The aqua complexes [M(η⁵-C₅Me₅)(PMe₃)(R_F)(H₂O)]⁺[X]⁻, {M = Rh, Ir; R_F = CF(CF₃)₂; X = BF₄; M = Ir; R_F = CF₂CF₃, CF₂CF₂CF₃; X = CF₃SO₃; M = Rh; R_F = CF₂CF₂CF₃; X = CF₃SO₃} have been prepared and their molecular structures determined by single crystal X-ray diffraction studies. In addition, the aqua complexes [M(η⁵-C₅Me₅)(PR₃)(R_F)(H₂O)]⁺[X]⁻·0.5H₂O {M = Ir; R = CH₃; R_F = CF(CF₃)₂; X = B(Ar_F)₄; M = Ir; R = C₆H₅; R_F = CF₂CF₂CF₃; X = BF₄} containing both inner and outer sphere water molecules have been prepared and crystallographically characterized. The complexes exhibit hydrogen bonding networks in the solid state involving the aqua ligand and the BF₄⁻ or CF₃SO₃⁻ anions, and in one case, to the BF₄⁻ anion and an outer sphere water molecule. In the presence of a non-coordinating anion, such as B(Ar_F)₄, hydrogen bonding to an outer sphere water molecule is still observed. A number of close contacts between the coordinated water molecule and α- and/or β-fluorines of the fluoroalkyl ligands are observed and discussed.