TY - JOUR
T1 - Involvement of conformational isomerism in the complexity of the crystal network of 1-(4-nitrophenyl)-1H-1,3-benzimidazole derivatives driven by C—H…A (A = NO2, Npy and π) and orthogonal Npy…NO2 and ONO…Csp2 interactions
AU - García-Aranda, Mónica I.
AU - Gómez-Castro, Carlos Z.
AU - García-Báez, Efrén V.
AU - Gómez, Yolanda Gómez y.
AU - Castrejón-Flores, José L.
AU - Padilla-Martínez, Itzia I.
N1 - Publisher Copyright:
© Garcá-Aranda et al. 2018
PY - 2018
Y1 - 2018
N2 - A detailed structural analysis of the benzimidazole nitroarenes 1-(4-nitrophenyl)-1H-1,3-benzimidazole, C13H9N3O2, (I), 1-(4-nitrophenyl)-2-phenyl-1H-1,3-benzimidazole, C19H13N3O2, (II), and 2-(3-methylphenyl)-1-(4-nitrophenyl)-1H-1,3-benzimidazole, C20H15N3O2, (III), has been performed. They are nonplanar structures whose crystal arrangement is governed by Csp2—H…A (A = NO2, Npy and π) hydrogen bonding. The inherent complexity of the supramolecular arrangements of compounds (I) (Z′ = 2) and (II) (Z′ = 4) into tapes, helices and sheets is the result of the additional participation of π– and n–π* (n = O and Npy; π* = Csp2 and) interactions that contribute to the stabilization of the equi-energetic conformations adopted by each of the independent molecules in the asymmetric unit. In contrast, compound (III) (Z′ = 1) is self-paired, probably due to the effect of the steric demand of the methyl group on the crystal packing. Theoretical ab initio calculations confirmed that the presence of the arene ring at the benzimidazole 2-position increases the rotational barrier of the nitrobenzene ring and also supports the electrostatic nature of the orthogonal ONO…Csp2 and Npy…NO2 interactions.
AB - A detailed structural analysis of the benzimidazole nitroarenes 1-(4-nitrophenyl)-1H-1,3-benzimidazole, C13H9N3O2, (I), 1-(4-nitrophenyl)-2-phenyl-1H-1,3-benzimidazole, C19H13N3O2, (II), and 2-(3-methylphenyl)-1-(4-nitrophenyl)-1H-1,3-benzimidazole, C20H15N3O2, (III), has been performed. They are nonplanar structures whose crystal arrangement is governed by Csp2—H…A (A = NO2, Npy and π) hydrogen bonding. The inherent complexity of the supramolecular arrangements of compounds (I) (Z′ = 2) and (II) (Z′ = 4) into tapes, helices and sheets is the result of the additional participation of π– and n–π* (n = O and Npy; π* = Csp2 and) interactions that contribute to the stabilization of the equi-energetic conformations adopted by each of the independent molecules in the asymmetric unit. In contrast, compound (III) (Z′ = 1) is self-paired, probably due to the effect of the steric demand of the methyl group on the crystal packing. Theoretical ab initio calculations confirmed that the presence of the arene ring at the benzimidazole 2-position increases the rotational barrier of the nitrobenzene ring and also supports the electrostatic nature of the orthogonal ONO…Csp2 and Npy…NO2 interactions.
KW - conformational isomerism
KW - crystal structure
KW - helix
KW - high-Z′ structure
KW - orthogonal nitro…C interaction
KW - orthogonal nitro…N interaction
KW - snapshot conformer
UR - http://www.scopus.com/inward/record.url?scp=85045349446&partnerID=8YFLogxK
U2 - 10.1107/S2053229618003406
DO - 10.1107/S2053229618003406
M3 - Artículo
C2 - 29620026
SN - 2053-2296
VL - 74
SP - 428
EP - 436
JO - Acta Crystallographica Section C: Structural Chemistry
JF - Acta Crystallographica Section C: Structural Chemistry
IS - 4
ER -