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

    57 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 ρ3 M = -355 and ρ3 P = +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 ρ1 M = +138, ρ1 P = -140 deg mm-1, and ρ2 M = -56, ρ2 P = +58 deg mm-1, much smaller than ρ3 M and ρ3 P. 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

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    Optical Rotation
    Hydrogen
    Crystals
    Acids
    Ammonium Compounds
    Salts
    Electrons
    Hydrogen bonds
    Polarimeters
    Direction compound
    tryptamine
    4-chlorobenzoic acid
    Molecules

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Optical activity induced by helical arrangements of tryptamine and 4-chlorobenzoic acid in their cocrystal. / Koshima, Hideko; Nagano, Masaki; Asahi, Toru.

    In: Journal of the American Chemical Society, Vol. 127, No. 8, 02.03.2005, p. 2455-2463.

    Research output: Contribution to journalArticle

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    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 ρ3 M = -355 and ρ3 P = +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 ρ1 M = +138, ρ1 P = -140 deg mm-1, and ρ2 M = -56, ρ2 P = +58 deg mm-1, much smaller than ρ3 M and ρ3 P. 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.",
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    N2 - 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 ρ3 M = -355 and ρ3 P = +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 ρ1 M = +138, ρ1 P = -140 deg mm-1, and ρ2 M = -56, ρ2 P = +58 deg mm-1, much smaller than ρ3 M and ρ3 P. 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.

    AB - 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 ρ3 M = -355 and ρ3 P = +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 ρ1 M = +138, ρ1 P = -140 deg mm-1, and ρ2 M = -56, ρ2 P = +58 deg mm-1, much smaller than ρ3 M and ρ3 P. 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.

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