Boron-nitrogen containing compounds with high hydrogen contents as represented by ammonia borane (NH3BH3) have recently attracted intense interest for potential hydrogen storage applications. One such compound is [(NH3)2BH2]B3H 8 with a capacity of 18.2 wt% H. Two safe and efficient synthetic routes to [(NH3)2BH2]B3H8 have been developed for the first time since it was discovered 50 years ago. The new synthetic routes avoid a dangerous starting chemical, tetraborane (B4H10), and afford a high yield. Single crystal X-ray diffraction analysis reveals N-Hδ+⋯Hδ-- B dihydrogen interactions in the [(NH3)2BH 2]B3H8·18-crown-6 adduct. Extended strong dihydrogen bonds were observed in pure [(NH3) 2BH2]B3H8 through crystal structure solution based upon powder X-ray analysis. Pyrolysis of [(NH3) 2BH2]B3H8 leads to the formation of hydrogen gas together with appreciable amounts of volatile boranes below 160 °C. © The Royal Society of Chemistry 2013.