Crystallographic studies of the structures of Au11(PPh3)7(SCN)3

[Display omitted] •This article presents definitive structural characterization of the gold cluster, Au11(PPh3)7(SCN)3.•Although this cluster was the first molecular gold cluster to be crystallographically identified, the data available at the time only showed the positions of the gold atoms and the phosphorus and sulfur atoms but without distinguishing between them.•We now have been able to crystallize this cluster in three different forms that differ significantly in the position of the thiocyanate ligands, which have a bent Au-S-CN structure.•The presence of ten large ligands on the cluster surface makes for a crowded environment but the thiocyanate ligands are able to reorient during crystal formation. The crystallization of two solvates of Au11(PPh3)7(SCN)3, 2Au11(PPh3)7(SCN)3·2C6H6·0.5EtOH (1) and Au11(PPh3)7(SCN)3·3EtOH (2), with (1) containing two independent molecules of the cluster, allows the positions of all of the ligands to finally be identified. Despite the bent nature of the thiocyanate ligands, they occupy similar sites to the ones that contain halogen ligands in Au11(PPh3)7Cl3, Au11(PPh3)7I3, and related molecules. However, the relative orientations of these thiocyanate ligands differ in the three cluster sites.