Ball and Socket Assembly of Binary Superatomic Solids Containing Trinuclear Nickel Cluster Cations and Fulleride Anions.

The superlattice structures of hierarchical cluster solids are dictated by short-range interactions between constituent building blocks. Here we show that shape complementary sites, as well as halogen and chalcogen bonding between exposed capping ligands and fullerides, govern the packing arrangement of the resulting binary solids. Four new superatomic solids, [Ni(μ-I)(μ-dppm)](C) (1·C), [Ni(μ-I)(μ-dppm)](C) (1·C), [Ni(μ-Te)(μ-dppm)](C) (2·C), and [Ni(μ-Te)(μdppm)](C) (2·C), (dppm = PhPCHPPh) were prepared and crystallized from solution.