The new trichlorosilane 2,6-Et 2C 6H 3N(SiMe 3)SiCl 3 (2) on controlled hydrolysis yields 2,6-Et 2C 6H 3N(SiMe 3)Si(OH) 3 (3). X-ray diffraction analysis of 3 reveals a rare structure type of aggregation where eight molecules of the silanetriol form an octameric cage through intermolecular O - H⋯O hydrogen bonding. Reaction of 3 with piperazine (PIP), 4,4′-bipyridine (BPY), and 1,4-diazabicyclo[2,2,2]octane (DABCO) yields [{2,6-Et 2C 6H 3N(SiMe 3)-Si(OH) 3}-{PIP}] (4), [{2,6-Et 2C 6H 3N(SiMe 3)Si(OH) 3}·{BPY}] (5), and [{2,6-Et 2C 6H 3N(SiMe 3)-Si(OH) 3}·{DABCO}] (6), respectively. Treatment of 6 with HAl iBu 2 affords the cubic aluminosiioxane [2,6-Et 2C 6H 3N(SiMe 3)SiO 3Al(DABCO)] 4·1,4-dioxane (7), The aluminum centers on the cubic core are coordinated by DABCO molecules in a monodentate fashion. © 2005 American Chemical Society.