Salvador James R, Kanatzidis Mercouri G
Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA.
Inorg Chem. 2006 Sep 4;45(18):7091-9. doi: 10.1021/ic0605017.
The quaternary compounds RE4Ni2InGe4 (RE = Dy, Ho, Er, and Tm) were obtained as large single crystals in high yields from reactions run in liquid In. The title compounds crystallize in the monoclinic C2/m space group with the Mg(5)Si(6) structure type with lattice parameters a = 15.420(2) A, b = 4.2224(7) A, c = 7.0191(11) A, and beta = 108.589(2) degrees for Dy4Ni2InGe4, a = 15.373(4) A, b = 4.2101(9) A, c = 6.9935(15) A, and beta = 108.600(3) degrees for Ho4Ni2InGe4, a = 15.334(7) A, b = 4.1937(19) A, c = 6.975(3) A, and beta =108.472(7) degrees for Er4Ni2InGe4, and a = 15.253(2) A, b = 4.1747(6) A, c = 6.9460(9) A, and beta = 108.535(2) degrees for Tm4Ni2InGe4. RE4Ni2InGe4 formed in liquid In from a melt that was rich in the rare-earth component. These compounds are polar intermetallic phases with a cationic rare-earth substructure embedded in a transition metal and main group matrix. The rare-earth atoms form a highly condensed network, leading to interatomic distances that are similar to those found in the elemental lanthanides themselves. The Dy and Ho analogues display two maxima in the susceptibility, suggesting antiferromagnetic ordering behavior and an accompanying spin reorientation. The Er analogue shows only one maximum in the susceptibility, and no magnetic ordering was observed for the Tm compound down to 2 K.
通过在液态铟中进行反应，高产率地获得了四元化合物RE4Ni2InGe4（RE = 镝、钬、铒和铥）的大单晶。标题化合物以Mg(5)Si(6)结构类型结晶于单斜C2/m空间群，对于Dy4Ni2InGe4，晶格参数a = 15.420(2) Å，b = 4.2224(7) Å，c = 7.0191(11) Å，β = 108.589(2)°；对于Ho4Ni2InGe4，a = 15.373(4) Å，b = 4.2101(9) Å，c = 6.9935(15) Å，β = 108.600(3)°；对于Er4Ni2InGe4，a = 15.334(7) Å，b = 4.1937(19) Å，c = 6.975(3) Å，β = 108.472(7)°；对于Tm4Ni2InGe4，a = 15.253(2) Å，b = 4.1747(6) Å，c = 6.9460(9) Å，β = 108.535(2)°。RE4Ni2InGe4在富含稀土成分的熔体中于液态铟中形成。这些化合物是极性金属间相，具有嵌入过渡金属和主族基体中的阳离子稀土子结构。稀土原子形成高度凝聚的网络，导致原子间距离与元素镧系元素本身中的原子间距离相似。Dy和Ho类似物在磁化率中显示两个最大值，表明反铁磁有序行为以及伴随自旋重取向。Er类似物在磁化率中仅显示一个最大值，并且对于Tm化合物，直至2 K均未观察到磁有序。
