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(a) Determine the radius of the smallest cation that can have (i) sixfold and (ii) eightfold coordination with the Cl\mathrm{Cl}^{-} ion (radius 181 pm). (b) Determine the radius of the smallest anion that can have (i) sixfold and (ii) eightfold coordination with the Rb+\mathrm{Rb}^{+} ion (radius 149 pm).

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E15C3\textbf{E15C3}

(a) The deviation of a structure from that expected on the basis of this rule is often taken to be an indication of a shift from ionic towards covalent bonding. A major source of unreliability, though, is the arbitrariness of ionic radii and their variation with coordination number.

The radius-ratio rule is derived by considering the geometrical problem of packing the maximum number of hard spheres of one radius around a hard sphere of a different radius.

Thus,

Radius-ratio, γ=rsmallerrlarger\gamma = \dfrac{r_{\text{smaller}}}{r_{\text{larger}}}

= rR\dfrac{r}{R}

where, rsmallerr_{\text{smaller}} is the radius of the smaller ions in the crystal and rlargerr_{\text{larger}} that of the larger ions.

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