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The concept that equates oxidation and pressure has been successfully utilized in explaining the structural changes observed in the M2S subnets of M2SO x ( x = 3, 4) compounds ( M = Na, K) when compared with the structures (room- and high-pressure phases) of their parent M2S `alloy' [Martínez-Cruz et al. (1994), J. Solid State Chem. 110, 397-398; Vegas (2000), Crystallogr. Rev. 7, 189-286; Vegas et al. (2002), Solid State Sci. 4, 1077-1081]. These structural changes suggest that if M2SO2 would exist, its cation array might well have an anti-CaF2 structure. On the other hand, in an analysis of the existing thermodynamic data for M2S, M2SO3 and M2SO4 we have identified, and report, a series of unique linear relationships between the known Δf Ho and Δf Go values of the alkali metal ( M) sulfide ( x = 0) and their oxyanion salts M2SO x ( x = 3 and 4), and the similarly between M2S2 disulfide ( x = 0) and disulfur oxyanion salts M2S2O x ( x = 3, 4, 5, 6 and 7) and the number of O atoms in their anions x. These linear relationships appear to be unique to sulfur compounds and their inherent simplicity permits us to interpolate thermochemical data (Δf Ho) for as yet unprepared compounds, M2SO ( x = 1) and M2SO2 ( x = 2). The excellent linearity indicates the reliability of the interpolated data. Making use of the volume-based thermodynamics, VBT [Jenkins et al. (1999), Inorg. Chem. 38, 3609-3620], the values of the absolute entropies were estimated and from them, the standard Δf So values, and then the Δf Go values of the salts. A tentative proposal is made for the synthesis of Na2SO2 which involves bubbling SO2 through a solution of sodium in liquid ammonia. For this attractive thermodynamic route, we estimate Δ Go to be approximately −500 kJ mol−1. However, examination of the stability of Na2SO2 raises doubts and Na2SeO2 emerges as a more attractive target material. Its synthesis is likely to be easier and it is stable to disproportionation into Na2S and Na2SeO4. Like Na2SO2, this compound is predicted to have an anti-CaF2 Na2Se subnet. [ABSTRACT FROM AUTHOR]

We introduce and discuss an interpretative model of the structure and bonding of inorganic crystals containing metallic elements. The central idea is the conception of the crystal structure of such an inorganic compound as a metallic matrix whose geometric and electronic structures govern the formation and localization of the anions in the lattice. This is the reason for labelling the model anions in metallic matrices (AMM). Taking the Al X3 crystal family ( X = F, Cl, OH) as a suitable test-bed class of compounds, we illustrate how this approach gives a direct interpretation of the crystalline structures and explains the variable coordination that Al exhibits in crystalline materials. An exhaustive analysis of the topology of the electron density allows us to provide a quantum-mechanical assessment of the main hypotheses of the AMM model and to uncover, using microscopic arguments, the behavior of anions as chemical pressure agents. [ABSTRACT FROM AUTHOR]