Mg(VS2)4 crystallizes in the orthorhombic Imm2 space group. Mg(1) is bonded in a distorted tetrahedral geometry to two equivalent V(1), two equivalent V(2), two equivalent S(2), and two equivalent S(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to one Mg(1), one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. In the second V site, V(2) is bonded in a 7-coordinate geometry to one Mg(1), one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Mg(1), one V(2), and two equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted single-bond geometry to one Mg(1), one V(1), and two equivalent V(2) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(2) atoms.
Mg(VS2)4 crystallizes in the orthorhombic Imm2 space group. Mg(1) is bonded in a distorted tetrahedral geometry to two equivalent V(1), two equivalent V(2), two equivalent S(2), and two equivalent S(3) atoms. Both Mg(1)-V(1) bond lengths are 2.56 Å. Both Mg(1)-V(2) bond lengths are 2.55 Å. Both Mg(1)-S(2) bond lengths are 2.23 Å. Both Mg(1)-S(3) bond lengths are 2.22 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to one Mg(1), one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms. The V(1)-S(3) bond length is 2.77 Å. The V(1)-S(4) bond length is 2.31 Å. Both V(1)-S(1) bond lengths are 2.31 Å. Both V(1)-S(2) bond lengths are 2.77 Å. In the second V site, V(2) is bonded in a 7-coordinate geometry to one Mg(1), one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms. The V(2)-S(1) bond length is 2.31 Å. The V(2)-S(2) bond length is 2.77 Å. Both V(2)-S(3) bond lengths are 2.78 Å. Both V(2)-S(4) bond lengths are 2.31 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Mg(1), one V(2), and two equivalent V(1) atoms. In the third S site, S(3) is bonded in a distorted single-bond geometry to one Mg(1), one V(1), and two equivalent V(2) atoms. In the fourth S site, S(4) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(2) atoms.