Structural study of optical resolution. VII. The crystal structure of (-)589-oxalatobis(ethylenediamine)cobalt(III) hydrogen-d-tratrate dihydrate and comparison between the crystal structures of the more- and less-soluble diastereoisomers.

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概要

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• The single crystals of the more-soluble diastereoisomeric salt including the hydrogen-<I>d</I>-tartrate anion as a resolving agent, (−)<SUB>589</SUB>-[Co(ox)en<SUB>2</SUB>]H-<I>d</I>-tart·2H<SUB>2</SUB>O, have been newly obtained, and the crystal structure has been determined by three-dimensional X-ray analysis. The crystals are orthorhombic, space group P2<SUB>1</SUB>2<SUB>1</SUB>2, <I>Z</I>=4, <I>a</I>=16.583(5), <I>b</I>=14.186(5), and <I>c</I>=7.403(2) Å. The structure was solved by the heavy-atom method and refined by the block-diagonal least-squares method to a conventional <I>R</I>-value of 0.044 for the 1907 independent reflections. One of the two ethylenediamine rings is of the <I>ob</I> form. The other ring has a conformational disorder, the proportion of the <I>ob</I> to the <I>lel</I> form being 50:50. The absolute configuration of the complex cation is denoted as <I>Δ</I>[(50%-δ, 50%-λ)δ]. The framework of the crystal structure is built up of a stack of complex cations and H-<I>d</I>-tart anions along the c-axis in a "head-to-tail" arrangement. The shortest interatomic distance between the H-<I>d</I>-tart anions is 2.473 Å(O–H···O), while that between the complex cations is 2.995 Å (N–H···O). A comparison of the crystal structure of the more-soluble diastereoisomer with that of the lesssoluble one revealed that the {H-<I>d</I>-tart}<SUB>∞</SUB> chain is structurally different from that in the latter; the chain is spiral in the latter, but not in the former. The structural feature in the {H-<I>d</I>-tart}<SUB>∞</SUB> chain is considered to play an important role in the discrimination of the chirality of the [Co(ox)en<SUB>2</SUB>]<SUP>+</SUP> cation. The conformational disorder is discussed in connection with the dehydration of crystals.

• 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

• Kuramoto Masahiro

  Department of Chemistry, Faculty of Science, Hiroshima University

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