Gd4(SiS4)3 crystallizes in the monoclinic Cc space group. There are four inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 9-coordinate geometry to one S(7), one S(8), one S(9), two equivalent S(4), two equivalent S(5), and two equivalent S(6) atoms. In the second Gd site, Gd(2) is bonded in a 7-coordinate geometry to one S(1), one S(11), one S(12), one S(3), one S(5), one S(7), and one S(8) atom. In the third Gd site, Gd(3) is bonded in a 7-coordinate geometry to one S(1), one S(10), one S(12), one S(2), one S(6), one S(7), and one S(8) atom. In the fourth Gd site, Gd(4) is bonded in a 7-coordinate geometry to one S(10), one S(11), one S(2), one S(3), one S(4), and two equivalent S(9) atoms. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a tetrahedral geometry to one S(1), one S(10), one S(4), and one S(7) atom. In the second Si site, Si(2) is bonded in a tetrahedral geometry to one S(12), one S(3), one S(5), and one S(8) atom. In the third Si site, Si(3) is bonded in a tetrahedral geometry to one S(11), one S(2), one S(6), and one S(9) atom. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(3), and one Si(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Gd(3), one Gd(4), and one Si(3) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(4), and one Si(2) atom. In the fourth S site, S(4) is bonded to one Gd(4), two equivalent Gd(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing SGd3Si tetrahedra. In the fifth S site, S(5) is bonded to one Gd(2), two equivalent Gd(1), and one Si(2) atom to form a mixture of distorted corner and edge-sharing SGd3Si tetrahedra. In the sixth S site, S(6) is bonded to one Gd(3), two equivalent Gd(1), and one Si(3) atom to form a mixture of distorted corner and edge-sharing SGd3Si tetrahedra. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one Si(1) atom. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one Si(2) atom. In the ninth S site, S(9) is bonded in a 4-coordinate geometry to one Gd(1), two equivalent Gd(4), and one Si(3) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Gd(3), one Gd(4), and one Si(1) atom. In the eleventh S site, S(11) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(4), and one Si(3) atom. In the twelfth S site, S(12) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(3), and one Si(2) atom.
Gd4(SiS4)3 crystallizes in the monoclinic Cc space group. There are four inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 9-coordinate geometry to one S(7), one S(8), one S(9), two equivalent S(4), two equivalent S(5), and two equivalent S(6) atoms. The Gd(1)-S(7) bond length is 3.35 Å. The Gd(1)-S(8) bond length is 3.35 Å. The Gd(1)-S(9) bond length is 3.35 Å. Both Gd(1)-S(4) bond lengths are 2.82 Å. Both Gd(1)-S(5) bond lengths are 2.82 Å. Both Gd(1)-S(6) bond lengths are 2.82 Å. In the second Gd site, Gd(2) is bonded in a 7-coordinate geometry to one S(1), one S(11), one S(12), one S(3), one S(5), one S(7), and one S(8) atom. The Gd(2)-S(1) bond length is 2.78 Å. The Gd(2)-S(11) bond length is 2.82 Å. The Gd(2)-S(12) bond length is 2.85 Å. The Gd(2)-S(3) bond length is 2.87 Å. The Gd(2)-S(5) bond length is 2.85 Å. The Gd(2)-S(7) bond length is 2.93 Å. The Gd(2)-S(8) bond length is 2.96 Å. In the third Gd site, Gd(3) is bonded in a 7-coordinate geometry to one S(1), one S(10), one S(12), one S(2), one S(6), one S(7), and one S(8) atom. The Gd(3)-S(1) bond length is 2.87 Å. The Gd(3)-S(10) bond length is 2.84 Å. The Gd(3)-S(12) bond length is 2.82 Å. The Gd(3)-S(2) bond length is 2.78 Å. The Gd(3)-S(6) bond length is 2.85 Å. The Gd(3)-S(7) bond length is 2.97 Å. The Gd(3)-S(8) bond length is 2.93 Å. In the fourth Gd site, Gd(4) is bonded in a 7-coordinate geometry to one S(10), one S(11), one S(2), one S(3), one S(4), and two equivalent S(9) atoms. The Gd(4)-S(10) bond length is 2.81 Å. The Gd(4)-S(11) bond length is 2.85 Å. The Gd(4)-S(2) bond length is 2.87 Å. The Gd(4)-S(3) bond length is 2.78 Å. The Gd(4)-S(4) bond length is 2.85 Å. There is one shorter (2.93 Å) and one longer (2.96 Å) Gd(4)-S(9) bond length. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded in a tetrahedral geometry to one S(1), one S(10), one S(4), and one S(7) atom. The Si(1)-S(1) bond length is 2.11 Å. The Si(1)-S(10) bond length is 2.12 Å. The Si(1)-S(4) bond length is 2.16 Å. The Si(1)-S(7) bond length is 2.10 Å. In the second Si site, Si(2) is bonded in a tetrahedral geometry to one S(12), one S(3), one S(5), and one S(8) atom. The Si(2)-S(12) bond length is 2.12 Å. The Si(2)-S(3) bond length is 2.11 Å. The Si(2)-S(5) bond length is 2.16 Å. The Si(2)-S(8) bond length is 2.10 Å. In the third Si site, Si(3) is bonded in a tetrahedral geometry to one S(11), one S(2), one S(6), and one S(9) atom. The Si(3)-S(11) bond length is 2.12 Å. The Si(3)-S(2) bond length is 2.11 Å. The Si(3)-S(6) bond length is 2.16 Å. The Si(3)-S(9) bond length is 2.10 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(3), and one Si(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Gd(3), one Gd(4), and one Si(3) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(4), and one Si(2) atom. In the fourth S site, S(4) is bonded to one Gd(4), two equivalent Gd(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing SGd3Si tetrahedra. In the fifth S site, S(5) is bonded to one Gd(2), two equivalent Gd(1), and one Si(2) atom to form a mixture of distorted corner and edge-sharing SGd3Si tetrahedra. In the sixth S site, S(6) is bonded to one Gd(3), two equivalent Gd(1), and one Si(3) atom to form a mixture of distorted corner and edge-sharing SGd3Si tetrahedra. In the seventh S site, S(7) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one Si(1) atom. In the eighth S site, S(8) is bonded in a 4-coordinate geometry to one Gd(1), one Gd(2), one Gd(3), and one Si(2) atom. In the ninth S site, S(9) is bonded in a 4-coordinate geometry to one Gd(1), two equivalent Gd(4), and one Si(3) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Gd(3), one Gd(4), and one Si(1) atom. In the eleventh S site, S(11) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(4), and one Si(3) atom. In the twelfth S site, S(12) is bonded in a 3-coordinate geometry to one Gd(2), one Gd(3), and one Si(2) atom.