NN-diethyldithiocarbamate complexes of trivalent lanthanide and actinide elements and the crystal structure of tetraethylammonium neptunium(III) tetrakis-(NN-diethyldithiocarbamate)

Abstract

Trivalent lanthanide and actinide complexes of the types M(dtc)₃ and NEt₄M(dtc)₄(M = Np, Pu, and La to Lu inclusive, except Pm; dtc =NN-diethyldithiocarbamate) have been prepared by reactions in nonaqueous solvents. Some chemical properties, i.r. and visible spectra, and crystallographic properties are reported. Three distinct crystal forms have been observed for different neutral complexes whereas the tetrakisdiethyldithiocarbamates are all isostructural. The structure of NEt₄Np(dtc)₄ has been determined by single-crystal X-ray diffraction methods. It crystallises in the monoclinic space group P2₁/c(C_2h⁵) with Z= 4 in a unit cell of dimensions a₀= 11·68, b₀= 20·49, c₀= 19·14 Å and β= 116·5°. The neptunium atoms are each bonded to eight sulphur atoms with a mean Np–S distance of 2·87 Å.