Shi Fa-Nian, Cunha-Silva Luís, Hardie Michaele J, Trindade Tito, Paz Filipe A Almeida, Rocha João
Department of Chemistry, University of Aveiro, CICECO, Aveiro, Portugal.
Inorg Chem. 2007 Aug 6;46(16):6502-15. doi: 10.1021/ic700507j. Epub 2007 Jul 10.
The hydrothermal synthesis and structural characterization of a number of complex compounds containing the divalent tris(oxalato-O,O')germanate anion, [Ge(C2O4)3]2-, or the neutral bis(oxalate-O,O')germanium fragment, [Ge(C2O4)2], with transition-metal (M) cationic complexes of 1,10'-phenanthroline (phen) is reported: [M(phen)3][Ge(C2O4)3].xH2O [where M2+ = Cu2+ (1a and 1b), Fe2+ (2a and 2b), Ni2+ (3), Co2+ (4); x = 0.2 for 2b], [MGe(phen)2(mu2-OH)2(C2O4)2] [where M2+ = Cd2+ (5) and Cu2+ (6)]. The isolation of two polymorphs with Cu2+ (1a and 1b) and other pseudo-polymorphs for Fe2+ (2a and 2b) was rationalized based on slightly different molar ratios for the starting materials. All compounds have been characterized using EDS, SEM, vibrational spectroscopy (FT-IR and FT-Raman), thermogravimetry, and CHN elemental composition and their structure determined on the basis of single-crystal X-ray diffraction studies. The crystal packing of the different chemical moieties for each series of compounds was discussed on the basis of the various intermolecular interactions present (strong C-H...pi and weak C-H...O hydrogen-bonding interactions, C-H...pi and pi-pi contacts).
报道了一系列含有二价三（草酸根 - O，O'）锗酸根阴离子[Ge（C₂O₄）₃]²⁻或中性双（草酸根 - O，O'）锗片段[Ge（C₂O₄）₂]与1,10'-菲咯啉（phen）的过渡金属（M）阳离子配合物的水热合成及结构表征：[M（phen）₃][Ge（C₂O₄）₃]·xH₂O [其中M²⁺ = Cu²⁺（1a和1b）、Fe²⁺（2a和2b）、Ni²⁺（3）、Co²⁺（4）；2b中x = 0.2]，[MGe（phen）₂（μ₂ - OH）₂（C₂O₄）₂] [其中M²⁺ = Cd²⁺（5）和Cu²⁺（6）]。基于起始原料的摩尔比略有不同，合理解释了含有Cu²⁺的两种多晶型物（1a和1b）以及Fe²⁺的其他假多晶型物（2a和2b）的分离情况。所有化合物均通过能谱分析（EDS）、扫描电子显微镜（SEM）、振动光谱（傅里叶变换红外光谱和傅里叶变换拉曼光谱）、热重分析以及CHN元素组成进行了表征，并基于单晶X射线衍射研究确定了它们的结构。根据存在的各种分子间相互作用（强C - H...π和弱C - H...O氢键相互作用、C - H...π和π - π接触）讨论了每个系列化合物中不同化学部分的晶体堆积情况。
