Azido compounds geometry

The vast majority of diazo (generically C—N=N) compounds studied by X-ray diffraction involve extensive delocalization through unsaturated groups involving the C atom. Very few diazoalkanes or azidoalkanes have been reported and even here the canonical forms contributing to the effective resonance hybrids involve considerable electron delocalization. For these reasons, the geometries of diazo and azido compounds for all types of substitution are covered in Section III.B.4. 

The data recorded in Table 1 describe the behaviour of the azido group in its equilibrium nuclear configuration. However the main interest in this group lies in those properties which depend on changes in its geometry, its bending to form cyclic compounds and its dissociation to — N + N2. Obviously this has no parallel in the halogen series. 

In coordination chemistry, azido complexes wherein azide ions are coordinated to metal sites are known for long. The azide ion was found in terminal as well as in bridging (l,l-/r, l,l,l-/r, l,3-/r) coordination geometries. It is well established in the literature that the stability of such compounds decreases with an increase of the covalence of the M-N3 bond and with an increasing M/N3 ratio. Binary systems of the type MtNslx usually decompose under formation of dinitrogen and elemental M. 

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