Molecular Structure of 1,5-Diazabicyclo[3.1.0]hexane as Determined by Gas Electron Diffraction and Quantum-Chemical Calculations

The equilibrium molecular structure and conformation of 1,5-diazabicyclo[3.1.0]hexane (DABH) has been studied by the gas-phase electron-diffraction method at 20 °C and quantum-chemical calculations. Three possible conformations of DABH were considered: boat, chair, and twist. According to the experimental and theoretical results, DABH exists exclusively as a boat conformation of C_s symmetry at the temperature of the experiment. The MP2 calculations predict the stable chair and twist conformations to be 3.8 and 49.5 kcal mol⁻¹ above the boat form, respectively. The most important semi-experimental geometrical parameters of DABH (r_e, Å and ∠_e, deg) are (N1−N5) = 1.506(13), (N1−C6) = 1.442(2), (N1−C2) = 1.469(4), (C2−C3) = 1.524(7), (C6−N1−C2) = 114.8(8), (N5−N1−C2) = 107.7(4), (N1−C2−C3) = 106.5(9), and (C2−C3−C4) = 104.0(10). The natural bond orbital (NBO) analysis has shown that the most important stabilization factor in the boat conformation is the n(N) → σ*(C−C) anomeric effect. The geometry calculations and NBO analysis have been performed also for the bicyclohexane molecule.