Supramolecular Assembling of Complex Tellurium Salts: Synthesis and Crystal Structures of {Cs[PhTeCl₄]·CH₃OH} and Cs[PhTeBr₄]

Abstract

The direct reaction between PhTeCl3 and CsCl in methanol affords {Cs[PhTeCl4]·CH3OH}. Cs[PhTeBr4] was prepared by refluxing [2‐Br‐C5NH5][PhTeBr4] and CsCl in ethanol in the presence of an excess of HBr. In {Cs[PhTeCl4]·CH3OH} the [PhTeCl4]— units form dimers by secondary Te···Cl bonds with methanol molecules bridging adjacent Cs+ cations. In both compounds, the alkali metal cation interacts secondarily with the chlorine and bromine Te‐ligands, achieving singular coordination polyhedrons and holding the lattices in supramolecular tridimensional assemblies. The new complexes, {Cs[PhTeCl4]·CH3OH} and Cs[PhTeBr4], crystallize in the space groups P21/c and P21/n, respectively. Only one such structure has been reported before.

One‐Pot Synthesis and Structure of Organochalcogen Halides with Mixed Valence States

“…Recently, as part of our research on the coordination of organotellurium compounds, we have reported the syntheses and the molecular structures of organotellurium trihalides13,14 and organotellurium monohalides,11,15,16 as well as several studies involving structures of phenyltellurate halides stabilized by different cations 17–19. Most of the crystal structures reported for the RTeX 3 species show that the occurrence of intra‐ and intermolecular interactions (secondary bonding), together with the nature of the organic groups bonded to the tellurium atoms, exert influence on the geometry around the tellurium( IV ) center and consequently define the structural patterns of these compounds 14,20–26.…”

New examples of mixed organochalcogene compounds: Synthesis, structural features and spectroscopic data of [PhSe(etu)][PhTeX4] (Ph=phenyl; etu=ethylenethiourea; X=Br, I)

“…are well known [5][6][7][8]. Most of these complex salts lie close to the ionic/covalent borderline and show properties of supramolecules due to interionic, fairly strong secondary bonds of the types N + -HÁÁÁTe, TeÁÁÁX or XÁÁÁX (X = Cl, Br, I), as well as TeÁÁÁp-aryl contacts [9,10].…”

“…C, 77 Se and 125 Te NMR measures were conducted in solutions of acetone-d6 and DMSO-d 6 in a 9:1 proportion, respectively. Since compounds 1 and 2 do not show many significant features in their1 H or 13 C NMR spectra, our attention was turned to the 77 Se and 125 Te NMR spectroscopy.…”