Solid-state structure and solution behaviour of organomercury(II) compounds containing 2-(Me2NCH2)C6H4- moieties. Supramolecular aspects

Abstract

Abstract The reaction of [2-(Me 2 NCH 2 )C 6 H 4 ]HgCl ( 1 ) with NH 4 Br and KI gave the analogous bromide ( 2 ) and iodide ( 3 ), respectively. To investigate the competitive coordination to the mercury centre of the nitrogen atom of the pendant arm and the donor atoms of a potentially chelating anionic ligand the dithiocarbamates [2-(Me 2 NCH 2 )C 6 H 4 ]HgS(S)CNR 2 [R = Me ( 4 ), Et ( 5 )] were prepared by reacting 1 with Na[S 2 CNR 2 ]·nH 2 O (R = Me, n = 2; R = Et, n = 3). The reaction between PhHgCl and the same sodium dithiocarbamates afforded PhHgS(S)CNR 2 [R = Me ( 6 ), Et ( 7 )]. The compounds were investigated by multinuclear NMR spectroscopy ( 1 H, 13 C, 199 Hg and 2D experiments) and mass spectrometry. The solid-state molecular structures of compounds 2 – 6 were established by single-crystal X-ray diffraction. In the compounds 2 – 5 the nitrogen atom of the pendant CH 2 NMe 2 arm is strongly coordinated to the mercury atom. The ( C,N )HgX core is non-planar in the dithiocarbamates 4 and 5 and thus the mercury atom becomes a stereocentre. Supramolecular associations based on Hg⋯X, Hg⋯S, C-H⋯X (X = Br, I), S⋯S and C-H⋯π interactions are discussed.