Sm4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(2) atoms. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), and two equivalent S(4) 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 in a 3-coordinate geometry to two equivalent Sm(2) and one Ge(1) atom. In the second S site, S(2) is bonded to one Sm(2), two equivalent Sm(1), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SSm3Ge tetrahedra. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Sm(1), two equivalent Sm(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Sm(2) and one Ge(1) atom.
Sm4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(2) atoms. All Sm(1)-S(3) bond lengths are 3.39 Å. There are three shorter (2.85 Å) and three longer (2.86 Å) Sm(1)-S(2) bond lengths. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms. The Sm(2)-S(2) bond length is 2.89 Å. There is one shorter (2.83 Å) and one longer (2.92 Å) Sm(2)-S(1) bond length. There is one shorter (2.96 Å) and one longer (3.02 Å) Sm(2)-S(3) bond length. There is one shorter (2.84 Å) and one longer (2.88 Å) Sm(2)-S(4) bond length. 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 2.20 Å. The Ge(1)-S(2) bond length is 2.25 Å. The Ge(1)-S(3) bond length is 2.20 Å. The Ge(1)-S(4) bond length is 2.21 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Sm(2) and one Ge(1) atom. In the second S site, S(2) is bonded to one Sm(2), two equivalent Sm(1), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SSm3Ge tetrahedra. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Sm(1), two equivalent Sm(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to two equivalent Sm(2) and one Ge(1) atom.