Interlocking inorganic screw helices: synthesis,structure, and magnetism of the novel framework uranium orthothiophoshates A11U7(PS4)13 (A = K,Rb)

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.