Structural characterization of pentacoordinate silicon in a calcium silicate

Abstract

IN silicate minerals formed at pressures typical of the Earth's crust, the silicon is usually coordinated by four oxygen atoms. In contrast, silicates formed at higher pressures, typical of the Earth's transition zone and lower mantle, contain predominantly six-coordinated silicon. Silicon coordinated by five oxygen atoms is not normally found as a structural element in crystalline phases, but is nevertheless believed to play a central role in many dynamic processes that occur in silicates. For example, pentacoordinate silicon is probably a component of aluminosili-cate melts and glasses at mantle temperatures and pressures1,2, where it will dominate their transport properties3–6; it is also believe to act as an intermediate activated state during oxygen diffusion in silicate minerals7,8. Here we report the complete structure determination of an inorganic crystalline silicate—CaSi2O5—containing SiO5 groups. Our results confirm the previous attribution1,2,9 of peaks in the 29Si NMR spectrum of this material to the presence of pentacoordinate silicon, and the detailed geometry that we determine for the SiO5 group should provide a firm basis for characterizing and quantifying the role of pentacoordinate silicon in silicate melts and glasses.