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Orange TlCu 3 Er 2 S 5  crystallizes in the orthorhombic space group Cmcm (a = 391:27(2), b = 1382:91(7), c = 1630:54(8) pm, Z = 4). Its crystal structure contains one Tl + , one Er 3+ , two Cu + , and three S 2-  ions as crystallographically unique components. All Cu +  cations are coordinated by four S 2-  anions to form [CuS 4 ] 7-  tetrahedra, which have vertex- and edge-connectivity to build up  2   ∞ {[Cu 3 S 5 ] 7- } layers parallel to the (010) plane. The Er 3+  cations are octahedrally surrounded by six S 2-  anions. These [ErS 6 ] 9 - units share trans-oriented edges forming linear chains, which are further linked by common vertices yielding  1   ∞ {[Er 2 S 10 ] 14- } double strands. Further fusion via common vertices results in  2   ∞ {[Er 2 S 5 ] 4- } layers parallel to the (010) plane. Alternatingly stacked along [010] and condensed via S 2-  anions, these two types of layers form a three-dimensional framework, leaving tunnels along [100], where the Tl +  cations fit in. These are each coordinated by eight S 2-  anions in the shape of bicapped trigonal prisms. Tl 2 Cu 5 Er 3 S 8  was obtained as black single crystals with metallic luster (monoclinic, Cm, a = 1381:69(7), b = 390:73(2), c = 1435:98(7) pm, β = 111:132(3)°, Z =2). Four of the five crystallographically different Cu +  cations are tetrahedrally surrounded by S 2-  anions, whereas (Cu 3 ) +  is situated in sulfur triangles. Connected via common vertices and edges, the copper-sulfur polyhedra form strongly corrugated  2   ∞ {[Cu 5 S 8 ] 11- } layers parallel to the (201) plane. All Er 3+  cations are again coordinated by six S 2-  anions in the shape of [ErS 6 ] 9-  octahedra. Their condensation via edges and vertices leads to  2   ∞ {[Er 3 S 8 ] 7- } layers spreading out parallel to the (010) plane. Both types of anionic layers result in a three-dimensional framework through sulfide fusion, which leaves tunnels running along [010] occupied by Tl +  cations. The two crystallographically different Tl +  cations both have eight coordinating S 2-  anions forming bicapped trigonal prisms. Remarkably enough, the ion closest to (Tl1) +  is not a S 2-  anion (shortest Tl + -S 2-  bond: 305 pm), but a (Cu 3 ) +  cation at a distance of just 291 pm.

A Structural Comparison of Two Thallium Copper Erbium Sulfides: TlCu 3 Er 2 S 5 and Tl 2 Cu 5 Er 3 S 8