Crystal structures of fourteen halochalcogenylphosphonium tetrahalogenidoaurates(III)

The structures of fourteen halochalcogenylphosphonium tetrahalogenidoaurates(III), phosphane chalcogenide derivatives with general formula [R13 – nR2nPEX][AuX4] (R1 = t-butyl; R2 = isopropyl; n = 0 to 3; E = S or Se; X = Cl or Br) are presented. The eight possible chlorido derivatives are: 17a, n = 3, E = S; 18a, n = 2, E = S; 19a, n = 1, E = S; 20a, n = 0, E = S; 21a, n = 3, E = Se; 22a, n = 2, E = Se; 23a, n = 1, E = Se; and 24a, n = 0, E = Se, and the corresponding bromido derivatives are 17b – 24b in the same order. Structures were obtained for all compounds except for the tri-t-butyl derivatives 24a and 24b. Isotypy is observed for 18a/18b/22a/22b, 19a/23a, 17b/21b and 19b/23b. In eleven of the compounds, X...X contacts (mostly very short) are observed between the cation and anion, whereby the E — X...X groups are approximately linear and the X...X — Au angles approximately 90 ° . The exceptions are 17a, 19a and 23a, which instead display short E...X contacts. Bond lengths in the cations correspond to single bonds P — E and E — X. For each group with constant E and X, the P — E — X bond-angle values increase monotonically with the steric bulk of the alkyl groups. The packing is analysed in terms of E...X, X...X (some between anions alone), H...X and H...Au contacts. Even for isotypic compounds, some significant differences can be discerned.

Source: Acta Crystallographica Section E - April 23, 2024 Category: Chemistry Authors: Upmann, D. Bockfeld, D. Jones, P.G. T â rcoveanu, E. Tags: crystal structure gold halochalcogenylphosphonium secondary interactions research communications Source Type: research