X-ray structural study on molecular stereochemistries of six-coordinate Zn(II) complexes of trans-ZnX2N4 type. Out-of-plane displacement of Zn(II) from a plane formed by in-plane four nitrogens.
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概要
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Molecular structures of <I>trans</I>-bis(isothiocyanato)(1,4,8,11-tetraazacyclotetradecane and 1,4,8,12-tetraazacyclopentadecane)zinc(II) complexes, [Zn(NCS)<SUB>2</SUB>(C<SUB>10</SUB>H<SUB>24</SUB>N<SUB>4</SUB>)] (<B>1</B>) and [Zn(NCS)<SUB>2</SUB>(C<SUB>11</SUB>H<SUB>26</SUB>N<SUB>4</SUB>)] (<B>2</B>), have been determined by X-ray analyses. Crystal data are: for <B>1</B>, orthorhombic, space group P2<SUB>1</SUB>nb, <I>a</I>=14.502(2), <I>b</I>=18.163(2), <I>c</I>=6.552(1) Å, <I>V</I>=1718.0(4) Å<SUP>3</SUP>, <I>Z</I>=4; for <B>2</B>, monoclinic, space group P2<SUB>1</SUB>/a, <I>a</I>=14.453(2), <I>b</I>=14.436(1), <I>c</I>=9.213(1) Å, β=104.82(1)°, <I>V</I>=1858.3(4) Å<SUP>3</SUP>, <I>Z</I>=4. Coordination geometries about Zn(II) in <B>1</B> and <B>2</B> are of the pseudo-octahedral type with two NCS groups at the trans positions, but the Zn(II) ion in each compound deviates from a plane defined by the four nitrogens of the macrocyclic ligand by 0.179 Å on the average in <B>1</B> and 0.193 Å in <B>2</B>. Structural features of <B>1</B> and <B>2</B> suggest, complemented with data reported previously for out-of-plane Zn(II) structures, that potential surface regarding the out-of-plane displacement is very flat. The Zn–NCS distance has been found to decrease as an in-plane Zn–N length (or cavity size of the ligand) increases. The observed negative correlation is substantially stronger than those for Ni(II) and Co(III) complexes and discloses the softness of a Zn(II) ion.
- 公益社団法人 日本化学会の論文
著者
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Kato Masako
Department Of Chemistry Faculty Of Science Nara Women's University
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Ito Tasuku
Department of Applied Molecular Science, Institute for Molecular Science
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Ito Haruko
Department of Applied Molecular Science, Institute for Molecular Science, Okazaki National Research Institutes
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Ito Haruko
Department of Applied Molecular Science, Institute for Molecular Science
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