title: Molecular structure of 1,5-diazabicyclo[3.1.0]hexane as determined by gas electron diffraction and quantum-chemical calculations.
abstract: 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 degrees 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), A and angle)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) --> sigma*(C-C) anomeric effect. The geometry calculations and NBO analysis have been performed also for the bicyclohexane molecule.
authors.affiliation: Chemieinformationssysteme, University of Ulm, D-89069 Ulm, Germany. yuri.vishnevskiy@gmail.com
authors.forename: Yuri V
authors.initials: YV
authors.lastname: Vishnevskiy
authors.forename: Natalja
authors.initials: N
authors.lastname: Vogt
authors.forename: Jürgen
authors.initials: J
authors.lastname: Vogt
authors.forename: Anatolii N
authors.initials: AN
authors.lastname: Rykov
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Kuznetsov
authors.forename: Nina N
authors.initials: NN
authors.lastname: Makhova
authors.forename: Lev V
authors.initials: LV
authors.lastname: Vilkov