Rb4MgV2(CuS4)2 crystallizes in the monoclinic C2 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), and four equivalent S(1) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(4), and four equivalent S(2) atoms. In the third Rb site, Rb(3) is bonded in a 10-coordinate geometry to two equivalent Mg(1), two equivalent S(2), two equivalent S(3), and four equivalent S(4) atoms. In the fourth Rb site, Rb(4) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(4), and four equivalent S(3) atoms. Mg(1) is bonded in a 4-coordinate geometry to two equivalent Rb(3), two equivalent S(2), and two equivalent S(4) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(3) and two equivalent S(4) atoms to form VS4 tetrahedra that share edges with two equivalent Cu(2)S4 tetrahedra. In the second V site, V(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form VS4 tetrahedra that share edges with two equivalent Cu(1)S4 tetrahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form distorted CuS4 tetrahedra that share edges with two equivalent V(2)S4 tetrahedra. In the second Cu site, Cu(2) is bonded to two equivalent S(3) and two equivalent S(4) atoms to form distorted CuS4 tetrahedra that share edges with two equivalent V(1)S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Rb(2), one Rb(4), two equivalent Rb(1), one V(2), and one Cu(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), one Mg(1), one V(2), and one Cu(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(4), one V(1), and one Cu(2) atom. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Rb(2), one Rb(4), two equivalent Rb(3), one Mg(1), one V(1), and one Cu(2) atom.
Rb4MgV2(CuS4)2 crystallizes in the monoclinic C2 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), and four equivalent S(1) atoms. Both Rb(1)-S(2) bond lengths are 3.81 Å. Both Rb(1)-S(3) bond lengths are 3.50 Å. There are two shorter (3.50 Å) and two longer (3.60 Å) Rb(1)-S(1) bond lengths. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(4), and four equivalent S(2) atoms. Both Rb(2)-S(1) bond lengths are 3.50 Å. Both Rb(2)-S(4) bond lengths are 3.49 Å. There are two shorter (3.47 Å) and two longer (3.67 Å) Rb(2)-S(2) bond lengths. In the third Rb site, Rb(3) is bonded in a 10-coordinate geometry to two equivalent Mg(1), two equivalent S(2), two equivalent S(3), and four equivalent S(4) atoms. Both Rb(3)-Mg(1) bond lengths are 3.32 Å. Both Rb(3)-S(2) bond lengths are 3.71 Å. Both Rb(3)-S(3) bond lengths are 3.25 Å. There are two shorter (3.32 Å) and two longer (3.59 Å) Rb(3)-S(4) bond lengths. In the fourth Rb site, Rb(4) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(4), and four equivalent S(3) atoms. Both Rb(4)-S(1) bond lengths are 3.47 Å. Both Rb(4)-S(4) bond lengths are 3.69 Å. There are two shorter (3.61 Å) and two longer (3.63 Å) Rb(4)-S(3) bond lengths. Mg(1) is bonded in a 4-coordinate geometry to two equivalent Rb(3), two equivalent S(2), and two equivalent S(4) atoms. Both Mg(1)-S(2) bond lengths are 2.45 Å. Both Mg(1)-S(4) bond lengths are 2.54 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent S(3) and two equivalent S(4) atoms to form VS4 tetrahedra that share edges with two equivalent Cu(2)S4 tetrahedra. Both V(1)-S(3) bond lengths are 2.19 Å. Both V(1)-S(4) bond lengths are 2.29 Å. In the second V site, V(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form VS4 tetrahedra that share edges with two equivalent Cu(1)S4 tetrahedra. Both V(2)-S(1) bond lengths are 2.20 Å. Both V(2)-S(2) bond lengths are 2.28 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form distorted CuS4 tetrahedra that share edges with two equivalent V(2)S4 tetrahedra. Both Cu(1)-S(1) bond lengths are 2.32 Å. Both Cu(1)-S(2) bond lengths are 2.40 Å. In the second Cu site, Cu(2) is bonded to two equivalent S(3) and two equivalent S(4) atoms to form distorted CuS4 tetrahedra that share edges with two equivalent V(1)S4 tetrahedra. Both Cu(2)-S(3) bond lengths are 2.30 Å. Both Cu(2)-S(4) bond lengths are 2.40 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Rb(2), one Rb(4), two equivalent Rb(1), one V(2), and one Cu(1) atom. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), one Mg(1), one V(2), and one Cu(1) atom. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(4), one V(1), and one Cu(2) atom. In the fourth S site, S(4) is bonded in a 7-coordinate geometry to one Rb(2), one Rb(4), two equivalent Rb(3), one Mg(1), one V(1), and one Cu(2) atom.