Mechanochemical synthesis and X‐ray structural characterization of three 3‐nitrophenol cocrystals with three aminal cage azaadamantanes: the role of the stereoelectronic effect on intermolecular hydrogen‐bonding patterns. Issue 12 (22nd November 2019)

• Record Type: Journal Article
• Authors: Rivera, Augusto; Rojas, Jicli José; Sadat-Bernal, John; Ríos-Motta, Jaime; Bolte, Michael
• Is Part Of: Acta crystallographica. Volume 75:Issue 12(2019)
• Page Start: 1635
• Page End: 1643
• Publication Date: 2019-11-22
• Subjects: mechanochemistry -- aminal cage -- azaadamantane -- HMTA -- TATD -- hydrogen bond -- anomeric effect -- crystal structure; Crystallography -- Periodicals; Crystals -- Periodicals; 548.3
• DOI: 10.1107/S205322961901516X
• Languages: English
• ISSNs: 2053-2296

Abstract

Abstract : The structures of the cocrystalline adducts of 3‐nitrophenol with 1, 3, 5, 7‐tetraazatricyclo[3.3.1.1 3, 7 ]decane, 1, 3, 6, 8‐tetraazatricyclo[4.3.1.1 3, 8 ]undecane and 1, 3, 6, 8‐tetraazatricyclo[4.4.1.1 3, 8 ]dodecane are reported. The three cocrystals were obtained by the solvent‐free assisted grinding method. Abstract : The structures of the cocrystalline adducts of 3‐nitrophenol (3‐NP) with 1, 3, 5, 7‐tetraazatricyclo[3.3.1.1 3, 7 ]decane [HMTA, (1 )] as the 2:1:1 hydrate, 2C6 H5 NO3 ·C6 H12 N4 ·H2 O, (1a ), with 1, 3, 6, 8‐tetraazatricyclo[4.3.1.1 3, 8 ]undecane [TATU (2 )] as the 2:1 cocrystal, 2C6 H5 NO3 ·C7 H14 N4, (2a ), and with 1, 3, 6, 8‐tetraazatricyclo[4.4.1.1 3, 8 ]dodecane [TATD, (3 )] as the 2:1 cocrystal, 2C6 H5 NO3 ·C8 H16 N4, (3a ), are reported. In the binary crystals (2a ) and (3a ), the 3‐nitrophenol molecules are linked via O—H…N hydrogen bonds into aminal cage azaadamantanes. In (1a ), the structure is stabilized by O—H…N and O—H…O hydrogen bonds, and generates ternary cocrystals. There are C—H…O hydrogen bonds present in all three cocrystals, and in (1a ), there are also C—H…O and C—H…π interactions present. The presence of an ethylene bridge in the structures of (2 ) and (3 ) defines the formation of a hydrogen‐bonded motif in the supramolecular architectures of (2a ) and (3a ). The differences in the C—N bond lengths of the aminal cage structures, as a result of hyperconjugative interactions and electron delocalization, were analysed. These three cocrystals were obtained by the solvent‐free assisted grinding method. Crystals suitable for single‐crystal X‐ray diffraction were grown by slow evaporation from a mixture of hexanes.