Abstract
Four compounds of composition [dienH2][Co(dien)2][Ge2S6] (dien = diethylenetriamine) were obtained under solvothermal conditions changing the reaction time and educt ratio in the reaction slurries. In three compounds the [Co(dien)2]2+ complexes adopt the s-fac and in one the u-fac configuration. The main differences between the samples are found in the number and type of protonated dien molecules. In one distinct cation of compound 1 as well as in compound 2 the terminal N atoms are protonated, whereas in the second cation of 1 as well as in 3 and 4, one terminal and the central N atom are protonated. Therefore, the compounds with different protonated cations are tautomers, whereas compounds 3 and 4 represent polymorphic modifications. The occurrence of tautomerism and polymorphism for compounds with identical chemical composition is unprecedented in the chemistry of thiometallates and was never reported until now. In the crystal structure of all compounds the (dienH2)2+ cations and the [Ge2S6]4− anions are linked by intermolecular N–H⋯S hydrogen bonding into different supramolecular networks.
Highlights
The thiometallate chemistry of main group elements Ge, Sn, In, As or Sb was substantially developed during the last two decades.[1,2,3,4,5,6] The main synthetic method applied for the generation of thiometallates is the solvothermal approach allowing the usage of different solvents and starting materials as well as structure directing molecules
The two NH3 groups of the dien molecule and the terminal S atoms of the anion exhibit N–H⋯S bonding interactions leading to formation of a two dimensional supramolecular layer-like arrangement within the (001) plane being characterized by rings composed of two dienH2 cations and two [Ge2S6]4− anions (Fig. 5)
In all compounds discrete [Co(dien)2]2+ cations and [Ge2S6]4− anions are observed and charge compensation is achieved by diprotonated dien molecules
Summary
The thiometallate chemistry of main group elements Ge, Sn, In, As or Sb was substantially developed during the last two decades.[1,2,3,4,5,6] The main synthetic method applied for the generation of thiometallates is the solvothermal approach allowing the usage of different solvents and starting materials as well as structure directing molecules. In the latter compound a GeS4 tetrahedron, one SbS3 pyramid and a SbS4 moiety are joined to form a [GeSb2S8] group and each of these groups is interconnected to three adjacent units via their four terminal S atoms to generate a 2-D anionic network with composition [GeSb2S6].24 A semi-cube like moiety [GeSb2S7] is the main structural motif in [Ni(dien)2]3[Ge3Sb8S21]·0.5H2O. We report the solvothermal syntheses and the crystal structures of these new compounds exhibiting dienH2 molecules being protonated at different N atoms.
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