Jiang Yau-Chen, Wang Sue-Lein, Lee Shang-Fan, Lii Kwang-Hwa
Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan, R.O.C.
Inorg Chem. 2003 Oct 6;42(20):6154-6. doi: 10.1021/ic030019d.
Two new layered transition metal oxalatophosphates, (H(3)TREN)[M(2)(HPO(4))(C(2)O(4))(2.5)].3H(2)O (M = Mn(II) and Fe(II)), have been synthesized by hydrothermal methods in the presence of a structure-directing organic amine, tris(2-aminoethyl)amine, and characterized by single-crystal X-ray diffraction and magnetic susceptibility. They are the first metal oxalatophosphates which adopt a two-dimensional honeycomb structure with the organic cations and water molecules intercalated in between. Within a layer, there are 12-membered pores made from 6 Mn, 1 phosphate, and 5 oxalate units. Measurements of field dependence of magnetization and variable-temperature susceptibilities under different fields were performed on a polycrystalline sample of the manganese compound. The results indicate a phase transition from a paramagnetic to an antiferromagnetic coupled state at about 12 K. Crystal data for the manganese compound follow: triclinic, space group Ponemacr; (No. 2), a = 8.8385(6) A, b = 9.0586(6) A, c = 16.020(1) A, alpha = 77.616(1) degrees, beta = 83.359(1) degrees, gamma = 68.251(1) degrees, and Z = 2. Crystal data for the iron compound are the same as those for the manganese compound except a = 8.7776(9) A, b = 8.9257(9) A, c = 15.884(2) A, alpha = 78.630(2) degrees, beta = 84.018(2) degrees, and gamma = 67.372(2) degrees.
通过水热法在结构导向有机胺三(2-氨基乙基)胺存在下合成了两种新型层状过渡金属草酸磷酸酯,(H(3)TREN)[M(2)(HPO(4))(C(2)O(4))(2.5)].3H(2)O(M = Mn(II)和Fe(II)),并通过单晶X射线衍射和磁化率进行了表征。它们是首批采用二维蜂窝结构且有机阳离子和水分子插层其中的金属草酸磷酸酯。在一层内,由6个Mn、1个磷酸根和5个草酸根单元构成12元孔。对锰化合物的多晶样品进行了不同磁场下的磁化强度场依赖性测量和变温磁化率测量。结果表明在约12 K时从顺磁态到反铁磁耦合态发生相变。锰化合物的晶体数据如下:三斜晶系,空间群P1(No. 2),a = 8.8385(6) Å,b = 9.0586(6) Å,c = 16.020(1) Å,α = 77.616(1)°,β = 83.359(1)°,γ = 68.251(1)°,Z = 2。铁化合物的晶体数据与锰化合物相同,只是a = 8.7776(9) Å,b = 8.9257(9) Å,c = 15.884(2) Å,α = 78.630(2)°,β = 84.018(2)°,γ = 67.372(2)°。