La4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. In the second La site, La(2) is bonded in a 9-coordinate geometry to three equivalent S(3) 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 La(1), two equivalent La(2), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SLa3Ge tetrahedra. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent La(1) and one Ge(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to three equivalent La(1) and one Ge(1) atom.
La4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. The La(1)-S(1) bond length is 2.94 Å. There is one shorter (2.89 Å) and one longer (2.99 Å) La(1)-S(2) bond length. There is one shorter (3.04 Å) and one longer (3.11 Å) La(1)-S(3) bond length. There are a spread of La(1)-S(4) bond distances ranging from 2.95-3.58 Å. In the second La site, La(2) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(1) atoms. All La(2)-S(3) bond lengths are 3.42 Å. All La(2)-S(1) bond lengths are 2.93 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 2.25 Å. The Ge(1)-S(2) bond length is 2.21 Å. The Ge(1)-S(3) bond length is 2.20 Å. The Ge(1)-S(4) bond length is 2.20 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one La(1), two equivalent La(2), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SLa3Ge tetrahedra. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent La(1) and one Ge(1) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one La(2), two equivalent La(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to three equivalent La(1) and one Ge(1) atom.