Optical activity induced by helical arrangements of tryptamine and 4-chlorobenzoic acid in their cocrystal

Hideko Koshima, Masaki Nagano, Toru Asahi

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

Optical rotatory powers of chiral cocrystals formed from the achiral molecules tryptamine and 4-chlorobenzoic acid were determined by the HAUP (high accuracy universal polarimeter) method. These cocrystals belonged to space group P212121, and their absolute configuration was confirmed by the Flack parameter. In the M-crystal, 2-fold helical arrangements are formed in a counterclockwise direction between the two components through the quaternary ammonium salt bridge, hydrogen bond, and the aromatic π-π interaction along the c axis, while clockwise helices alone exist in the P-crystal. Large rotatory powers ρ3M = -355 and ρ3P = +352 deg mm-1 were obtained along the c axis in the M- and P-crystal, respectively, at 632.8 nm and 303 K. The magnitude was 10 to 100 times larger than those for ordinary organic crystals. Further, it was confirmed that the negative sign was induced by the counterclockwise helical structures and the positive sign by the clockwise helices. In contrast, the rotations along the a and b axis which are in perpendicular directions to the screw axis were ρ1M = +138, ρ1P = -140 deg mm-1, and ρ2M = -56, ρ2P = +58 deg mm-1, much smaller than ρ3M and ρ3P. The results revealed that the helically arranged aromatic π electrons as well as the helical ionic and hydrogen bond networks in the crystal contributed to the enhancement of the magnitude of these rotations.

Original languageEnglish
Pages (from-to)2455-2463
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number8
DOIs
Publication statusPublished - 2005 Mar 2

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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