Diphenyltellurium(IV) monothiocarbamates. The molecular structures of Ph2Te[SCONEt2]2, Ph2TeCl[SCONEt2], Ph2TeCl[SCONCH2(CH2)2CH2)]·CHCl3, and Ph2TeCl[SCONCH2(CH2)3CH2)]

N,N-Alkyl monothiocarbamate derivatives of diphenyltellurium, Ph2Te[SCONR2]2 and Ph2TeCl[SCONR2], where NR=NEt2, NCH2(CH2)2CH2, and NCH2(CH2)3CH2, were obtained by the reaction of NaSCONR2 with Ph2TeCl2 and characterized by vibrational, 1H and 13C NMR spectroscopy. Molecular structures were determined by single-crystal X-ray diffraction. 2Ph2Te[SCONEt2]2 (1) and Ph2TeCl[SCONCH2(CH2)2CH2]·CHCl3 (5) crystallize as monoclinic in space groups P21 and P21/c, respectively. 2Ph2TeCl[SCONEt2] (4) and Ph2TeCl[SCONCH2(CH2)3CH2)] (6) crystallize as orthorhombic in space groups Pna21 and P212121, respectively. The immediate environment about tellurium is the typical saw-horse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position along with the two phenyl groups. The sulfur atoms in 1 occupy the axial positions, with STeS angle of 172.7(2) and 167.4(2)°. In 4–6, a chlorine atom occupies one of these positions to give STeCl angles ranging from 172.7(2) to 175.8(2)°. The orientations of monothiocarbamate groups indicate secondary Te⋯O intramolecular interactions. Inclusion of oxygen atoms in the coordination sphere results in the five atoms around Te in 4–6 forming a distorted square planar arrangement. In 1, the six atoms around Te in one of the two independent molecules form a distorted octahedron but, in the other, a pentagonal bipyramid is formed. The TeS bond lengths in 4–6 are considerably shorter than in 1, while the TeCl bonds are considerably longer than those in Ph2TeCl2.