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Issue 25, 2014
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Polymorphism and tautomerism in [dienH2][Co(dien)2][Ge2S6] leading to different hydrogen bonded networks

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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.

Graphical abstract: Polymorphism and tautomerism in [dienH2][Co(dien)2][Ge2S6] leading to different hydrogen bonded networks

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Article information


Submitted
11 Feb 2014
Accepted
02 May 2014
First published
02 May 2014

This article is Open Access

CrystEngComm, 2014,16, 5551-5559
Article type
Paper

Polymorphism and tautomerism in [dienH2][Co(dien)2][Ge2S6] leading to different hydrogen bonded networks

J. Lichte, C. Näther and W. Bensch, CrystEngComm, 2014, 16, 5551
DOI: 10.1039/C4CE00312H

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