Ba2Mg(VS3)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one S(3), two equivalent S(2), two equivalent S(4), and four equivalent S(1) atoms. Mg(1) is bonded to one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted MgS5 square pyramids that share corners with two equivalent V(1)S6 octahedra, corners with three equivalent V(2)S6 octahedra,  an edgeedge with one V(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-50°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form VS6 octahedra that share corners with two equivalent Mg(1)S5 square pyramids, faces with two equivalent V(2)S6 octahedra, and  a faceface with one Mg(1)S5 square pyramid. In the second V site, V(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form VS6 octahedra that share corners with three equivalent Mg(1)S5 square pyramids,  an edgeedge with one Mg(1)S5 square pyramid, and faces with two equivalent V(1)S6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ba(1), two equivalent Ba(2), one Mg(1), one V(1), and one V(2) atom. In the second S site, S(2) is bonded to one Ba(1), one Ba(2), one Mg(1), one V(1), and one V(2) atom to form a mixture of distorted edge and face-sharing SBa2MgV2 square pyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(1), one V(1), and one V(2) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(1), two equivalent Ba(2), one Mg(1), one V(1), and one V(2) atom.
Ba2Mg(VS3)2 crystallizes in the monoclinic Cm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Ba(1)-S(4) bond length is 3.08 Å. Both Ba(1)-S(1) bond lengths are 3.28 Å. Both Ba(1)-S(2) bond lengths are 3.07 Å. Both Ba(1)-S(3) bond lengths are 3.47 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one S(3), two equivalent S(2), two equivalent S(4), and four equivalent S(1) atoms. The Ba(2)-S(3) bond length is 3.06 Å. Both Ba(2)-S(2) bond lengths are 3.21 Å. Both Ba(2)-S(4) bond lengths are 3.45 Å. There are two shorter (3.30 Å) and two longer (3.79 Å) Ba(2)-S(1) bond lengths. Mg(1) is bonded to one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted MgS5 square pyramids that share corners with two equivalent V(1)S6 octahedra, corners with three equivalent V(2)S6 octahedra,  an edgeedge with one V(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-50°. The Mg(1)-S(4) bond length is 2.42 Å. Both Mg(1)-S(1) bond lengths are 2.60 Å. Both Mg(1)-S(2) bond lengths are 2.56 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form VS6 octahedra that share corners with two equivalent Mg(1)S5 square pyramids, faces with two equivalent V(2)S6 octahedra, and  a faceface with one Mg(1)S5 square pyramid. The V(1)-S(3) bond length is 2.30 Å. The V(1)-S(4) bond length is 2.47 Å. Both V(1)-S(1) bond lengths are 2.51 Å. Both V(1)-S(2) bond lengths are 2.50 Å. In the second V site, V(2) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form VS6 octahedra that share corners with three equivalent Mg(1)S5 square pyramids,  an edgeedge with one Mg(1)S5 square pyramid, and faces with two equivalent V(1)S6 octahedra. The V(2)-S(3) bond length is 2.34 Å. The V(2)-S(4) bond length is 2.42 Å. Both V(2)-S(1) bond lengths are 2.60 Å. Both V(2)-S(2) bond lengths are 2.45 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ba(1), two equivalent Ba(2), one Mg(1), one V(1), and one V(2) atom. In the second S site, S(2) is bonded to one Ba(1), one Ba(2), one Mg(1), one V(1), and one V(2) atom to form a mixture of distorted edge and face-sharing SBa2MgV2 square pyramids. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(1), one V(1), and one V(2) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(1), two equivalent Ba(2), one Mg(1), one V(1), and one V(2) atom.