SCHNEIDER, M and LUTZ, HD and COCKCROFT, JK (1993) POLYMORPHISM AND PSEUDOSYMMETRY OF LI2COCL4. Z KRISTALLOGR , 203 183 - 197.
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The crystal structures of Li2CoCl4 at room temperature and at 400-degrees-C were redetermined by X-ray measurements of a twinned trilling crystal and by neutron powder diffraction. The low-temperature polymorph Li2CoC14 oC14 crystallizes in an ordered NaCl defect structure of SnMn2S4 type (space group Cmmm, Z = 2, a = 724.1 (1), b = 1 027.8(1) and c = 358.69(3) pm, R(I) = 5.2%). Because of a pronounced pseudosymmetry this structure could only be solved by combination of several independent methods taking into account group theoretical aspects of the phase transitions involved. The high-temperature polymorph Li2CoC14 cF56 obtained above 310-degrees-C crystallizes in the Li2MnBr4 HTM I type (space group Fd3mBAR, Z = 8, a = 1 043.53(7) pm (400-degrees-C), R(I) = 5.1 %). Whether a fully disordered deficient NaCl structure (aristotype) is reached before melting has not been fully established. The mechanisms of the phase transitions are discussed in terms of symmetry reduction and ordering of the metal ions.
|Title:||POLYMORPHISM AND PSEUDOSYMMETRY OF LI2COCL4|
|Keywords:||LITHIUM TETRACHLOROCOBALTATE, TRILLING X-RAY STRUCTURE DETERMINATION, NEUTRON POWDER DIFFRACTION, PHASE TRANSITIONS, SPINEL STRUCTURE, DIFFRACTION, SPECTRA|
|UCL classification:||UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry|
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