(1)-Ge(1) bond lengths are 3.09 Å. In the second Ce site, Ce(2) is bonded in a 12-coordinate geometry to six equivalent Li(1), two equivalent Ge(2), and four equivalent Ge(1) atoms. Both Ce(2)-Ge(2) bond lengths are 3.19 Å. All Ce(2)-Ge(1) bond lengths are 3.20 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a 9-coordinate geometry to two equivalent Li(1), two equivalent Ce(1), four equivalent Ce(2), and one Ge(1) atom. The Ge(1)-Ge(1) bond length is 2.56 Å. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to six equivalent Li(1), one Ce(1), and two equivalent Ce(2) atoms.