title: The coordination number of silicon in silicon-oxygen compounds: the special case of 6-fold coordination in thaumasite.
abstract: In most silicon-oxygen compounds, the silicon atom is 4-fold coordinated. Exceptionally, silicon is found in 6-fold coordination, as in the mineral thaumasite, which also may be formed in the degradation, and sometimes subsequent weakening, of certain concretes. The connection between coordination number and chemical bonding in oxidic compounds generally is explored using the optical basicity concept to estimate the extent of negative charge provided by oxide(-II) donor atoms in the coordination sphere. A correlation is established between this charge and the heat of formation of silicate (per oxide(-II) atom), which indicates that reduction in charge decreases thermodynamic stability. Calculations for thaumasite show that 4-fold coordination would provide a very small charge, but that 6-fold provides a charge comparable with that for stable 4-fold coordinated silicates such as K2Si2O5.
authors.affiliation: Department of Chemistry, University of Aberdeen, Meston Walk, Aberdeen, AB24 3UE, United Kingdom. j.a.duffy@abdn.ac.uk
authors.forename: J A
authors.initials: JA
authors.lastname: Duffy
authors.forename: D E
authors.initials: DE
authors.lastname: Macphee