Rb4Mn(AsS4)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one S(2), one S(3), one S(5), one S(6), one S(7), two equivalent S(1), and two equivalent S(8) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one S(5), one S(7), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one S(2), one S(4), one S(6), one S(8), two equivalent S(3), and two equivalent S(5) atoms. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one S(1), one S(4), one S(6), two equivalent S(5), and two equivalent S(7) atoms. Mn(1) is bonded to one S(2), one S(3), one S(4), one S(8), and two equivalent S(6) atoms to form MnS6 octahedra that share  an edgeedge with one Mn(1)S6 octahedra,  an edgeedge with one As(2)S4 tetrahedra, and edges with two equivalent As(1)S4 tetrahedra. There are two inequivalent As sites. In the first As site, As(1) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form AsS4 tetrahedra that share edges with two equivalent Mn(1)S6 octahedra. In the second As site, As(2) is bonded to one S(4), one S(5), one S(7), and one S(8) atom to form AsS4 tetrahedra that share  an edgeedge with one Mn(1)S6 octahedra. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Rb(4), two equivalent Rb(1), two equivalent Rb(2), and one As(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), one Mn(1), and one As(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(3), one Mn(1), and one As(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Rb(3), one Rb(4), two equivalent Rb(2), one Mn(1), and one As(2) atom. In the fifth S site, S(5) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(3), two equivalent Rb(4), and one As(2) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), one Rb(4), two equivalent Mn(1), and one As(1) atom. In the seventh S site, S(7) is bonded to one Rb(1), one Rb(2), two equivalent Rb(4), and one As(2) atom to form distorted edge-sharing SRb4As square pyramids. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Rb(3), two equivalent Rb(1), one Mn(1), and one As(2) atom.
Rb4Mn(AsS4)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one S(2), one S(3), one S(5), one S(6), one S(7), two equivalent S(1), and two equivalent S(8) atoms. The Rb(1)-S(2) bond length is 3.44 Å. The Rb(1)-S(3) bond length is 3.67 Å. The Rb(1)-S(5) bond length is 3.40 Å. The Rb(1)-S(6) bond length is 3.78 Å. The Rb(1)-S(7) bond length is 3.31 Å. There is one shorter (3.42 Å) and one longer (3.65 Å) Rb(1)-S(1) bond length. There is one shorter (3.40 Å) and one longer (3.54 Å) Rb(1)-S(8) bond length. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one S(5), one S(7), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. The Rb(2)-S(5) bond length is 3.87 Å. The Rb(2)-S(7) bond length is 3.24 Å. There is one shorter (3.43 Å) and one longer (3.54 Å) Rb(2)-S(1) bond length. There is one shorter (3.55 Å) and one longer (3.59 Å) Rb(2)-S(2) bond length. There is one shorter (3.44 Å) and one longer (3.81 Å) Rb(2)-S(4) bond length. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one S(2), one S(4), one S(6), one S(8), two equivalent S(3), and two equivalent S(5) atoms. The Rb(3)-S(2) bond length is 3.56 Å. The Rb(3)-S(4) bond length is 3.64 Å. The Rb(3)-S(6) bond length is 3.57 Å. The Rb(3)-S(8) bond length is 3.71 Å. There is one shorter (3.44 Å) and one longer (3.54 Å) Rb(3)-S(3) bond length. There is one shorter (3.47 Å) and one longer (3.63 Å) Rb(3)-S(5) bond length. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one S(1), one S(4), one S(6), two equivalent S(5), and two equivalent S(7) atoms. The Rb(4)-S(1) bond length is 3.51 Å. The Rb(4)-S(4) bond length is 3.58 Å. The Rb(4)-S(6) bond length is 3.31 Å. There is one shorter (3.63 Å) and one longer (3.82 Å) Rb(4)-S(5) bond length. There is one shorter (3.31 Å) and one longer (3.35 Å) Rb(4)-S(7) bond length. Mn(1) is bonded to one S(2), one S(3), one S(4), one S(8), and two equivalent S(6) atoms to form MnS6 octahedra that share  an edgeedge with one Mn(1)S6 octahedra,  an edgeedge with one As(2)S4 tetrahedra, and edges with two equivalent As(1)S4 tetrahedra. The Mn(1)-S(2) bond length is 2.60 Å. The Mn(1)-S(3) bond length is 2.60 Å. The Mn(1)-S(4) bond length is 2.60 Å. The Mn(1)-S(8) bond length is 2.60 Å. There is one shorter (2.67 Å) and one longer (2.78 Å) Mn(1)-S(6) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form AsS4 tetrahedra that share edges with two equivalent Mn(1)S6 octahedra. The As(1)-S(1) bond length is 2.13 Å. The As(1)-S(2) bond length is 2.17 Å. The As(1)-S(3) bond length is 2.17 Å. The As(1)-S(6) bond length is 2.19 Å. In the second As site, As(2) is bonded to one S(4), one S(5), one S(7), and one S(8) atom to form AsS4 tetrahedra that share  an edgeedge with one Mn(1)S6 octahedra. The As(2)-S(4) bond length is 2.20 Å. The As(2)-S(5) bond length is 2.16 Å. The As(2)-S(7) bond length is 2.14 Å. The As(2)-S(8) bond length is 2.18 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Rb(4), two equivalent Rb(1), two equivalent Rb(2), and one As(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), one Mn(1), and one As(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(3), one Mn(1), and one As(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Rb(3), one Rb(4), two equivalent Rb(2), one Mn(1), and one As(2) atom. In the fifth S site, S(5) is bonded in a 7-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(3), two equivalent Rb(4), and one As(2) atom. In the sixth S site, S(6) is bonded in a 6-coordinate geometry to one Rb(1), one Rb(3), one Rb(4), two equivalent Mn(1), and one As(1) atom. In the seventh S site, S(7) is bonded to one Rb(1), one Rb(2), two equivalent Rb(4), and one As(2) atom to form distorted edge-sharing SRb4As square pyramids. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Rb(3), two equivalent Rb(1), one Mn(1), and one As(2) atom.