Some new complexes of thorium tetrachloride with substituted ureas; the crystal and molecular structure of tris( N,N′-dimethyl- N,N′-diphenylurea)-tetrachlorothorium(IV)

Abstract

Thorium tetrachloride forms a 1:3 complex, ThCl 4·3L, with N,N-diethyl N′, N′-dimethylurea (dedmu); and 1:2 complexes with dedmu, N,N-diisopropyl N′, N′-dimethyl (dibdmu), N,N-diisobutyl- N′, N′-dimethyl (dibdmu), N,N-diisopropyl N′, N′-diphenyl (dipdpu), N,N,N′, N′-tetramethyl (tmu) and N,N,N′, N′-tetraethylurea (teu) have been obtained. A dichloromethane solvate, ThCl 4·3L·CH 2Cl 2, where L= N,N′-dimethyl- N′, N-diphenylurea (dmdpu), has also been obtained. The crystal and molecular structure of ThCl 4(dmdpu) 3·n-pentane has been determined from three dimensional X-ray diffraction data. The cell is triclinic, space group P 1 , with a=16.826(3), b=16.019(3), c=12.131(2) Å, α=11O.4(1), β=106.6(1) and γ=59.4(1)° and Z=2. Full matrix least-squares refinement with 7963 intensity observations reached convergency with R=0.053 and R w=0.058. The coordination polyhedron about the seven-coordinate thorium atom is a pentagonal bipyramid with two chlorine atoms in apical positions. The average bonding distances are ThO=2.392(5), ThCl eq=2.743(3) and ThCl ax=2.696(3) Å. The IR spectra of the complexes are also reported.