Piccoli P M, Abney K D, Schoonover J R, Dorhout P K
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Inorg Chem. 2000 Jul 10;39(14):2970-6. doi: 10.1021/ic990767w.
Single crystals of A2ThP3Se9 (A = K (I), Rb (II)) and Cs4Th2PsSe17 (III) form from the reaction of Th and P in a molten A2Se3/Se (A = K, Rb, Cs) flux at 750 degrees C for 100 h. Compound I crystallizes in the triclinic space group P1 (No. 2) with unit cell parameters a = 10.4582(5) A, b = 16.5384(8) A, c = 10.2245(5) A, alpha = 107.637(1); beta = 91.652(1); gamma = 90.343(1) degrees, and Z = 2. Compound II crystallizes in the triclinic space group P1 (No. 2) with the unit cell parameters a = 10.5369(5) A, b = 16.6914(8) A, c = 10.2864(5) A, alpha = 107.614(1) degrees, beta = 92.059(1) degrees, gamma = 90.409(1) degrees, and Z = 2. These structures consist of infinite chains of corner-sharing [Th2Se14] units linked by (P2Se6)4- anions in two directions to form a ribbonlike structure along the [100] direction. Compounds I and II are isostructural with the previously reported K2UP3Se9. Compound III crystallizes in the monoclinic space group P2(1)/c (No. 14) with unit cell parameters a = 10.238(1) A, b = 32.182(2) A, c = 10.749(1) A; beta = 95.832(1) degrees, and Z = 4. Cs4Th2P5Se17 consists of infinite chains of corner-sharing, polyhedral [Th2Se13] units that are also linked by (P2Se6)4- anions in the [100] and [010] directions to form a layered structure. The structure of III features an (Se2)2- anion that is bound eta 2 to Th(2) and eta 1 to Th(1). This anion influences the coordination sphere of the 9-coordinate Th(2) atom such that it is best described as bicapped trigonal prismatic where the eta 2-bound anion occupies one coordination site. The composition of III may be formulated as Cs4Th2(P2Se6)5/2(Se2) due to the presence of the (Se2)2- unit. Raman spectra for these compounds and their interpretation are reported.
A2ThP3Se9（A = K（I），Rb（II））和Cs4Th2P5Se17（III）的单晶是通过在750℃下，使Th和P在熔融的A2Se3/Se（A = K、Rb、Cs）助熔剂中反应100小时形成的。化合物I结晶于三斜空间群P1（编号2），晶胞参数为a = 10.4582(5) Å，b = 16.5384(8) Å，c = 10.2245(5) Å，α = 107.637(1)°；β = 91.652(1)°；γ = 90.343(1)°，Z = 2。化合物II结晶于三斜空间群P1（编号2），晶胞参数为a = 10.5369(5) Å，b = 16.6914(8) Å，c = 10.2864(5) Å，α = 107.614(1)°，β = 92.059(1)°，γ = 90.409(1)°，Z = 2。这些结构由通过（P2Se6）4-阴离子在两个方向连接的角共享[Th2Se14]单元的无限链组成，从而沿[100]方向形成带状结构。化合物I和II与先前报道的K2UP3Se9同构。化合物III结晶于单斜空间群P2(1)/c（编号14），晶胞参数为a = 10.238(1) Å，b = 32.182(2) Å，c = 10.749(1) Å；β = 95.832(1)°，Z = 4。Cs,4Th2P5Se17由角共享的多面体[Th2Se13]单元的无限链组成，这些单元也通过（P2Se6）4-阴离子在[100]和[010]方向连接，形成层状结构。III的结构具有一个（Se2）2-阴离子，它以η2方式与Th(2)键合，以η1方式与Th(1)键合。该阴离子影响九配位Th(2)原子的配位球，使得它最好被描述为双帽三棱柱，其中以η2方式键合的阴离子占据一个配位位点。由于存在（Se2）2-单元，III的组成可表示为Cs4Th2(P2Se6)5/2(Se2)。报道了这些化合物的拉曼光谱及其解释。
