K₁₀M₄Sn₄S₁₇ (M = Mn, Fe, Co, Zn):  Soluble Quaternary Sulfides with the Discrete [M₄Sn₄S₁₇]^10- Supertetrahedral Clusters

Abstract

Four cubic compounds are reported that contain the supertetrahedral cluster [M(4)Sn(4)S(17)](10)(-) where M = Mn, Fe, Co, Zn. The cluster features a central quadruply bridging sulfide ion (mu(4)-S) that holds together four divalent M atoms in a tetrahedral arrangement. This core is capped with four tridentate [SnS(4)](4)(-) fragments to complete the structure.

Ortho‐Chalcogenostannates as Ligands: Syntheses, Crystal Structures, Electronic Properties, and Magnetism of Novel Compounds Containing Ternary Anionic Substructures [M4(μ4‐Se)(SnSe4)4]10− (M=Mn, Zn, Cd, Hg), ${{{\hfill 3\atop \hfill \infty }}}${[Hg4(μ4‐Se)(SnSe4)3]6−}, or ${{{\hfill 1\atop \hfill \infty }}}${[HgSnSe4]2−}

“…This indicates that both separation of discrete M/Sn/Se anions by (solvated) K + ions and incorporation of tenside micelles in a three‐dimensional aggregation affect the optical behavior in a similar manner. As expected, the energy differences are somewhat smaller than those observed for the sulfur analogues K 4 [Zn 4 Sn 4 S 17 ] (3.1 eV) and K 4 [Mn 4 Sn 4 S 17 ] (2.3 eV) 11…”

“…In the highly charged, purely inorganic M/Sn/Se anions of 1 – 3 , chalcogenostannate anions were shown to function as ligands in molecular coordination compounds for the first time by single‐crystal X‐ray analysis. Recently, a number of solvent‐free sulfur homologues K 10 [M 4 Sn 4 S 17 ] (M=Mn, Fe, Co, Zn) were reported; however, these were prepared by combining the elements in a K 2 S flux 11. These inorganic selenide and sulfide compounds are structural analogues of the carbosilane “scaphane” cluster [Si 8 C 17 H 36 ]12 and oxides such as Na 10 [Be 4 Si 4 O 17 ] 13…”

Assembly of a Heterometallic Polynuclear SnIV−CuI Cluster Based on Sn(edt)2 (edt = Ethane-1,2-dithiolate) as a Metalloligand

“…3 By utilizing thiometalates MS 4-x O x 2-(M ) Mo, W; x ) 0, 1) as a "metalloligand", we have synthesized and characterized many types of heterotransition-metal complexes. 3,4 Owing to the importance of tin sulfide based clusters in optoelectronic devices, 5 6 [M 5 Sn(µ 3 -S) 4 (SnS 4 ) 4 ] 10-(M ) Zn, Co), 7 and K 2 Ag 6 Sn 3 S 10 8 synthesized by solid-state reactions, hydrothermal or solvothermal methods from Sn, S, and metal, or the corresponding inorganic salt. 9 Thus, a new synthetic route is of interest, especially for metal-organic heteropolynuclear tin clusters.…”

Pentasupertetrahedral Clusters as Building Blocks for a Three‐Dimensional Sulfide Superlattice

“…[15][16][17][18][19][20][21] The highly mobile extraframework cations results in the ionic conductivity of ICF-26 being higher than that of any previously known crystalline lithium compound at room temperature. [24][25][26] The P2 cluster contains four T2 clusters (M 4 X 10 ) and one anti-T2 cluster (X 4 M 10 ), thus giving the composition (M 4 X 10 ) 4 (X 4 M 10 ) (namely, M 26 X 44 ; Figure 1). The P2 cluster (that is, Li 4 In 22 S 44 18À ) is the second member of a mathematical series of pentasupertetrahedral clusters Pn, thus termed because they can be conceptually constructed by coupling four supertetrahedral clusters onto the faces of an antisupertetrahedral cluster of the same order ( Figure 1).…”

“…[24][25][26] The P2 cluster contains four T2 clusters (M 4 X 10 ) and one anti-T2 cluster (X 4 M 10 ), thus giving the composition (M 4 X 10 ) 4 (X 4 M 10 ) (namely, M 26 X 44 ; Figure 1). Examples of P1 clusters include [SCd 8 (SBu) 12 ](CN) 4/2 , K 10 M 4 Sn 4 S 17 (M = Mn, Fe, Co, Zn), and [M 4 (Se)(SnSe 4 ) 4 ] 10À (M = Zn, Mn).…”