New Three-Dimensional Thiostannates Composed of Linked Cu₈S₁₂ Clusters and the First Example of a Mixed-Metal Cu₇SnS₁₂ Cluster

Abstract

Three new compounds (enH)(6+n)Cu(40)Sn(15)S(60) (1), (enH)(3)Cu(7)Sn(4)S(12) (2), and (trenH(3))Cu(7)Sn(4)S(12) (tren = tris(2-aminoethyl)amine) (3) containing Cu(8)S(12) and Cu(7)SnS(12) clusters have been prepared from direct solvothermal reaction of the elements in amine solvents. In 1, the cubic close-packed arrangement of Cu(8)S(12) clusters, interconnected by capping SnS(4) tetrahedra and CuS(3) triangles, form two interpenetrating channel networks that are presumably filled with disordered solvent molecules. Structures 2 and 3 contain well-ordered, protonated amine molecules and Cu(7)SnS(12) clusters. The clusters are connected by SnS(4) tetrahedra to form a three-dimensional structure with ReO(3) topology. (119)Sn Mössbauer measurement is consistent with Sn(IV) atoms linking, and Sn(II) atoms within, the mixed-metal Cu(7)SnS(12) clusters.

Copper‐Rich Framework Selenoarsenates Based on Icosahedral Cu8Se13 Clusters

“…Compounds 1-3 represent the first example of copper-rich framework selenides based on icosahedral Cu-Se cluster, in spite of the fact that several icosahedral Cu-S cluster-based framework sufides were reported, such as [M(NH 3 Copper-Rich Framework Selenoarsenates (enH) 3 [28] It is worth noting that high valent main group cations with tetrahedral coordination are indispensable for the formation of these icosahedral Cu-Q clusters in the frameworks. Because high valent cations in mononuclear MQ 4 or dimeric Ge 2 S 6 units can decrease the negative charge of the chalcogenide ions they bonded and limit the angle, which are critical for the formation of icosahedral clusters.…”

“…[39][40][41][42]48,49] Furthermore, the valent state of main group cations can also influence the kind of icosahedral clusters. For example, Ge 4+ and Sn 4+ can induce icosahedral Cu 8 S 12 cluster built up from corner sharing of eight CuS 3 triangle, [26][27][28]33] while As 5+ or Sb 5+ can induce Cu 8 Se 13 and Cu 8 S 13 cluster, [25] respectively, in which an additional Se 2-or S 2-were incorporated at the core site of the cluster, and lead to distorted tetrahedral coordination of each copper ions. In comparison, high valent As 5+ Thermogravimetric analyses indicate that compound 1 undergo one step of weight loss about 11.6 % between 270 and 290°C ( Figure S2, Supporting Information), which is in good agreement with the removal of en and small quantity of selenium (calcd.…”

“…They are quite different from tetrahedral-shaped clusters, because tetrahedral-shaped clusters can decorate tetrahedral sites and favor diamondoid or zeolitetype topologies. In compounds [M(NH 3 ) 6 ]Cu 8 Sb 3 S 13 (M = Mn, Fe, Ni), CuGeS-1, A 4 Cu 8 Ge 3 S 12 (A = K, Rb), (enH) 3 -Cu 7 Sn 4 S 12 , and (trenH 3 )Cu 7 Sn 4 S 12 , the icosahedral Cu-S clusters adopt octahedral coordination to form Perovskite structure or ReO 3 -topology frameworks; [25][26][27][28] whereas in (H 2 en) 2 -Cu 8 Sn 3 S 12 , the icosahedral Cu 8 S 12 cluster displays hexagonal connectivity to form an unusual (6,4) network. [32] Furthermore, a new synthetic strategy to expand the icosahedral Cu 8 S 12 cluster-based framework has also been proved feasible recently.…”

Two types of lanthanide selenidostannates(iv) first prepared under the same solvothermal conditions

“…Synthesis of [Y 2 (tepa) 2 (μ-OH) 2 Sn 2 Se 6 ] (Ia) and [Y 2 (tepa) 2 -(μ 2 -OH) 2 Cl 2 ] 2 [Sn 4 Se 10 ]·4H 2 O (IIa). The reagents of SnCl 4 ·5H 2 O (0.0530 g), Se (0.0500 g), YCl 3 (0.0820 g), Ag (0.0300 g) and tepa (2.0 mL) were placed in a thick Pyrex tube (ca.…”

“…IIa contains adamantane-like [Sn 4 Se 10 ] 4− anion, binuclear yttrium(III) complex [Y 2 (tepa) 2 (μ 2 -OH) 2 Cl 2 ] 2+ cations as counterions and free water molecules (Fig. 2b) (Fig.…”