Die Kristallstruktur von p‐Tolylbis(diethyldithiocarbamato)‐thallium(III) und Phenylbis(methylxanthogenato)bismut(III)

Abstract

data of single crystals. FlOm the interatomic distances follows that the dithiocarbamate and xantho· genate ligands coordinate asymmetrically bidentate to the metal as presumed and exclusively through the sulfur atoms. Differences in the coordination sphere of bismut and thallium give evidence for a "stereochemically active lone pair" on the bismut atom.

Bis(μ-N-benzyl-N-methyldithiocarbamato)-1:2κ3S,S′:S′;1:2κ3S:S,S′-bis[bis(N-benzyl-N-methyldithiocarbamato-κ2S,S′)thallium(III)]

“…The values of the Tl-S bond lengths involving the bidentate chelating ligands (Table 1) range from 2.6210 (8) to 2.9240 (10) Å, in agreement with those observed in other Tl-dithiocarbamato complexes (Burschka, 1982;Kepert et al, 1978;Griffin et al, 1980;Abrahamson et al, 1975;Casas et al, 1994). The Tl-S bond lengths involving the bridging S3 atom [3.0242 (8) and 3.1605 ( 8) Å] are consistent with the values reported in the literature for similar thallium(I) derivatives (Ivanov et al, 2006;Jennische et al, 1972;Pritzkow & Jennische, 1975;Nilson & Hesse, 1969).…”

“…For the crystal structures of Tl-dithiocarbamate complexes, see: Abrahamson et al (1975); Burschka (1982); Casas et al (1994); Griffin et al (1980); Ivanov et al (2006); Jennische et al (1972); Kepert et al (1978); Nilson & Hesse (1969); Pritzkow & Jennische (1975).…”

Structural Chemistry of Bismuth Compounds. I. Organobismuth Derivatives

“…The molecular unit of the xanthogenato derivative PhBi[S(S)COMe] 2 is similar to those of the previously related dithiophosphinato and dithiocarbamato compounds, i.e., anisobidentate dithio ligands, with short and long bismuth-sulfur distances and a large S‚‚‚Bi‚‚‚S angle of 155.1°. 135 However, in the crystal, distinct layers are formed as a result of long intermolecular Bi‚‚‚S contacts of about 3.83 Å (Figure 69): each bismuth atom displays two such weak interactions, one in the equatorial plane dividing the large S‚‚‚Bi‚‚‚S angle and the other one trans to the carbon atom attached to the metal atom (C-Bi‚‚‚S 163.3°). If these interactions are also considered, the coordination geometry is a distorted pentagonal bipyramid.…”

Dimethyl‐tellur‐bis(alkylxanthogenate)

“…publiziert worden [3, 4J. TeIV-Xanthogenat-Verbindungen sind bislang nicht bekannt. Im Rahmen unserer Untersuchungen über Xanthogenate von Organometallaten der schwereren Va-Elemente Sb und Bi [5,6,12] sollte versucht werden, dabei gewonnene Erfahrungen auf ein Element der 6. Hauptgruppe, nämlich das Tellur, zu über-tragen.…”

“…Um festzustellen, ob sich Parallelen zu früher von uns untersuchten Organobi8mutxanthogenaten [6,[10][11][12] Einf' Vermf'sstmg der halben Reflexionssphäre im Bereich 5° < ~O < 45° ergab ~~:22 Intensitäten, die nach der ",-seau-Methode bezüglich Absorption korrigiert wurden (liMo = 2,98 mm-I). 1!J89 davon waren symmetrieunabhängig und 1890 erfüllten das Kriterium lObS ~ 3a(r obs )' Die Lösung der und Te-S4 zu dem kürzesten intermolekularen Abstand Te-S1' (3,755(1) A) ist dementsprechend nur gering (etwa 0,4 A).…”