Lii Kwang-Hwa, Wang Sue-Lein, Liao Fen-Ling
Department of Chemistry, National Central University, Chungli, Taiwan, ROC.
Inorg Chem. 2004 Apr 19;43(8):2499-502. doi: 10.1021/ic035438p.
Cs(2)Pd(3)(P(2)O(7))(2) (1) and Cs(2)Pd(3)(As(2)O(7))(2) (2) have been synthesized by molten flux reactions and characterized by single-crystal X-ray diffraction. The structure of 1 consists of discrete Pd(II)O(4) squares which are linked by P(2)O(7) groups via corner-sharing to generate a 3D framework containing 12-ring channels in which Cs(+) cations are located. Compound 2 adopts a 2D layer structure with the interlayer space filled with Cs(+) cations. Within a layer there are PdO(4) squares and As(2)O(7) groups fused together via corner-sharing. Adjacent layers are stacked such that strings of Pd atoms are formed. The PdO(4) squares show eclipsed and staggered stacks with alternate short and long Pd...Pd distances. The two compounds adopt considerably different structures although they have the same general formula: Cs(2)Pd(3)(X(2)O(7))(2). Compound 2 is the first palladium arsenate reported. Crystal data for 1: orthorhombic, space group Cmc2(1) (No. 36), a = 7.6061(4) A, b = 14.2820(7) A, c = 14.1840(7) A, and Z = 4. Crystal data for 2: tetragonal, space group P4/n (No. 85), a = 16.251(1) A, c = 5.9681(5) A, and Z = 4.
通过熔盐反应合成了Cs₂Pd₃(P₂O₇)₂ (1) 和Cs₂Pd₃(As₂O₇)₂ (2)，并通过单晶X射线衍射对其进行了表征。1的结构由离散的Pd(II)O₄正方形组成，这些正方形通过P₂O₇基团通过角共享连接在一起，形成一个包含12元环通道的三维框架，Cs⁺阳离子位于其中。化合物2采用二维层状结构，层间空间填充有Cs⁺阳离子。在一层内，有通过角共享融合在一起的PdO₄正方形和As₂O₇基团。相邻层堆叠在一起，形成Pd原子链。PdO₄正方形呈现出重叠和交错的堆叠，Pd…Pd距离交替出现短和长。尽管这两种化合物具有相同的通式：Cs₂Pd₃(X₂O₇)₂，但它们采用了截然不同的结构。化合物2是报道的首例钯砷酸盐。1的晶体数据：正交晶系，空间群Cmc2(1)（编号36），a = 7.6061(4) Å，b = 14.2820(7) Å，c = 14.1840(7) Å，Z = 4。2的晶体数据：四方晶系，空间群P4/n（编号85），a = 16.251(1) Å，c = 5.9681(5) Å，Z = 4。
