Two Novel Transition‐Metal Phosphite Compounds with 4‐, 6‐ and 12‐Membered Rings: Hydrothermal Syntheses, Crystal Structures and Magnetic Properties of Na2[M(HPO3)2] (M = Fe, Co)
Two Novel Transition‐Metal Phosphite Compounds with 4‐, 6‐ and 12‐Membered Rings: Hydrothermal Syntheses, Crystal Structures and Magnetic Properties of Na2[M(HPO3)2] (M = Fe, Co)
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DOI：
10.1002/ejic.200400644
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发表时间：
2005-03
影响因子：
2.3
通讯作者：
Wei Liu;Haohong Chen;Xinxin Yang;Jingtai Zhao
中科院分区：
文献类型：
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作者：
Wei Liu;Haohong Chen;Xinxin Yang;Jingtai Zhao
在温和的水热条件下合成了两种具有新结构类型的过渡金属亚磷酸盐Na 2 [M（HPO 3）2]（M = Fe，Co），并通过单晶X射线衍射研究了其固态结构。铁化合物1为正交晶系，Pnma，a = 12.169（4），B = 5.441（2），c = 9.146（3）A;钴化合物2为正交晶系，Z = 4，a = 12.091（3），B = 5.400（4），c = 9.115（2）A。这些化合物的晶体结构是同型的，并且从具有顶点连接的MO 6和HPO 3构建单元的4-、6-和12-元多面体环的3D开放框架构建。无机骨架含有钠离子所在的12元环通道系统。这种结构类型的拓扑结构是非常相似的易解石CaTa 2 O 6与更大的通道。Na_2 [Co（HPO_3）_2]在低温（5-30 K）和高温（100-320 K）范围内的磁性测量显示出不同的磁性特征，表明可能存在复杂的磁性结构。在θ = 2.6K时，反铁磁有序在χ-1中表现为一个加宽的尖点。对于Na_2 [Fe（HPO_3）_2]，在100-320 K范围内，其磁性符合居里-外斯定律，μeff = 5.41 μB。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2005）
Two transition-metal phosphites, Na2[M(HPO3)2] (M = Fe, Co) with a new structure type have been synthesised under mild hydrothermal conditions and the solid-state structures have been elucidated by single-crystal X-ray diffraction studies. The structures are of a new type with the following data: orthorhombic, Pnma, a = 12.169(4), b = 5.441(2) and c = 9.146(3) A for the iron species 1 and a = 12.091(3), b = 5.400(4) and c = 9.115(2) A for the cobalt compound 2, with Z = 4. The crystal structures of these compounds are isotypic and built up from a 3D open framework with 4-, 6- and 12-membered polyhedral rings of vertex-linked MO6 and HPO3 building units. The inorganic frameworks contains 12-membered ring channel systems in which the sodium ions are located. The topology of this structure type is remarkably similar to that of the aeschynite CaTa2O6 with much larger channels. Magnetic measurements of Na2[Co(HPO3)2] show different magnetic features in the low-temperature (5–30 K) and high-temperature ranges (100–320 K) suggesting the possible existence of a complex magnetic structure. Antiferromagnetic ordering can be observed as a broadened cusp in χ–1 at θ = 2.6 K. For Na2[Fe(HPO3)2], the magnetic behavior follows the Curie–Weiss law with μeff = 5.41 μB, fitted for 100–320 K. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)