CaAl12Si4O27, a New High-Pressure Phase Containing Al6O19 Clusters

CaAl12Si4O27, a new high-pressure phase in the CaO-Al2O3-SiO2 system, was prepared at 1550°C and 14 GPa. It has trigonal symmetry, P-3, with a=7.223(1) and c=8.614(3) ?. Its structure was solved using crystal chemistry principles and refined using the Rietveld method applied to powder X-ray diffraction data, Rwp=6.1%, RB=2.7%. The structure is a new type based on a close-packed anion lattice with a mixed layer stacking sequence ABACA(hc)2 and with Ca atoms ordered in one-seventh of the anion sites in alternate c-stacked layers. The Si atoms are ordered in both octahedral and tetrahedral sites while the Al atoms are ordered in two independent octahedral sites. Octahedral edge-shared clusters, Al6O19, occur in the structure, interconnected within the close-packed layers by corner-linking to SiO4 tetrahedra. The clusters are also connected by corner-sharing to nine-member rings of edge-shared Al- and Si-centered octahedra in adjacent layers. The new phase has structural features in common with the barium titanium ferrite of similar composition, BaFe11Ti3O23, as well as with the mineral simpsonite, Al4Ta3O13(OH), and alkali metal niobates which contain Nb6O19 clusters.