Gd4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(2) atoms. In the second Gd site, Gd(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 Gd(2) and one Ge(1) atom. In the second S site, S(2) is bonded to one Gd(2), two equivalent Gd(1), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SGd3Ge tetrahedra. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Gd(1), two equivalent Gd(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a distorted trigonal planar geometry to two equivalent Gd(2) and one Ge(1) atom.
Gd4(GeS4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 9-coordinate geometry to three equivalent S(3) and six equivalent S(2) atoms. All Gd(1)-S(3) bond lengths are 3.37 Å. There are three shorter (2.83 Å) and three longer (2.84 Å) Gd(1)-S(2) bond lengths. In the second Gd site, Gd(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 Gd(2)-S(2) bond length is 2.86 Å. There is one shorter (2.82 Å) and one longer (2.93 Å) Gd(2)-S(1) bond length. There is one shorter (2.94 Å) and one longer (3.01 Å) Gd(2)-S(3) bond length. There is one shorter (2.81 Å) and one longer (2.85 Å) Gd(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 2.22 Å. The Ge(1)-S(2) bond length is 2.27 Å. The Ge(1)-S(3) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.24 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Gd(2) and one Ge(1) atom. In the second S site, S(2) is bonded to one Gd(2), two equivalent Gd(1), and one Ge(1) atom to form a mixture of distorted edge and corner-sharing SGd3Ge tetrahedra. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Gd(1), two equivalent Gd(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a distorted trigonal planar geometry to two equivalent Gd(2) and one Ge(1) atom.