Structural study of optical resolution. XI. The crystal structures of (+)589-tris(biguanide)cobalt(III) chloride d-tartrate trihydrate and racemic tris(biguanide)cobalt(III) trichloride.

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概要

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• The crystal structures of the more-soluble diastereomeric salt, (+)<SUB>589</SUB>-[Co(Hbg)<SUB>3</SUB>]Cl(<I>d</I>-tart)·3H<SUB>2</SUB>O (<B>1</B>), and the racemic chloride salt, [Co(Hbg)<SUB>3</SUB>]Cl<SUB>3</SUB> (<B>2</B>), have been determined by X-ray analysis (<I>R</I>=0.033, 2788 reflections for <B>1</B> and <I>R</I>=0.056, 2785 reflections for <B>2</B>), where Hbg=C<SUB>2</SUB>H<SUB>7</SUB>N<SUB>5</SUB>, <I>d</I>-tart=C<SUB>4</SUB>H<SUB>4</SUB>O<SUB>6</SUB><SUP>2−</SUP>. The more-soluble salt <B>1</B> is orthorhombic, with the space group P2<SUB>1</SUB>2<SUB>1</SUB>2<SUB>1</SUB> <I>Z</I>=4, <I>a</I>=15.654(2), <I>b</I>=13.758(2), and <I>c</I>=11.010(1) Å. The racemic salt <B>2</B> is monoclinic, with the space group C2/c, <I>Z</I>=8, <I>a</I>=19.441(9), <I>b</I>=14.901(7), <I>c</I>=15.911(6) Å, and β=127.63(2)°. In <B>1</B>, the complex cations and the Cl<SUP>−</SUP> ions are arranged alternately to form an infinite spiral chain, {<I>Δ</I>-[Co(Hbg)<SUB>3</SUB>]Cl}<SUB>∞</SUB>. Each <I>d</I>-tartrate is hydrogen-bonded to a twofold-screw-axis-related neighbor (–OH···OOC– 2.792 Å) to form an infinite chain, (<I>d</I>-tart)<SUB>∞</SUB>. In <B>2</B> two kinds of similar infinite spiral chains, {<I>Δ</I>-[Co(Hbg)<SUB>3</SUB>]Cl}<SUB>∞</SUB> and {<I>Λ</I>-[Co(Hbg)<SUB>3</SUB>]Cl}<SUB>∞</SUB>, which are mirror images of each other are found. The structures of these two salts <B>1</B> and <B>2</B> are compared with those of the less-soluble diastereomeric chloride <I>d</I>-tartrate and the optically active chloride in both of which a similar infinite chain has been found, and the mechanism of chiral discrimination <I>via</I> the diastereomer formation is discussed.

• 公益社団法人 日本化学会の論文

著者

• YONEDA Hayami

  Department of Chemistry, Faculty of Science, Hiroshima University

• Kushi Yoshihiko

  Department Of Chemistry Graduate School Of Science Osaka University

• Tada Toshiji

  Department Of Biological Science Graduate School Of Science Osaka Prefecture University

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