Crystal structures of fourteen halochalcogenylphos-pho-nium tetra-halogenidoaurates(III).

The structures of fourteen halochalcogenyl-phospho-nium tetra-halogen-ido-aurates(III), phosphane chalcogenide derivatives with general formula [ P][Au ] ( = -butyl; = isopropyl; = 0 to 3; = S or Se; = Cl or Br) are presented. The eight possible chlorido derivatives are: , = 3, = S; , = 2, = S; , = 1, = S; , = 0, = S; , = 3, = Se; , = 2, = Se; , = 1, = Se; and , = 0, = Se, and the corresponding bromido derivatives are - in the same order. Structures were obtained for all compounds except for the tri--butyl derivatives and . Isotypy is observed for / / / , / , / and / . In eleven of the compounds, ⋯ contacts (mostly very short) are observed between the cation and anion, whereby the -⋯ groups are approximately linear and the ⋯-Au angles approximately 90°. The exceptions are , and , which instead display short ⋯ contacts. Bond lengths in the cations correspond to single bonds P- and -. For each group with constant and , the P-- bond-angle values increase monotonically with the steric bulk of the alkyl groups. The packing is analysed in terms of ⋯, ⋯ (some between anions alone), H⋯ and H⋯Au contacts. Even for isotypic compounds, some significant differences can be discerned.