In solid state PCl₅ exists as ionic solid i.e., [X]⁺ [Y]^–, shapes of X⁺ and Y^– are respectively

In the solid state, PCl5 exists as an ionic solid, [PCl₄]⁺[PCl₆]⁻ in which the cation [PCl₄]⁺ is tetrahedral while the anion [PCl₆]⁻ is octahedral