MnTl2As2S5 crystallizes in the orthorhombic Cmce space group. Mn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form edge-sharing MnS6 octahedra. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted L-shaped geometry to two equivalent S(1) atoms. In the second Tl site, Tl(2) is bonded in an L-shaped geometry to two equivalent S(2) atoms. As(1) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Mn(1), one Tl(1), and one As(1) atom. In the second S site, S(2) is bonded to two equivalent Mn(1), one Tl(2), and one As(1) atom to form a mixture of distorted edge and corner-sharing SMn2TlAs trigonal pyramids. In the third S site, S(3) is bonded in a water-like geometry to two equivalent As(1) atoms.
MnTl2As2S5 crystallizes in the orthorhombic Cmce space group. Mn(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form edge-sharing MnS6 octahedra. Both Mn(1)-S(1) bond lengths are 2.55 Å. There are two shorter (2.60 Å) and two longer (2.65 Å) Mn(1)-S(2) bond lengths. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted L-shaped geometry to two equivalent S(1) atoms. Both Tl(1)-S(1) bond lengths are 3.02 Å. In the second Tl site, Tl(2) is bonded in an L-shaped geometry to two equivalent S(2) atoms. Both Tl(2)-S(2) bond lengths are 3.00 Å. As(1) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. The As(1)-S(1) bond length is 2.25 Å. The As(1)-S(2) bond length is 2.29 Å. The As(1)-S(3) bond length is 2.34 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to one Mn(1), one Tl(1), and one As(1) atom. In the second S site, S(2) is bonded to two equivalent Mn(1), one Tl(2), and one As(1) atom to form a mixture of distorted edge and corner-sharing SMn2TlAs trigonal pyramids. In the third S site, S(3) is bonded in a water-like geometry to two equivalent As(1) atoms.