Abstract
A new bismuth oxide sulfate of stoichiometry Bi14O20(SO4) has been synthesized from thermal treatment of an intimate mixture of α-Bi2O3 and (NH4)2SO4 in the mole ratio 1:0.14, and its structure determined using a combination of electron diffraction, X-ray powder diffraction, and neutron powder diffraction. The body-centered tetragonal unit cell (I4/m; a = 8.664(1) Å, c = 17.282(2) Å) is a commensurate superstructure of the cubic fluorite subcell of δ-Bi2O3 (a0): a = ( /2)a0, c = 3a0. The structure contains discrete sulfate anions at the unit cell corners and body center, and a Bi−O framework of linked BiO4e (e = lone pair of electrons) square pyramids and trigonal bipyramids. The square pyramids are aggregated into clusters of composition Bi6O8, comprising O2- ions arranged in the form of a cube, the faces of which are capped by Bi3+ ions. In contrast, the trigonal bipyramids are corner linked to form layers perpendicular to [001]. The structure is thought to represent just one of several related phases in this system.
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