Crystal structure and magnetic properties of an octacyanometalate-based three-dimensional tungstate(V)-manganese(II) bimetallic assembly.
Crystal structure and magnetic properties of an octacyanometalate-based three-dimensional tungstate(V)-manganese(II) bimetallic assembly.
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DOI：
10.1021/ic0005994
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发表时间：
2000-10
影响因子：
4.6
通讯作者：
Z. Zhong;H. Seino;Y. Mizobe;M. Hidai;M. Verdaguer;S. Ohkoshi;K. Hashimoto
中科院分区：
文献类型：
--
作者：
Z. Zhong;H. Seino;Y. Mizobe;M. Hidai;M. Verdaguer;S. Ohkoshi;K. Hashimoto
标题化合物[MnII6(H2O)9[W(V)(CN)8]4 x 13H2O]n在含有八氰钨、Na3[W(CN)8]x3H2O和Mn(ClO4)2 x6H2O的水溶液中合成。该化合物属单斜晶系，空间群P2(1)/c，晶胞常数a=15.438(2)A，b=14.691(2)A，c=33.046(2)A，β=94.832(9)度，Z=4。晶体由W(V)-CN-MnII连接的三维网络[[MnII(H2O)]3[MnII(H2O)2]3[W(V)(CN)8]4]n和H2O分子组成。有两种类型的W位：一种是接近十二面体几何构型，有六个桥联和两个末端CN配体；另一种是接近双冠三棱柱结构，有七个桥联和一个末端CN配体。场冷磁化强度测量表明，该化合物的自发磁化强度低于T_c=54K。进一步的场变磁化测量表明，该化合物为亚铁磁体，其中所有的MnII离子与所有的W(V)离子是反平行的。
A single crystal of the title compound [MnII6(H2O)9[W(V)(CN)8]4 x 13H2O]n was synthesized in a hot aqueous solution containing octacyanotungstate, Na3[W(CN)8] x 3H2O, and Mn(ClO4)2 x 6H2O. The compound crystallized in the monoclinic system, space group P2(1)/c with cell constants a = 15.438(2) A, b = 14.691(2) A, c = 33.046(2) A, beta = 94.832(9) degrees, and Z = 4. The crystal consists of a W(V)-CN-MnII linked three-dimensional network [[MnII(H2O)]3[MnII(H2O)2]3[W(V)(CN)8]4]n and H2O molecules as crystal solvates. There are two kinds of W sites: one is close to a dodecahedron geometry with six bridging and two terminal CN ligands; the other is close to a bicapped trigonal prism with seven bridging and one terminal CN ligands. The field-cooled magnetization measurement showed that the compound exhibits a spontaneous magnetization below Tc = 54 K. Further magnetization measurements on the field dependence reveal it to be a ferrimagnet where all of the MnII ions are antiparallel to all the W(V) ions.