Electron diffraction measurements of the vapour at 255 K established that digallane is structurally similar to diborane with 2 bridging hydrogen atoms (so-called three-center two-electron bonds). The terminal Ga-H bond length is 152 pm, the Ga-H bridging is 171 pm and the Ga-H-Ga angle is 98°. The Ga-Ga distance is 258 pm. The H NMR spectrum of a solution of digallane in toluene shows two peaks attributable to terminal and bridging hydrogen atoms.
In the solid state, digallane appears to adopt a polymeric or oligomeric structure. The vibrational spectrum is consistent with tetramer (i.e. ). The vibrational data indicate the presence of terminal hydride ligands. In contrast, the hydrogen atoms are all bridging in α-alane, a high-melting, relatively stable polymeric form of aluminium hydride wherein the aluminium centers are 6-coordinated. Digallane decomposes at ambient temperatures: