Condensed cluster phases in reduced oxoniobates: synthesis and studies of Sr4−xNb17O26 (x=0.0(1), 0.3(1)) and Eu4−xNb17O26 (x=0.3(1))

Sr4−xNb17O26 (x=0.0, 0.3) and Eu4−xNb17O26 (x = 0.3) were synthesised from SrCO3/Eu2O3 and Nb2O5 in a vacuum furnace at temperatures up to 1600°C (1500°C for Eu) using acetylene soot or Nb as reducing agents. The synthetic studies show that these phases are only formed via an intermediate disordered ‘phase’ (or phasoid). Sr4−xNb17O26 and Eu4−xNb17O26 are isostructural with Ba4Nb17O26 and crystallise in space group P 4/m (83) with the unit cell parameters for x=0.3: a=12.023(l) A, c=4.1411(4) A and a=12.015(2) A c=4.1351l) A, Z = 1, respectively. The crystal structure can be described as an intergrowth between ANbO3 and NbO. Characteristic building blocks are quadruple chains of corner-sharing Nb6-octahedra. ?The structures of Sr4−xNb17O26 and Eu4−xNb17O26 were refined using X-ray powder diffraction and neutron diffraction data (only Sr4−xNb17O26). The Rietveld refiniments and microanalyses showed x in Eu4−xNb17O26 to be 0.3(l) while the Sr analogue both x= 0.0(1) and 0.3(1) were found. High resolution electron microscopy studies showed that the compounds frequently contained structural defects. The magnetic susceptibility of Eu4−xNb17O26 (x=0.3) shows a Curie-Weiss behaviour, with a magnetic moment in good agreement with the expected μeff=7.9 μB for Eu2+/ The Sr analogie is temperature-independent paramagnetic at room temperature, Sr4−xNb17O26 (x=0.3) and Eu4−xNb17O26 (x=0.3) are metallic, with a resistivity increasing with temperature.