Synthesis and X-ray crystal structure of isomeric pyridine-based leuco-TAM dyes, 2,2-(2-(pyridinyl)propane-1,3-diylidene)bis(5-chloro-1,3,3-trimethyl indoline) derivatives and unusual stability of 4-pyridinyl compound

Abstract

The solid-state structures and unequivocal stereochemistries of isomeric pyridine-based leuco-triarylmethane (LTAM) dyes 2,2'-(2-(pyridin-4 or 3-yl)propane-1,3-diylidene)bis(5-chloro-1,3,3-trimethylindoline) derivatives were established by X-ray crystallography. Surprisingly, the EE isomer was formed for the 4-pyridinyl compound, whereas the 3-pyridinyl compound formed ZE isomers. In addition, the latter have a so-called three-bladed propeller conformation, whereas the former possess a Y-shaped conformation. These pyridine-based LTAM compounds stack to form a dimer, adopting either an orthorhombic, with Pcmn space group, or monoclinic crystal system with P2(1)/n space group in the crystal unit cell. (C) 2013 Elsevier B.V. All rights reserved.