Mao Jiang-Gao, Wang Zhike, Clearfield Abraham
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77843-3255, USA.
Inorg Chem. 2002 May 6;41(9):2334-40. doi: 10.1021/ic011202e.
Reactions of N-methyliminobis(methylenephosphonic acid), CH(3)N(CH(2)PO(3)H(2))(2) (H(4)L), with divalent metal acetates under different conditions result in metal diphosphonates with different structures. Mn(H(3)L)(2).2H(2)O (complex 1) with a layer structure was prepared by a layering technique. It is triclinic, P1 macro with a = 9.224(3) A, b = 9.780(3) A, c = 10.554(3) A, alpha = 82.009(6) degrees, beta = 74.356(6) degrees, gamma = 89.853(6) degrees, Z = 2. The Mn(II) ion is octahedrally coordinated by six phosphonate oxygen atoms from four ligands, two of them in a bidentate and two in a unidentate fashion. Each MnO(6) octahedron is further linked to four neighboring MnO(6) octahedra through four bridging phosphonate groups, resulting in a two-dimensional metal phosphonate (002) layer. These layers are held together by strong hydrogen bonds between uncoordinated phosphonate oxygen atoms. The zinc complex Zn(3)(HL)(2) (complex 2) was synthesized by hydrothermal reactions (4 days, 438 K, autogenous pressure). It is monoclinic, P2(1)/n with a = 7.7788(9) A, b = 17.025(2) A, c = 13.041(2) A, beta = 94.597(2) degrees, Z = 4. The structure of complex 2 features a 3D network built from ZnO(4) tetrahedra linked together by bridging phosphonate groups. Each zinc cation is tetrahedrally coordinated by four phosphonate oxygen atoms from four ligands, each of which connects with six zinc atoms, resulting in voids of various sizes. Magnetic measurements for the manganese complex shows an antiferromagnetic interaction at low temperature. The effect of the extent of deprotonation of phosphonic acids on the type of complex formed is discussed.
N-甲基亚氨基双（亚甲基膦酸），即CH(3)N(CH(2)PO(3)H(2))(2)（H(4)L），在不同条件下与二价金属醋酸盐反应会生成具有不同结构的金属双膦酸盐。通过分层技术制备了具有层状结构的Mn(H(3)L)(2).2H(2)O（配合物1）。它属于三斜晶系，P1空间群，a = 9.224(3) Å，b = 9.780(3) Å，c = 10.554(3) Å，α = 82.009(6)°，β = 74.356(6)°，γ = 89.853(6)°，Z = 2。Mn(II)离子由来自四个配体的六个膦酸酯氧原子八面体配位，其中两个以双齿形式，两个以单齿形式。每个MnO(6)八面体通过四个桥连膦酸酯基团进一步与四个相邻的MnO(6)八面体相连，形成二维金属膦酸盐（002）层。这些层通过未配位膦酸酯氧原子之间的强氢键结合在一起。锌配合物Zn(3)(HL)(2)（配合物2）是通过水热反应（4天，438 K，自生压力）合成的。它属于单斜晶系，P2(1)/n空间群，a = 7.7788(9) Å，b = 17.025(2) Å，c = 13.041(2) Å，β = 94.597(2)°，Z = 4。配合物2的结构具有由通过桥连膦酸酯基团连接在一起的ZnO(4)四面体构成的三维网络。每个锌阳离子由来自四个配体的四个膦酸酯氧原子四面体配位，每个配体与六个锌原子相连，形成各种尺寸的空隙。对锰配合物的磁性测量表明在低温下存在反铁磁相互作用。讨论了膦酸去质子化程度对形成的配合物类型的影响。
