K 10 M 4 M' 4 S 17 (M  Mn, Fe, Co, Zn; M'  Sn, Ge) and Cs 10 Cd 4 Sn 4 S 17 : Compounds with a Discrete Supertetrahedral Cluster Oleg Palchik, Ratnasabapathy G. Iyer, Christian G. Canlas, David P. Weliky, and Mercouri G. Kanatzidis* East Lansing, Michigan / USA, Department of Chemistry, Michigan State University Received May 10 th , 2004. Dedicated to Professor Martin Jansen on the Occasion of his 60th Birthday Abstract. The cluster compounds K 10 Zn 4 Sn 4 S 17 ,K 10 Mn 4 Sn 4 S 17 , K 10 Fe 4 Sn 4 S 17 ,K 10 Co 4 Sn 4 S 17 , Cs 10 Cd 4 Sn 4 S 17 and K 10 Zn 4 Ge 4 S 17 are described. The structures of these compounds, refined by single-crystal X-ray diffraction techniques, contain the discrete cluster [M 4 M' 4 S 17 ] 10- (M = Zn, Mn, Co, Fe, Cd; M'= Sn or Ge) which has the structure of Si 8 C 17 H 36 . It is built from the sulfur- connected tetrahedral SnS 4 and MS 4 units with the additional qua- druply bridging sulfur atom at the center of the cluster. All com- pound show some solubility and stability in water and formamide. K 10 M 4 M' 4 S 17 (M  Mn, Fe, Co, Zn; M'  Sn, Ge) und Cs 10 Cd 4 Sn 4 S 17 : Verbindungen mit einem diskreten supertetraedrischen Cluster Inhaltsübersicht. Die Cluster-Verbindungen K 10 Zn 4 Sn 4 S 17 , K 10 Mn 4 Sn 4 S 17 ,K 10 Fe 4 Sn 4 S 17 ,K 10 Co 4 Sn 4 S 17 , Cs 10 Cd 4 Sn 4 S 17 und K 10 Zn 4 Ge 4 S 17 werden beschrieben. Die Strukturen dieser Verbin- dungen wurden durch Einkristall-Röntgenstrukturanalyse be- stimmt. Sie enthalten diskrete Cluster von [M 4 M' 4 S 17 ] 10- (M = Zn, Mn, Co, Fe, Cd; M'= Sn or Ge), die die Struktur von Si 8 C 17 H 36 haben. Sie werden aus über Schwefelatomen verbunde- nen tetraedrischen SnS 4 - und MS 4 -Einheiten aufgebaut mit dem zusätzlich vierfach verbrückenden Schwefelatom im Zentrum des Introduction The availability of large metal chalcogenido clusters that can be put into solution is of general chemical interest be- cause they could serve as convenient precursors for the preparation of novel nano- or mesoporous materials [1, 2]. The use of such precursors may allow more rational syn- thetic approaches for a wide variety of solids with semicon- ducting and/or micro/mesoporous properties. Recently a group of chalcogenide cluster-based solids with large pores filled with exchangeable organic cations has emerged with novel properties and structural features [3, 4, 5]. The clus- ters in these materials are generally adamantine-type be- longing to the Tn homologous series where n is the cluster “generation” [6]. A T1 cluster is the simple tetrahedral unit [GeS 4 ] 4- , the T2 cluster refers to the adamantane cluster * Prof. Dr. Mercouri G. Kanatzidis Department of Chemistry Michigan State University East Lansing, Michigan 48824 / USA E-mail: kanatzidis@chemistry.msu.edu Z. Anorg. Allg. Chem. 2004, 630, 2237-2247 DOI: 10.1002/zaac.200400154  2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 2237 Cs 10 Cd 4 Sn 4 S 17 and K 10 Zn 4 Ge 4 S 17 show photoluminescence at room temperature.The magnetic properties of K 10 Mn 4 Sn 4 S 17 , K 10 Fe 4 Sn 4 S 17 ,K 10 Co 4 Sn 4 S 17 indicate strong antiferromagnetic in- teractions arising from spin coupling within the cluster but their magnetic susceptibility is characterized with a discrepancy between field-cooled and zero field-cooled measurements. Keywords: Cluster compound; Tin; Germanium; Sulfides Clusters. Alle Verbindungen sind etwas löslich und stabil in Wasser und Formamid. Cs 10 Cd 4 Sn 4 S 17 und K 10 Zn 4 Ge 4 S 17 zeigen Photolu- mineszens bei Zimmertemperatur. Die magnetischen Eigenschaften von K 10 Mn 4 Sn 4 S 17 ,K 10 Fe 4 Sn 4 S 17 , K 10 Co 4 Sn 4 S 17 zeigen starke antiferromagnetische Wechselwirkungen aufgrund der Spin-Kupp- lung in den Clustern, während ihre magnetischen Suszeptibilitäten durch eine Diskrepanz zwischen Kaltfeld- und Null-Kaltfeld-Mes- sungen charakterisiert wird. [Ge 4 S 10 ] 4- . When n  3, the term “supertetrahedral” is used with some examples being [In 10 S 20 ] 10- (T3) 6 , [Cd 4 In 16 S 35 ] 14- [7], [Zn 4 In 16 S 33 ] 10- (T4) [8] and [In 28 Cd 6 S 54 ] 12- (T5) [9, 10]. These clusters (with n  3) con- tain trivalent metals (e.g. Ga, In) or a combination of di- valent and trivalent (e.g. Cd and In) ions and are always linked in three-dimensional frameworks. They have not been isolated as discrete molecular clusters. The family of compounds K 10 M 4 Sn 4 S 17 (M = Mn, Fe, Co, Zn) offers the discrete supertetrahedral [M 4 Sn 4 S 17 ] 10- cluster which is sol- uble in polar solvents where the Co and Fe analogs possess the highest solubility [11]. The [M 4 M' 4 S 17 ] 10- cluster combines divalent and tetra- valent metals (M: divalent and M': tetravalent) and it fea- tures four terminal sulfide atoms, which can potentially serve as linking points to build extended frameworks. For example, we prepared K 6 Zn 4 Sn 5 S 17 [12] a dense extended network compound composed of [Zn 4 Sn 4 S 17 ] 10- clusters, linked in three dimensions by Sn 4+ ions. Despite its T d point group symmetry and tetrahedral top- ology, the cluster does not belong to the Tn homologous series, and in this context it represents an alternative build-