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两种新型双(2,9-二甲基-1,10-菲咯啉)铜(I)配合物:[Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN 和 [Cu(dmp)₂][N(CN)₂]

Two novel bis(2,9-dimethyl-1,10-phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2.0.5(bpmh).CH3CN and [Cu(dmp)2][N(CN)2].

作者信息

King Graham, Gembicky Milan, Coppens Philip

机构信息

University of Buffalo, 732 Natural Sciences Complex, Buffalo, NY 14260-3000, USA.

出版信息

Acta Crystallogr C. 2005 Jul;61(Pt 7):m329-32. doi: 10.1107/S0108270105010760. Epub 2005 Jun 11.

Abstract

Two new salts of the cation [CuI(dmp)2]+ (dmp is 2,9-dimethyl-1,10-phenanthroline, C14H12N2), namely bis[bis(2,9-dimethyl-1,10-phenanthroline-kappa2N,N')copper(I)] bis(hexafluorophosphate) hemi[bis(4-pyridylmethylidene)hydrazine] acetonitrile solvate, [Cu(C14H12N2)2]2(PF6)2.0.5C12H10N4.C2H3N or [Cu(dmp)2]2(PF6)2.0.5(bpmh).CH3CN [bpmh is bis(4-pyridylmethylidene)hydrazine, C12H10N4], (I), and bis(2,9-dimethyl-1,10-phenanthroline-2N,N')copper(I) dicyanamide, Cu(C14H12N2)2 or [Cu(dmp)2][N(CN)2], (II), are reported. The Cu-N bond lengths and the distortion from idealized tetrahedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is pi-pi stacked with a dmp ligand at a distance of 3.4 A, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide molecule is present as an uncoordinated counter-ion.

摘要

报道了阳离子[CuI(dmp)₂]⁺(dmp为2,9 - 二甲基 - 1,10 - 菲啰啉,C₁₄H₁₂N₂)的两种新盐,即双[双(2,9 - 二甲基 - 1,10 - 菲啰啉 - κ²N,N')铜(I)]双(六氟磷酸根)半[双(4 - 吡啶基亚甲基)肼]乙腈溶剂合物,[Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N或[Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh为双(4 - 吡啶基亚甲基)肼,C₁₂H₁₀N₄],(I),以及双(2,9 - 二甲基 - 1,10 - 菲啰啉 - 2N,N')铜(I)双氰胺盐,Cu(C₁₄H₁₂N₂)₂或[Cu(dmp)₂][N(CN)₂],(II)。讨论了Cu - N键长以及dmp配体偏离理想四面体几何构型的情况,并与相关化合物进行了比较。(I)中的bpmh分子与一个dmp配体以3.4 Å的距离进行π - π堆积,而不是与金属原子配位。该分子位于晶体的一个对称中心上。在(II)中,通常配位的双氰胺分子以未配位的抗衡离子形式存在。

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