Abstract N, N-Dimethylaminopropylsilane H 3 Si (CH 2) 3 NMe 2 was synthesised by the reaction of (MeO) 3 Si (CH 2) 3 NMe 2 with lithium aluminium hydride. Its solid-state structure was determined by X-ray diffraction, which revealed a five-membered ring with an Si⋅⋅⋅ N distance of 2.712 (2) Å. Investigation of the structure by gas-phase electron diffraction (GED), ab initio and density functional calculations and IR spectroscopy ...