Two square pyramidal trinuclear dioxovanadium(V) complexes with [N2O3]-donor set ligand environment 1, (Et3NH)2[V3O6(SaltagBr)] {H5SaltagBr = tris(5-bromo-2-hydroxybenzylidene)triaminoguanidine} and 2, (nBu4N)2[V3O6(SaltagBr)] have been synthesized and the X-ray structures of both 1 & BULL;H2O and 2 & BULL;H2O have been determined. SaltagBr is a pentaanionic tritopic ligand with C3-symmetry containing three [NNO]-donor set tridentate pockets, thereby making it a suitable ligand for holding three VO2+ groups in their pockets. Crystal packing in the complex 1 & BULL;H2O, (Et3NH)2[V3O6(SaltagBr)]& BULL;H2O is partially stabilized by intermolecular H-bonds and intermolecular 7C-7C stacking interactions between the phenyl rings with a centroid-to-centroid distance of 3.700 & ANGS;. In the crystal structure of complex 2 & BULL;H2O, (n-Bu4N)2[V3O6(SaltagBr)]& BULL;H2O, intermolecular H-bonds partially contribute to the stabilization of crystal packing.