Unusual Syntheses, Structures, and Electronic Properties of Compounds Containing Ternary, T3-Type Supertetrahedral M/Sn/S Anions [M5Sn(μ3-S)4(SnS4)4]10- (M = Zn, Co)
datasetposted on 08.08.2005 by Christian Zimmermann, Christopher E. Anson, Florian Weigend, Rodolphe Clérac, Stefanie Dehnen
Datasets usually provide raw data for analysis. This raw data often comes in spreadsheet form, but can be any collection of data, on which analysis can be performed.
A recently discovered series of quaternary compounds of the general type [Km(ROH)n][MxSnySez] (R = H, Me), containing ternary anions with [SnSe4]4--coordinated transition metal centers (M = Co, Mn, Zn, Cd, Hg) has now been extended by the synthesis and characterization of the two ortho-thiostannate-coordinated species, [Na10(H2O)32][M5Sn(μ3-S)4(SnS4)4]·2H2O (M = Zn (1), Co (2)). The central structural motifs of compounds 1 and 2 are highly charged [M5Sn(μ3-S)4(SnS4)4]10- anions, being the first T3-type supertetrahedral ternary anions reported to date. The exposure of single crystals of 2 to a dynamic vacuum for several hours resulted in the reversible formation of a partially dehydrated, but still monocrystalline material of the composition [Na10(H2O)6][Co5Sn(μ3-S)4(SnS4)4] (3). The loss of 28 of the 34 water molecules only slightly affects the internal structure of the ternary anion in 3 and leads to a significant compacting of the crystal structure with closer linkage of the [Co5Sn5S20]10- cluster units via the Na+ cations. Magnetic measurements on 3 show that the ground state of the Co/Sn/S cluster is S = 1/2, indicating a significant antiferromagnetic coupling between the Co centers, which has also been rationalized by DFT investigations of the electronic situation in the ternary subunits of 1−3.