Hydrogen bonds and ?-? inter-actions in two new crystalline phases of methyl-ene blue.

ABSTRACT: Two unprecedented solid phases involving the 3,7-bis-(di-methyl-amino)-pheno-thia-zin-5-ium cation, i.e. methyl-ene blue (MB+ ), have been obtained and structurally characterized. In the crystals of 3,7-bis-(di-methyl-amino)-pheno-thia-zin-5-ium chloride dihydrate, C16H18N3S+·Cl-·2H2O (I) and 3,7-bis-(di-methyl-amino)-pheno-thia-zinium bis-ulfite, C16H18N3S+·HSO4- (II), the cationic dye mol-ecules are planar and disposed in an anti-parallel mode, showing ?-? stacking inter-actions, with mean inter-planar distances of 3.326?(4) and 3.550?(3)?Å in (I) and (II), respectively. In compound (I), whose phase was found affected by merohedral twinning [BASF = 0.185?(3)], the presence of water mol-ecules allows a network of hydrogen bonds involving MB+ as both a donor and an acceptor, whereas in compound (II), the homo-inter-action of the anions causes an effective absence of classical hydrogen-bond donors. This substantial difference has important consequences for the stacking geometry and supra-molecular inter-actions of the MB+ cations, which are analysed by Hirshfeld fingerprint plots and subsequently discussed.

SUBMITTER: Canossa S 

PROVIDER: S-EPMC5947468 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature