Konar Sanjit, Zoń Jerzy, Prosvirin Andrey V, Dunbar Kim R, Clearfield Abraham
Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
Inorg Chem. 2007 Jun 25;46(13):5229-36. doi: 10.1021/ic070132u. Epub 2007 Jun 1.
A series of metal-organic hybrid compounds were synthesized using two new phosphonic acids, pyridyl-4-phosphonic acid and p-xylylenediphosphonic acid (H(2)O(3)PCH(2)C(6)H(4)CH(2)PO(3)H(2)). The phosphonic acid ligands have been synthesized from their corresponding bromides following two different types of reactions. The reaction of pyridyl-4-phosphonic acid with three different divalent metal salts results in the formation of molecular structures of different dimensionality. The reaction of Cu(II) with the phosphonic acid under hydrothermal conditions yields a three-dimensional (3D) open framework structure having the molecular formula [Cu(4)(NC(5)H(4)-PO(3))(4)(H(2)O)(10)] (1). The reactions with Mn(II) and Zn(II) salts with the same phosphonic acid resulted in a two-dimensional layered and a dinuclear compound with molecular formulas [Mn(3)(NC(5)H(4)-PO(3))(4)(H(2)O)(6)(ClO(4))(2)] (2) and [Zn(2)(NHC(5)H(4)-PO(3)H)(2)Cl(4)] (3), respectively. Compound 1 crystallizes in the triclinic crystal system having space group P with structural parameters a = 7.4564(15) Angstrom, b = 9.1845(19) Angstrom, c = 11.582(2) Angstrom, alpha = 100.842(3) degrees, beta = 104.303(3) degrees, gamma = 94.774(3) degrees, and Z = 1. Compound 2 crystallizes in the triclinic crystal system, space group P, with structural parameters a = 7.6871(14) Angstrom, b = 10.576(2) Angstrom, c = 14.470(3)Angstrom, alpha = 81.340(3) degrees, beta = 81.561(3) degrees, gamma = 68.757(3) degrees, and Z = 2, whereas compound 3 crystallizes in a monoclinic crystal system with space group P2(1)/n. The structural parameters are as follows: a = 8.4969 (5) Angstrom, b = 9.3911 (5) Angstrom, c = 12.3779 (6) Angstrom, beta = 90.860(17) degrees, and Z = 4. The pyridylphosphonate ligand shows different ligation behavior toward the three divalent metal ions. On the other hand, p-xylylenediphosphonic acid on reaction with Co(II) formed a 3D compound [Co(2)(O(3)PCH(2)C(6)H(4)CH(2)PO(3))(2)(H(2)O)(2)] (4) with a layered and pillared structure. Compound 4 crystallizes in an orthorhombic crystal system with space group Pnma. The structural parameters are a = 21.744(4) Angstrom, b = 5.6744(10) Angstrom, c = 4.7927(9) Angstrom, and Z = 4.
使用两种新型膦酸，即吡啶 - 4 - 膦酸和对苯二甲撑二膦酸（H₂O₃PCH₂C₆H₄CH₂PO₃H₂）合成了一系列金属 - 有机杂化化合物。膦酸配体是通过两种不同类型的反应从其相应的溴化物合成的。吡啶 - 4 - 膦酸与三种不同的二价金属盐反应会形成不同维度的分子结构。在水热条件下，铜（II）与膦酸反应生成分子式为[Cu₄(NC₅H₄ - PO₃)₄(H₂O)₁₀]（1）的三维（3D）开放框架结构。相同膦酸与锰（II）和锌（II）盐反应分别生成分子式为[Mn₃(NC₅H₄ - PO₃)₄(H₂O)₆(ClO₄)₂]（2）的二维层状化合物和[Zn₂(NHC₅H₄ - PO₃H)₂Cl₄]（3）的双核化合物。化合物1结晶于三斜晶系，空间群为P，结构参数为a = 7.4564(15) Å，b = 9.1845(19) Å，c = 11.582(2) Å，α = 100.842(3)°，β = 104.303(3)°，γ = 94.774(3)°，Z = 1。化合物2结晶于三斜晶系，空间群为P，结构参数为a = 7.6871(14) Å，b = 10.576(2) Å，c = 14.470(3) Å，α = 81.340(3)°，β = 81.561(3)°，γ = 68.757(3)°，Z = 2，而化合物3结晶于单斜晶系，空间群为P2(1)/n。结构参数如下：a = 8.4969 (5) Å，b = 9.3911 (5) Å，c = 12.3779 (6) Å，β = 90.860(17)°，Z = 4。吡啶膦酸酯配体对三种二价金属离子表现出不同的配位行为。另一方面，对苯二甲撑二膦酸与钴（II）反应形成具有层状和柱状结构的3D化合物[Co₂(O₃PCH₂C₆H₄CH₂PO₃)₂(H₂O)₂]（4）。化合物4结晶于正交晶系，空间群为Pnma。结构参数为a = 21.744(4) Å，b = 5.6744(10) Å，c = 4.7927(9) Å，Z = 4。
