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Charge‐assisted hydrogen bonding in three diaminobenzene salts
Author(s) -
Zick Patricia L.,
Geiger David K.
Publication year - 2018
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/s2053229618015553
Subject(s) - hydrogen bond , perchlorate , crystallography , chemistry , benzene , crystal structure , salt (chemistry) , molecule , ion , amine gas treating , density functional theory , computational chemistry , organic chemistry
Hydrogen‐bonding interactions play an important role in the rational design of crystal systems with desirable architectures. The crystal structures of benzene‐1,2‐diaminium sulfate sesquihydrate, C 6 H 20 N 2 2+ ·SO 4 2− ·1.5H 2 O, ( 1 ), benzene‐1,3‐diaminium tetrachloridozincate(II), (C 6 H 20 N 2 )[ZnCl 4 ], ( 3 ), and 3‐aminoanilinium perchlorate, C 6 H 9 N 2 + ·ClO 4 − , ( 4 ), are reported. Hydrated salt ( 1 ) is a polymorph (space group C 2/ c ) of a previously reported [Anderson et al. (2011). Cryst. Growth Des. 11 , 4904–4919] crystalline modification of salt ( 2 ) (space group P 2 1 / c ). The contents of the asymmetric unit of ( 2 ) are twice that of ( 1 ). In each, the extended structures exhibit hydrogen bonds, resulting in chains of ions and hydrogen‐bonded rings with an R 4 4 (8) motif involving water molecules. Hirshfeld surface analysis shows that a significant difference between the two is the degree of C…C interaction. Salt ( 3 ) exhibits an extended structure having hydrogen‐bonded rings and parallel benzene rings, with a centroid‐to‐centroid separation of 3.860 (2) Å. Salt ( 4 ) displays a three‐dimensional superstructure that results from linked planes of ions joined by an extensive hydrogen‐bonding network involving N—H…O, N—H…N and C—H…π interactions. The cation–anion and N—H…N interaction energies in ( 4 ), determined using density functional theory (DFT), show significantly stronger aminium–perchlorate than amine–perchlorate interactions.