A 32 vertex polyhedron via supramolecular assembly of silanedithiolate silanolate unitsElectronic supplementary information (ESI) available: Details of the synthesis, crystallographic data for 4 and detailed tables with geometric parameters, Tables S1-S4, Fig. S1 and S2. See DOI: 10.1039/c2cc33883a

A high yield synthesis of the first silanedithiolate silanolate is reported which spontaneously assembles forming an inorganic rugby ball shaped 32 vertex polyhedral cluster stabilized by sterically demanding 2,6-dimesitylphenyl substituents and two LiCl units. A silanedithiolate silanolate assembles spontaneously forming an inorganic rugby ball shaped 32 vertex polyhedral cluster stabilized by organic substituents and LiCl.