Mg(ScS2)2 crystallizes in the orthorhombic Pnma space group. Mg(1) is bonded to two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms to form distorted MgS7 pentagonal bipyramids that share corners with four equivalent Sc(1)S6 octahedra, corners with four equivalent Sc(2)S6 octahedra,  an edgeedge with one Sc(1)S6 octahedra, edges with four equivalent Sc(2)S6 octahedra, edges with two equivalent Mg(1)S7 pentagonal bipyramids, and faces with two equivalent Mg(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 11-65°. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(2) atoms to form ScS6 octahedra that share corners with three equivalent Sc(2)S6 octahedra, corners with four equivalent Mg(1)S7 pentagonal bipyramids, edges with two equivalent Sc(2)S6 octahedra, edges with four equivalent Sc(1)S6 octahedra, and  an edgeedge with one Mg(1)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 52-59°. In the second Sc site, Sc(2) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form ScS6 octahedra that share corners with three equivalent Sc(1)S6 octahedra, corners with four equivalent Mg(1)S7 pentagonal bipyramids, edges with two equivalent Sc(1)S6 octahedra, edges with two equivalent Sc(2)S6 octahedra, and edges with four equivalent Mg(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 52-59°. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Mg(1) and two equivalent Sc(2) atoms to form SMg3Sc2 square pyramids that share corners with two equivalent S(4)Mg2Sc3 square pyramids, corners with six equivalent S(3)Mg2Sc3 trigonal bipyramids, edges with three equivalent S(4)Mg2Sc3 square pyramids, edges with four equivalent S(1)Mg3Sc2 square pyramids, and edges with two equivalent S(3)Mg2Sc3 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Sc(2) and three equivalent Sc(1) atoms. In the third S site, S(3) is bonded to two equivalent Mg(1), one Sc(1), and two equivalent Sc(2) atoms to form distorted SMg2Sc3 trigonal bipyramids that share corners with two equivalent S(4)Mg2Sc3 square pyramids, corners with six equivalent S(1)Mg3Sc2 square pyramids, edges with two equivalent S(1)Mg3Sc2 square pyramids, edges with three equivalent S(4)Mg2Sc3 square pyramids, and edges with two equivalent S(3)Mg2Sc3 trigonal bipyramids. In the fourth S site, S(4) is bonded to two equivalent Mg(1), one Sc(2), and two equivalent Sc(1) atoms to form SMg2Sc3 square pyramids that share corners with two equivalent S(1)Mg3Sc2 square pyramids, corners with two equivalent S(3)Mg2Sc3 trigonal bipyramids, edges with two equivalent S(4)Mg2Sc3 square pyramids, edges with three equivalent S(1)Mg3Sc2 square pyramids, and edges with three equivalent S(3)Mg2Sc3 trigonal bipyramids.
Mg(ScS2)2 crystallizes in the orthorhombic Pnma space group. Mg(1) is bonded to two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms to form distorted MgS7 pentagonal bipyramids that share corners with four equivalent Sc(1)S6 octahedra, corners with four equivalent Sc(2)S6 octahedra,  an edgeedge with one Sc(1)S6 octahedra, edges with four equivalent Sc(2)S6 octahedra, edges with two equivalent Mg(1)S7 pentagonal bipyramids, and faces with two equivalent Mg(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 11-65°. Both Mg(1)-S(3) bond lengths are 2.99 Å. Both Mg(1)-S(4) bond lengths are 2.67 Å. There are two shorter (2.62 Å) and one longer (2.66 Å) Mg(1)-S(1) bond length. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(2) atoms to form ScS6 octahedra that share corners with three equivalent Sc(2)S6 octahedra, corners with four equivalent Mg(1)S7 pentagonal bipyramids, edges with two equivalent Sc(2)S6 octahedra, edges with four equivalent Sc(1)S6 octahedra, and  an edgeedge with one Mg(1)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 52-59°. The Sc(1)-S(3) bond length is 2.61 Å. Both Sc(1)-S(4) bond lengths are 2.58 Å. There are two shorter (2.55 Å) and one longer (2.66 Å) Sc(1)-S(2) bond length. In the second Sc site, Sc(2) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form ScS6 octahedra that share corners with three equivalent Sc(1)S6 octahedra, corners with four equivalent Mg(1)S7 pentagonal bipyramids, edges with two equivalent Sc(1)S6 octahedra, edges with two equivalent Sc(2)S6 octahedra, and edges with four equivalent Mg(1)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 52-59°. The Sc(2)-S(2) bond length is 2.64 Å. The Sc(2)-S(4) bond length is 2.60 Å. Both Sc(2)-S(1) bond lengths are 2.59 Å. Both Sc(2)-S(3) bond lengths are 2.56 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Mg(1) and two equivalent Sc(2) atoms to form SMg3Sc2 square pyramids that share corners with two equivalent S(4)Mg2Sc3 square pyramids, corners with six equivalent S(3)Mg2Sc3 trigonal bipyramids, edges with three equivalent S(4)Mg2Sc3 square pyramids, edges with four equivalent S(1)Mg3Sc2 square pyramids, and edges with two equivalent S(3)Mg2Sc3 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Sc(2) and three equivalent Sc(1) atoms. In the third S site, S(3) is bonded to two equivalent Mg(1), one Sc(1), and two equivalent Sc(2) atoms to form distorted SMg2Sc3 trigonal bipyramids that share corners with two equivalent S(4)Mg2Sc3 square pyramids, corners with six equivalent S(1)Mg3Sc2 square pyramids, edges with two equivalent S(1)Mg3Sc2 square pyramids, edges with three equivalent S(4)Mg2Sc3 square pyramids, and edges with two equivalent S(3)Mg2Sc3 trigonal bipyramids. In the fourth S site, S(4) is bonded to two equivalent Mg(1), one Sc(2), and two equivalent Sc(1) atoms to form SMg2Sc3 square pyramids that share corners with two equivalent S(1)Mg3Sc2 square pyramids, corners with two equivalent S(3)Mg2Sc3 trigonal bipyramids, edges with two equivalent S(4)Mg2Sc3 square pyramids, edges with three equivalent S(1)Mg3Sc2 square pyramids, and edges with three equivalent S(3)Mg2Sc3 trigonal bipyramids.