Sc4N2S3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded in a 6-coordinate geometry to three equivalent N(1), one S(1), and two equivalent S(2) atoms. In the second Sc site, Sc(2) is bonded in a 6-coordinate geometry to one N(1), two equivalent S(1), and three equivalent S(2) atoms. N(1) is bonded to one Sc(2) and three equivalent Sc(1) atoms to form NSc4 tetrahedra that share  a cornercorner with one S(1)Sc6 octahedra, corners with seven equivalent S(2)Sc5 square pyramids, corners with two equivalent N(1)Sc4 tetrahedra, edges with two equivalent S(1)Sc6 octahedra,  an edgeedge with one S(2)Sc5 square pyramid, and edges with two equivalent N(1)Sc4 tetrahedra. The corner-sharing octahedral tilt angles are 21°. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Sc(1) and four equivalent Sc(2) atoms to form SSc6 octahedra that share corners with four equivalent S(2)Sc5 square pyramids, corners with two equivalent N(1)Sc4 tetrahedra, edges with two equivalent S(1)Sc6 octahedra, edges with six equivalent S(2)Sc5 square pyramids, and edges with four equivalent N(1)Sc4 tetrahedra. In the second S site, S(2) is bonded to two equivalent Sc(1) and three equivalent Sc(2) atoms to form SSc5 square pyramids that share corners with two equivalent S(1)Sc6 octahedra, corners with seven equivalent N(1)Sc4 tetrahedra, edges with three equivalent S(1)Sc6 octahedra, edges with four equivalent S(2)Sc5 square pyramids, and  an edgeedge with one N(1)Sc4 tetrahedra. The corner-sharing octahedral tilt angles are 14°.
Sc4N2S3 crystallizes in the monoclinic C2/m space group. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded in a 6-coordinate geometry to three equivalent N(1), one S(1), and two equivalent S(2) atoms. There is one shorter (2.07 Å) and two longer (2.18 Å) Sc(1)-N(1) bond lengths. The Sc(1)-S(1) bond length is 2.70 Å. Both Sc(1)-S(2) bond lengths are 2.75 Å. In the second Sc site, Sc(2) is bonded in a 6-coordinate geometry to one N(1), two equivalent S(1), and three equivalent S(2) atoms. The Sc(2)-N(1) bond length is 2.00 Å. Both Sc(2)-S(1) bond lengths are 2.64 Å. There are two shorter (2.55 Å) and one longer (2.91 Å) Sc(2)-S(2) bond length. N(1) is bonded to one Sc(2) and three equivalent Sc(1) atoms to form NSc4 tetrahedra that share  a cornercorner with one S(1)Sc6 octahedra, corners with seven equivalent S(2)Sc5 square pyramids, corners with two equivalent N(1)Sc4 tetrahedra, edges with two equivalent S(1)Sc6 octahedra,  an edgeedge with one S(2)Sc5 square pyramid, and edges with two equivalent N(1)Sc4 tetrahedra. The corner-sharing octahedral tilt angles are 21°. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Sc(1) and four equivalent Sc(2) atoms to form SSc6 octahedra that share corners with four equivalent S(2)Sc5 square pyramids, corners with two equivalent N(1)Sc4 tetrahedra, edges with two equivalent S(1)Sc6 octahedra, edges with six equivalent S(2)Sc5 square pyramids, and edges with four equivalent N(1)Sc4 tetrahedra. In the second S site, S(2) is bonded to two equivalent Sc(1) and three equivalent Sc(2) atoms to form SSc5 square pyramids that share corners with two equivalent S(1)Sc6 octahedra, corners with seven equivalent N(1)Sc4 tetrahedra, edges with three equivalent S(1)Sc6 octahedra, edges with four equivalent S(2)Sc5 square pyramids, and  an edgeedge with one N(1)Sc4 tetrahedra. The corner-sharing octahedral tilt angles are 14°.