Dithiocarbamates as Innocent Anions: The Synthesis and Structural Properties of (8-Methyl-3,6,10,13,16,19-hexaazabicyclo[6.6.6]-icosan-1-amine)cobalt(Ii I) Tris(N,N-diethyldithiocarbamate), [Co(AMMEsar)][Et₂dtc]₃

Abstract

Sodium diethyldithiocarbamate, Na[Et₂dtc], reacts with (8-methyl-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosan-1-aminium)cobalt(III) chloride, [Co( AMMEsarH )]Cl₄, in aqueous solution to form the compound [Co( AMMEsar )][Et₂dtc]₃ which is readily soluble in organic solvents. Crystals are trigonal, space group R3c (3m, No. 167) with a 13.864(4), c 36.42(2)Ǻ, Z 6. A full-matrix least-squares refinement on 952 reflections, with I > 2.5σ(I), converged with final R of 0.037. The structure consists of the [Co( AMMEsar )]³⁺ cation and three [Et₂dtc]^- anions. The primary aminium group on one trigonal cap of the cage is deprotonated to an amine. Strong hydrogen bonds exist between the sulfur atoms of the diethyldithiocarbamate anions and the protons of the secondary amines of the complex cation, which is stabilized in the lel conformation.