The crystal structure of p-diethylaminobenzenediazonium hexafluorophosphate

Abstract

p-Diethylaminobenzenediazonium hexafluorophosphate, C10H14N3+•PF6−, crystallized in space group [Formula: see text] with a = 12.105(4), b = 12.340(5), c = 10.439(4) Å, α = 96.53(3), β = 104.11(3), γ = 64.44(3)°, and Z = 4. The structure was solved using direct methods and refined with full-matrix least-squares techniques on F, to a final R of 0.054 for 1917 reflections with F2 > 3σ(F2). The mean bond lengths for the diazo group are: N—N 1.096(6); C—N 1.357(7) Å. The geometry of the molecule is discussed in terms of the possible resonance forms and it is shown to be consistent with a form in which the N—N triple bond is essentially intact and the aminobenzene moiety has "quinoidal" character.

Interpretation of neighboring group interactions in crystal structures. A solid state and quantum-chemical study of "incipient nucleophilic attack" in 2-diazonium benzoic acid and its benzoate

“…The placement of nucleophiles in 1,3-bridging positions is common, and structures are known of several diazonium ions with polyfluoro anions in which the F atoms are placed ~~~~~~~~~~~~~in the two CNN bridging positions and, if both of these are occupied, in the proximity of Np. The crystal structures of I11 (22) and IV (23) both contain F atoms in such bridging positions with nearly equal F-N, and F-Np distances. The crystal structure of PhN,+BF,-(24), V, provides an excellent example for the placement of counterions in the proximity of both N, group nitrogens and this bridging was regarded as the result of electrostatic interactions of F with N, and Np.…”