The crystal structure of a new bismuth tellurium oxychloride Bi0.87Te2O4.9Cl0.87 from neutron powder diffraction data

A new bismuth tellurium oxychloride was obtained by reaction of BiOCl and TeO2 in air. According to energy dispersive X-ray spectroscopy and neutron powder diffraction refinement the composition of the substance was determined as Bi0.87Te2O4.9Cl0.87. The new compound crystallizes in the trigonal system space group R (3) over bar (#148), Z = 6, a = 4.10793(4), c = 31.1273(4)angstrom, chi(2)=3.20, wR(P) = 0.0369. Bi0.87Te2O4.9Cl0.87 has a new type of layered structure constructed by Bi-Te-O layers separated by chloride ions. The Te atoms in Bi0.87Te2O4.9Cl0.87 show an unusual umbrella-like environment. A comparison with known related structures has been made. (C) 2007 Elsevier Inc. All rights reserved.</p

A reinvestigation of quaternary layered bismuth oxyhalides of the Sillén X1 type

A family of layered bismuth oxyhalides, (L0.5Bi1.5O2X)-Bi-I and (LBiO2X)-Bi-II has been reinvestigated. Formation of X1-type Sillen compounds has been established for L-I = Li, Na, L-II = Ca, Sr, Ba, and X = Cl, Br, I, but the details of their crystal structures are different. While all (L0.5Bi1.5O2X)-Bi-I, CaBiO2Br, and CaBiO2I adopt the disordered tetragonal Nd2O2Te structure, all compounds of L-II = Sr and Ba are orthorhombic and isostructural to PbSbO2Cl, due to L/Bi cation ordering. Crystal structures have been determined for CaBiO2I, SrBiO2Br, SrBiO2I, and BaBiO2I. We discuss the factors which determine the occurrence and type of cation ordering in the quaternary bismuth,and antimony X1-type oxyhalides. We also predict that more isostructural compounds can be prepared with antimony. (C) 2003 Elsevier Inc. All rights reserved.</p