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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
Author(s) -
Rivera Augusto,
Rojas Jicli José,
Sadat-Bernal John,
Ríos-Motta Jaime,
Bolte Michael
Publication year - 2019
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s205322961901516x
Subject(s) - aminal , intermolecular force , hydrogen bond , cage , characterization (materials science) , crystallography , materials science , nanotechnology , chemistry , chemical physics , stereochemistry , molecule , organic chemistry , engineering , structural engineering
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, 2C 6 H 5 NO 3 ·C 6 H 12 N 4 ·H 2 O, ( 1a ), with 1,3,6,8‐tetraazatricyclo[4.3.1.1 3,8 ]undecane [TATU ( 2 )] as the 2:1 cocrystal, 2C 6 H 5 NO 3 ·C 7 H 14 N 4 , ( 2a ), and with 1,3,6,8‐tetraazatricyclo[4.4.1.1 3,8 ]dodecane [TATD, ( 3 )] as the 2:1 cocrystal, 2C 6 H 5 NO 3 ·C 8 H 16 N 4 , ( 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.