Two new secondary Mannich bases, 4-bromo-2-[(aminopropyl)methyl]-phenol
(1) and 4-nitro-2-[(aminopropyl)methyl]-phenol (2), were synthesized. Crystal structures were determined at
liquid nitrogen temperature. It was found that in both compounds the
proton transfer forms exist in the solid state. In the case of 1, this was unexpected, because of the weak acidity of p-bromophenol being the parent component of this Mannich
base. The reason for that was found to be the formation of the O–···H–N+ hydrogen bonded
tetramer in the solid state. Two cyclic aggregates R4
2(8) and R2
2(12) describe the pattern
of hydrogen bonded interactions in the crystals of both compounds.
Additionally, C–H···π interactions stabilize
the crystal structures. The hydrogen bonds in 1 are slightly
stronger (N···O distances 2.708 and 2.733 Å) than
in 2 (2.721 and 2.765 Å, respectively) despite the
fact that p-nitrophenol participating in 2 is a stronger acid. The influence of permittivity of surroundings
and the hydrogen bonding pattern on the properties of intermolecular
hydrogen bonds are discussed on the basis of B3LYP and MP2 calculations
with basis sets 6-31+G(d,p) and 6-31++G(2d,2p). The coupling between
hydrogen bonds in crystals was studied with the application of the
IR spectra of isotopically diluted species. It was found that such
a coupling is stronger for 2, forming weaker hydrogen
bonds. Both the theory of IR spectra and quantum chemical calculations
demonstrate that the source of the observed behavior is electronic
participation in vibronic absorption.