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CeGe crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Ce is bonded in a 5-coordinate geometry to seven equivalent Ge atoms. There are a spread of Ce–Ge bond distances ranging from 3.07–3.31 Å. Ge is bonded in a 9-coordinate geometry to seven equivalent Ce and two equivalent Ge atoms. Both Ge–Ge bond lengths are 2.70 Å.
Ce4LiGe4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Li is bonded in a T-shaped geometry to five Ge atoms. There are a spread of Li–Ge bond distances ranging from 2.76–3.26 Å. There are two inequivalent Ce sites. In the first Ce site, Ce is bonded in a 7-coordinate geometry to seven Ge atoms. There are a spread of Ce–Ge bond distances ranging from 3.06–3.54 Å. In the second Ce site, Ce is bonded in a 6-coordinate geometry to six Ge atoms. There are a spread of Ce–Ge bond distances ranging from 2.95–3.14 Å. There are three inequivalent Ge sites. In the first Ge site, Ge is bonded in a 9-coordinate geometry to two equivalent Li, six Ce, and one Ge atom. The Ge–Ge bond length is 2.59 Å. In the second Ge site, Ge is bonded in a 9-coordinate geometry to one Li, seven Ce, and one Ge atom. The Ge–Ge bond length is 2.67 Å. In the third Ge site, Ge is bonded in a 8-coordinate geometry to one Li, six Ce, and one Ge atom.