Metal Pyrazolato Complexes. Synthesis, Characterization, and X-ray Powder Diffraction Studies of Group 12 Coordination Polymers.
Metal Pyrazolato Complexes. Synthesis, Characterization, and X-ray Powder Diffraction Studies of Group 12 Coordination Polymers.
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金属吡唑配合物。
DOI：
10.1021/ic990258u
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发表时间：
1999
影响因子：
4.6
通讯作者：
A. Sironi
中科院分区：
文献类型：
--
作者：
N. Masciocchi;G. Ardizzoia;A. Maspero;G. Lamonica;A. Sironi
已经制备了许多聚合吡唑配合物，并通过光谱、热分析（DSC和TGA）和X射线粉末衍射（XRPD）方法表征。从头算XRPD研究表明，[Zn（pz）（2）]（n）（）和[Cd（pz）（2）]（n）（）物种（Hpz =吡唑）是含有四面体配位金属和M（&mgr;-pz）（2）M的一维聚合物（M = Zn，Cd）桥，很像[Cu（pz）（2）]（n）（）[正交晶系，Ibam，a = 7.4829（4），B = 14.3844（6），c = 7.3831（3）][Zn]和a = 7.8591（6），B = 13.652（1），c = 7.9165（4）<$（Cd）];不同的是，Hg（pz）（2）[三斜晶系，P&onemacr;，a = 7.4097（3），B = 9.4474（3），c = 5.8345（3）<$，α = 96.310（2），β = 96.752（3），γ = 73.694（2）度]最好描述为单核络合物，含有两个单齿吡唑基配体，通过与相邻分子的长（较长）Hg.N接触而松散地相互作用。在后者的合成过程中，得到了一个中间相Hg（pz）NO（3），它含有基于Hg（-pz）Hg桥的聚合阳离子[Hg（pz）]（n）（n）（）（+）和未配位的NO（3）（-）基团（斜方晶系，Pcmn，a = 17.2985（9），B = 5.2538（3），c = 7.3912（4））。所有结构最终通过Rietveld方法精制。
A number of polymeric pyrazolato complexes have been prepared and characterized by spectroscopy, thermal analyses (DSC and TGA), and X-ray powder diffraction (XRPD) methods. Ab initio XRPD studies showed that the (isomorphous) [Zn(pz)(2)](n)() and [Cd(pz)(2)](n)() species (Hpz = pyrazole) are 1-D polymers containing tetrahedrally coordinated metals and M(&mgr;-pz)(2)M (M = Zn, Cd) bridges, much alike [Cu(pz)(2)](n)() [orthorhombic, Ibam, a = 7.4829(4), b = 14.3844(6), c = 7.3831(3) Å (Zn) and a = 7.8591(6), b = 13.652(1), c = 7.9165(4) Å (Cd)]; differently, Hg(pz)(2) [triclinic, P&onemacr;, a = 7.4097(3), b = 9.4474(3), c = 5.8345(3) Å, alpha = 96.310(2), beta = 96.752(3), and gamma = 73.694(2) degrees ] is best described as a mononuclear complex, containing two monodentate pyrazolato ligands loosely interacting, through long(er) Hg.N contacts with neighboring molecules. During the synthesis of the latter, an intermediate phase was obtained, and characterized as Hg(pz)NO(3), which contains a polymeric polycation, [Hg(pz)](n)()(n)()(+), based on Hg(&mgr;-pz)Hg bridges, and uncoordinated NO(3)(-) groups (orthorhombic, Pcmn, a = 17.2985(9), b = 5.2538(3), c = 7.3912(4) Å). All structures were ultimately refined by the Rietveld method.