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

N,N-Alkyl monothiocarbamate derivatives of diphenyltellurium, Ph2Te[SCONR2] (2) and Ph2TcCl[SCONR2], where NR = NEt2, NCH2(CH2)(2)CH2, and NCH2(CH2)(3) CH2, were obtained by the reaction of NaSCONR2 with Ph2TeCl2 and characteri zed by vibrational, H-1 and C-13 NMR spectroscopy. Molecular structures wer e determined by single-crystal X-ray diffraction. 2Ph(2)Te[SCONEt2](2) (1) and Ph2TeCl[SCONCH2(CH2)(2)CH2]. CHCl3 (5) crystallize as monoclinic in spa ce groups P2(1) and P2(1)/c, respectively. 2Ph(2)TeCl[SCONEt2] (4) and Ph2T eCl[SCONCH2(CH2),CH2)] (6) crystallize as orthorhombic in space groups Pna2 (1) and P2(1)2(1)2(1), respectively. The immediate environment about tellur ium is the typical saw-horse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position along with th e two phenyl groups. The sulfur atoms in I occupy the axial positions, with S-Te-S angle of 172.7(2) and 167.4(2)degrees. In 4-6, a chlorine atom occu pies one of these positions to give S-Te-Cl angles ranging from 172.7(2) to 175.8(2)degrees. The orientations of monothiocarbamate groups indicate sec ondary Te . . .O(-)intramolecular interactions. Inclusion of oxygen atoms i n the coordination sphere results in the five atoms around Te in 4-6 formin g a distorted square planar arrangement. In 1, the six atoms around Te in o ne 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 long er than those in Ph2TeCl2. (C) 2001 Elsevier Science B.V. All rights reserv ed.