A structural study of cyanotrichite from Dachang by conventional and automated electron diffraction

The crystal structure of cyanotrichite, having general formula Cu4Al2(SO4)(OH)(12)center dot 2H(2)O, from the Dachang deposit (China) was studied by means of conventional transmission electron microscopy, automated electron diffraction tomography (ADT) and synchrotron X-ray powder diffraction (XRPD). ADT revealed the presence of two different cyanotrichite-like phases. The same phases were also recognized in the XRPD pattern, allowing the perfect indexing of all peaks leading, after refinement to the following cell parameters: (1) a = 12.417(2) a"<<, b = 2.907(1) a"<<, c = 10.157(1) a"<< and beta = 98.12(1); (2) a = 12.660(2) a"<<, b = 2.897(1) a"<<, c = 10.162(1) a"<< and beta = 92.42(1)A degrees. Only for the former phase, labeled cyanotrichite-98, a partial structure, corresponding to the [Cu4Al2(OH) (12) (2+) ] cluster, was obtained ab initio by direct methods in space group C2/m on the basis of electron diffraction data. Geometric and charge-balance considerations allowed to reach the whole structure model for the cyanotrichite-98 phase. The sulfate group and water molecule result to be statistically disordered over two possible positions, but keeping the average structure consistent with the C-centering symmetry, in agreement with ADT results.