SYNTHESIS AND CHARACTERIZATIONS OF A POLYMORPHIC SODIUM COBALT PHOSPHATE WITH EDGE-SHARING CO2+ OCTAHEDRAL CHAINS

摘要

A new sodium cobalt phosphate with a three-dimensional framework structure has been prepared by the hydrothermal method and characterized by thermal analysis, susceptibility measurements, and single crystal X-ray diffraction. The oxide framework is built from octahedral and tetrahedral atoms (Co2+ and P5+) and consists of cross-linked infinite Co-O-Co chains that propagate along the crystallographic b-axis. The framework connectivity can be correlated to that of potassium titanyl phosphate (KTP) type structure. The structure of NaCoPO4 is also compared to other divalent metal phosphates and a summary of structures isotypic to NaCoPO4 is given. Magnetic susceptibility measurements show that the compound displays Curie-Weiss behavior down to a temperature of 13K at which an antiferromagnetic phase transition occurs. The thermal analysis shows that the octahedral polymorph is a product of a phase transformation of the trigonal bipyramidal polymorph at about 710 degrees C. The octahedral polymorph transforms into the tetrahedral polymorph at about 920 degrees C. Crystal data for NaCoPO4: M=176.89, space group Pnma (No. 62), a = 8.8957(12), b = 6.8007(9), c = 5.0341(7), V = 304.55(7)Angstrom(3), Z=4, D-c = 3.858 g cm(-3) pink thin plate, MoK alpha, lambda=0.71073 Angstrom, mu = 6.128 mm(-1), 2 theta(max) = 56.38 degrees, R(F)= 3.68% for 41 parameters and 328 reflections with I>2 sigma(I). (C) 1997 Academic Press. [References: 27]