Gd3NS3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 7-coordinate geometry to one N(1), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In the second Gd site, Gd(2) is bonded in a 7-coordinate geometry to two equivalent N(1), one S(2), one S(3), and three equivalent S(1) atoms. In the third Gd site, Gd(3) is bonded to one N(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted edge-sharing GdS5N octahedra. N(1) is bonded to one Gd(1), one Gd(3), and two equivalent Gd(2) atoms to form NGd4 tetrahedra that share corners with three equivalent S(3)Gd6 octahedra, corners with two equivalent S(1)Gd5 square pyramids, corners with two equivalent N(1)Gd4 tetrahedra, edges with two equivalent S(3)Gd6 octahedra, and edges with three equivalent S(1)Gd5 square pyramids. The corner-sharing octahedral tilt angles range from 6-40°. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Gd(1) and three equivalent Gd(2) atoms to form SGd5 square pyramids that share corners with five equivalent S(3)Gd6 octahedra, corners with two equivalent N(1)Gd4 tetrahedra,  an edgeedge with one S(3)Gd6 octahedra, edges with four equivalent S(1)Gd5 square pyramids, and edges with three equivalent N(1)Gd4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-53°. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Gd(2), two equivalent Gd(1), and two equivalent Gd(3) atoms. In the third S site, S(3) is bonded to one Gd(2), two equivalent Gd(1), and three equivalent Gd(3) atoms to form distorted SGd6 octahedra that share corners with five equivalent S(1)Gd5 square pyramids, corners with three equivalent N(1)Gd4 tetrahedra, edges with four equivalent S(3)Gd6 octahedra,  an edgeedge with one S(1)Gd5 square pyramid, and edges with two equivalent N(1)Gd4 tetrahedra.
Gd3NS3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 7-coordinate geometry to one N(1), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Gd(1)-N(1) bond length is 2.26 Å. Both Gd(1)-S(1) bond lengths are 2.75 Å. Both Gd(1)-S(2) bond lengths are 2.92 Å. Both Gd(1)-S(3) bond lengths are 3.11 Å. In the second Gd site, Gd(2) is bonded in a 7-coordinate geometry to two equivalent N(1), one S(2), one S(3), and three equivalent S(1) atoms. Both Gd(2)-N(1) bond lengths are 2.32 Å. The Gd(2)-S(2) bond length is 2.82 Å. The Gd(2)-S(3) bond length is 3.26 Å. There is one shorter (2.80 Å) and two longer (2.97 Å) Gd(2)-S(1) bond lengths. In the third Gd site, Gd(3) is bonded to one N(1), two equivalent S(2), and three equivalent S(3) atoms to form distorted edge-sharing GdS5N octahedra. The Gd(3)-N(1) bond length is 2.20 Å. Both Gd(3)-S(2) bond lengths are 2.81 Å. There are two shorter (2.77 Å) and one longer (2.99 Å) Gd(3)-S(3) bond length. N(1) is bonded to one Gd(1), one Gd(3), and two equivalent Gd(2) atoms to form NGd4 tetrahedra that share corners with three equivalent S(3)Gd6 octahedra, corners with two equivalent S(1)Gd5 square pyramids, corners with two equivalent N(1)Gd4 tetrahedra, edges with two equivalent S(3)Gd6 octahedra, and edges with three equivalent S(1)Gd5 square pyramids. The corner-sharing octahedral tilt angles range from 6-40°. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Gd(1) and three equivalent Gd(2) atoms to form SGd5 square pyramids that share corners with five equivalent S(3)Gd6 octahedra, corners with two equivalent N(1)Gd4 tetrahedra,  an edgeedge with one S(3)Gd6 octahedra, edges with four equivalent S(1)Gd5 square pyramids, and edges with three equivalent N(1)Gd4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-53°. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Gd(2), two equivalent Gd(1), and two equivalent Gd(3) atoms. In the third S site, S(3) is bonded to one Gd(2), two equivalent Gd(1), and three equivalent Gd(3) atoms to form distorted SGd6 octahedra that share corners with five equivalent S(1)Gd5 square pyramids, corners with three equivalent N(1)Gd4 tetrahedra, edges with four equivalent S(3)Gd6 octahedra,  an edgeedge with one S(1)Gd5 square pyramid, and edges with two equivalent N(1)Gd4 tetrahedra.