Koner Rajesh, Goldberg Israel
School of Chemistry, Sackler Faculty of Exact Sciences, Tel-Aviv University, Ramat-Aviv, 69978 Tel-Aviv, Israel.
Acta Crystallogr C. 2009 Apr;65(Pt 4):m160-4. doi: 10.1107/S0108270109008798. Epub 2009 Mar 21.
The title compounds, poly[[tetraaquadi-mu-2-hydroxypropanedioato-mu-oxalato-dilanthanum(III)] tetrahydrate], {[La(2)(C(2)O(4))(C(3)H(2)O(5))(2)(H(2)O)(4)].4H(2)O}(n), (I), and poly[[tetra-mu-acetato-tetraaqua-mu-oxalato-dilanthanum(III)] dihydrate], {[La(2)(C(2)O(4))(C(2)H(3)O(2))(4)(H(2)O)(4)].2H(2)O}(n), (II), represent crystalline hydrates of coordination polymers of diaqualanthanum(3+) ions with different combinations of bridging carboxylate ligands, viz. 2-hydroxypropanedioate and oxalate in a 2:2:1 ratio in (I), and acetate and oxalate in a 2:4:1 ratio in (II). While the acetate component was one of the reactants used, the other ligands were obtained in situ by aerial oxidation of the dihydroxyfumaric acid present in the reactions. The crystal structure of (I) consists of two-dimensional polymeric arrays with water molecules intercalated between and hydrogen bonded to the arrays. The oxalate components are located on inversion centres. The crystal structure of (II) reveals an open three-dimensional polymeric connectivity between the interacting components, with the solvent water molecules incorporated within the intralattice voids and hydrogen bonded to the polymeric framework. The La(III) ion and the noncoordinated water molecules are located on axes of twofold symmetry. The oxalate group is centred at the 222 symmetry site, the intersection of the three rotation axes. The coordination number of the La(III) ion in the two structures is 10. The significance of this study lies mainly in the characterization of two new coordination polymers, as well as in the confirmation that dihydroxyfumaric acid tends to rearrange to form smaller components in standard laboratory procedures, and should be considered a poor reagent for formulating hybrid coordination polymers with metal ions.
标题化合物,聚[[四水二-μ-2-羟基丙二酸根-μ-草酸根-二镧(III)]四水合物],{[La₂(C₂O₄)(C₃H₂O₅)₂(H₂O)₄]·4H₂O}ₙ,(I),以及聚[[四-μ-乙酸根-四水-μ-草酸根-二镧(III)]二水合物],{[La₂(C₂O₄)(C₂H₃O₂)₄(H₂O)₄]·2H₂O}ₙ,(II),分别代表二水合镧(3+)离子与不同组合的桥连羧酸根配体形成的配位聚合物的结晶水合物,即(I)中2-羟基丙二酸根和草酸根以2:2:1的比例,(II)中乙酸根和草酸根以2:4:1的比例。虽然乙酸根是所用反应物之一,但其他配体是通过反应中存在的二羟基富马酸的空气氧化原位生成的。(I)的晶体结构由二维聚合物阵列组成,水分子插层在阵列之间并与阵列形成氢键。草酸根组分位于对称中心。(II)的晶体结构显示相互作用组分之间存在开放的三维聚合物连接,溶剂水分子纳入晶格内空隙并与聚合物骨架形成氢键。La(III)离子和未配位的水分子位于二次对称轴上。草酸根基团位于222对称位点,即三个旋转轴的交点。两种结构中La(III)离子的配位数均为10。本研究的意义主要在于表征了两种新的配位聚合物,以及证实了在标准实验室程序中二羟基富马酸倾向于重排形成较小的组分,并且应被视为与金属离子形成杂化配位聚合物的不良试剂。