Ce4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(4), and three equivalent S(3) atoms. In the second Ce site, Ce(2) is bonded in a 9-coordinate geometry to three equivalent S(2) and six equivalent S(1) atoms. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent Ce(2), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SCe3Ge tetrahedra. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Ce(2), two equivalent Ce(1), and one Ge(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to three equivalent Ce(1) and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Ce(1) and one Ge(1) atom.
Ce4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(4), and three equivalent S(3) atoms. The Ce(1)-S(1) bond length is 2.92 Å. There is one shorter (3.00 Å) and one longer (3.09 Å) Ce(1)-S(2) bond length. There is one shorter (2.84 Å) and one longer (2.94 Å) Ce(1)-S(4) bond length. There are a spread of Ce(1)-S(3) bond distances ranging from 2.90-3.58 Å. In the second Ce site, Ce(2) is bonded in a 9-coordinate geometry to three equivalent S(2) and six equivalent S(1) atoms. All Ce(2)-S(2) bond lengths are 3.39 Å. All Ce(2)-S(1) bond lengths are 2.89 Å. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Ge(1)-S(1) bond length is 2.28 Å. The Ge(1)-S(2) bond length is 2.23 Å. The Ge(1)-S(3) bond length is 2.23 Å. The Ge(1)-S(4) bond length is 2.25 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ce(1), two equivalent Ce(2), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SCe3Ge tetrahedra. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Ce(2), two equivalent Ce(1), and one Ge(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to three equivalent Ce(1) and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Ce(1) and one Ge(1) atom.