Gieck Christine, Tremel Wolfgang
Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universität Duesbergweg 10-14, 55099 Mainz, Germany.
Chemistry. 2002 Jul 2;8(13):2980-7. doi: 10.1002/1521-3765(20020703)8:13<2980::AID-CHEM2980>3.0.CO;2-D.
The novel quaternary uranium thiophosphate K11U7(PS4)13 has been synthesized by reacting uranium metal, K2S, S, and P2S5 at 700 degrees C in an evacuated silica tube. The crystal structure was determined by single crystal X-ray diffraction techniques. K11U7(PS4)13 crystallizes in the tetragonal space group I42d (a = 32.048(2) A, c = 17.321(1) A, Z = 8). The structure contains a tunnel framework composed of eight interlocking uranium U7(PS4)13 screw helices, with alkali metal cations residing inside the framework channels. The uranium atoms are coordinated in a bi- or tricapped trigonal prismatic fashion. The screw helices are built up from uranium atoms interconnected by PS4 tetrahedral units. Magnetic susceptibility measurements indicate modified Curie-Weiss-type behavior between 300 and 70 K, with an effective magnetic moment of 2.54 microB per U atom at room temperature and C = 3.78, theta = -14.54, chi 0 = 0.01. The isostructural compound Rb11U7(PS4)13 (a = 32.1641(11) A, c = 17.7244(9) A, Z = 8) was prepared by heating a mixture of the formal composition UPS5 in eutectic LiCl/RbCl melts at 700 degrees C.
新型磷酸硫代铀酸钾K11U7(PS4)13是通过在700摄氏度的真空石英管中使金属铀、K2S、S和P2S5反应合成的。其晶体结构通过单晶X射线衍射技术确定。K11U7(PS4)13属于四方晶系，空间群为I42d（a = 32.048(2) Å，c = 17.321(1) Å，Z = 8）。该结构包含一个由八个相互连接的铀U7(PS4)13螺旋组成的隧道框架，碱金属阳离子位于框架通道内。铀原子以双帽或三帽三角棱柱的方式配位。螺旋由通过PS4四面体单元相互连接的铀原子构成。磁化率测量表明，在300至70 K之间呈现修正的居里 - 外斯型行为，室温下每个U原子的有效磁矩为2.54 μB，C = 3.78，θ = -14.54，χ0 = 0.01。通过在700摄氏度的LiCl/RbCl共熔物中加热化学计量比的UPS5混合物制备了同构化合物Rb11U7(PS4)13（a = 32.1641(11) Å，c = 17.7244(9) Å，Z = 8）。
