The structural behaviour of tetrahedral framework compounds — a review Part II. Framework structures

Abstract

AbstractTetrahedral framework compounds, as defined in this paper, generally exist as tilted and distorted versions of ideal fully expanded structures at room temperature and atmospheric pressure. How pressure, temperature, and composition (P, T, andX) affect the tilting and distortion is critically reviewed. It is shown that although the effects ofP, T, andXon the cell parameters are broadly analogous, the underlying structural changes are generally different. An important, and frequently neglected thermal effect is the apparent shortening of the framework bonds by the anisotropic thermal motion of the framework oxygens. Tilting models of framework compounds are critically examined and their failure to match the observed structural behaviour is attributed to changes in tetrahedral distortion. For quartz it appears that during compression the change in tetrahedral distortion is virtually all angular (O-Si-O angles), whereas during thermal expansion the change in distortion is in the Si-O distances. Such behaviour may typify the behaviour of many other framework compounds but the structural data needed to establish this are lacking. The review is illustrated by reference to the quartz and cristobalite analogues; to the sodalite, leucite, nepheline, scapolite, and feldspar families; and to the nitrides and oxynitrides of silicon and germanium. It is concluded that our understanding of the structural behaviour of framework compounds is still superficial and that much theoretical and experimental work remains to be done.