Abstract
In the title ternary co-crystalline adduct, C7H14N4·2C6H5NO3, mol-ecules are linked by two inter-molecular O-H⋯N hydrogen bonds, forming a tricomponent aggregates in the asymmetric unit. The hydrogen-bond formation to one of the N atoms is enough to induce structural stereoelectronic effects in the normal donor→acceptor direction. In the title adduct, the two independent nitro-phenol mol-ecules are essentially planar, with maximum deviations of 0.0157 (13) and 0.0039 (13) Å. The dihedral angles between the planes of the nitro group and the attached benzene rings are 4.04 (17) and 5.79 (17)°. In the crystal, aggregates are connected by C-H⋯O hydrogen bonds, forming a supra-molecular dimer enclosing an R 6 (6)(32) ring motif. Additional C-H⋯O inter-molecular hydrogen-bonding inter-actions form a second supra-molecular inversion dimer with an R 2 (2)(10) motif. These units are linked via C-H⋯O and C-H⋯N hydrogen bonds, forming a three-dimensional network.
Highlights
In the title ternary co-crystalline adduct, C7H14N42C6H5NO3, molecules are linked by two intermolecular O—H N hydrogen bonds, forming a tricomponent aggregates in the asymmetric unit
Electron density at the free ortho position of the phenol and the reactivity of the phenolic hydroxy group played a crucial role and the reaction does not occur in the absence of the hydroxy group (Deng et al 2014)
The phenol–N complex has served as a good model for the investigation of proton and electron-transfer processes occurring in living matter, it being generally assumed that this interaction consists solely of the attraction between the lone pair of the amine N atom and the phenolic hydroxy proton (Lu et al 2006)
Summary
The chemistry of the aminoalkylation of aromatic substrates by the Mannich reaction is of great interest and chemical importance (Tramontini et al, 1988). We have undertaken a long-term project designed to systematically investigate the structures, chemical properties and reactivity of macrocyclic aminals as preformed electrophilic reagents for the synthesis of phenolic Mannich bases through simple and efficient methodologies As part of this investigation we have recently reported the synthesis of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU), (II) (Rivera et al 2004). Because of the acidity of the phenolic group, the proton potential of the hydrogen-bonded system can be fundamentally changed by substituents in the 4-position of the phenol ring (Xiong et al, 2002) Because of this and as a logical extension of our previous efforts to understand the hydrogenbonding interactions between TATU and phenols, we investigated the reaction of TATU with 4-nitrophenol. The aminal moiety is linked to two 4-nitrophenol molecules via O—H N hydrogen bonds where one interaction is to a more basic site (N3) and the other one to an N atom adjacent to the ethylene bridge (N1)
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
