X-ray crystal structure determination and NMR solution studies of 3′,3″5′,5″-tetrabromophenolphthalein ethyl ester

Abstract

The crystal structure of 3′,3″,5′,5″-tetrabromophenolphthalein ethyl ester (TBPE) has been determined by X-ray diffraction at room temperature. This compound crystallizes in space group [Formula: see text], with a = 12.361(4), b = 12.533(4), c = 9.986(2) Å, α = 99.57(3), β = 112.76(2), γ = 100.73(3) °, and Z = 2. The structure was solved by direct methods and refined by full-matrix least-squares calculations to a residual of 0.034 for 1862 observed reflections. TBPE is propeller shaped about the central carbon and crstallizes with one molecule of benzene solvent per asymmetric unit. In 1:1 CD2Cl2:CDCl3 solution complete 1H and 13C NMR signal assignments have been made via 1H1H COSY and 1H13C HETCOR experiments. The quinoidal and phenolic integrities are retained on the NMR timescale. By contrast for an acetone-d6 solution only 14 13C resonances are found and the colour of the solution changed from green to dark blue. These changes in acetone solution are attributed to the presence of a trace of base which induces the loss of the phenolic proton of TBPE and the existence of resonance forms which render the phenolic and quinoidal rings equivalent. Key words: crystal structure, NMR, 3′3″5′5″-tetrabromophenolphthalein ethyl ester.