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The solid\u2010state structure of [Ru(Cp*)(\u03b7<jats:sup>6<\/jats:sup>\u2010fluorobenzene)][PF<jats:sub>6<\/jats:sub>] (<jats:bold>1\u2009c<\/jats:bold>) is reported. The extent of the ion pairing and the relative positions of the ions are shown to depend on the arene. For the solvent dichloromethane, new and literature PGSE data for PF<jats:sub>6<\/jats:sub><jats:sup>\u2212<\/jats:sup> salts of transition\u2010metal, inorganic, and organic salts are compared. Taken together, these new results show that the charge distribution and the ability of the anion to approach the positively charged positions (steric effects due to molecular shape) are the determining factors in deciding the amount of ion pairing. DFT calculations of the charges in four salts of type <jats:bold>1<\/jats:bold>, as well as in a variety of other salts, using a natural population analysis (NPA), support this view. 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