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The title compound, 1,1,1-tris[chloro-gold(I)-dimethylphosphanylmethyl]ethane (1) has been prepared from the tripodal tertiary phosphine ligand and three equivalents of chloro(dimethylsulfide)gold(I) in good yield. The complex has been characterized by means of its  1 H,  13 C, and  31 P NMR, and  197 Au Mößbauer spectra, by elemental analysis, and by a single crystal X-ray structure analysis. The crystals have a layer structure. In each of the crystallographically equivalent individual molecules two of the gold(I) centers are associated via a short intramolecular Au · · · Au contact [3.077(2) Å]. These pairs of gold atoms are aligned in chains through intermolecular Au ··· Au contacts of similar distances [3.084(2) Å]. According to this structural principle, strings of complex molecules are formed. The third Au(I) center of each of these molecules is associated with a similar unit of a neighbouring chain through interstrand Au ··· Au contacts [3.179(3) Å], thus crosslinking the chains to give a layer structure. The Au · · · Au contacts are recognized to be the main structure-determining force for the conformation of the molecules and their packing in this solid phase.

Gold Chains and Gold Pairs in the Layer Structure of 1,1,1-Tris[chloro-gold(I)-dimethylphosphanylmethyl]ethane