Accompanied　by　solid-state　structural　phase　transitions,the　switchable　molecular　dynamics(MD)and　order-disorder　transformation　of(i-PrNHMe2)+cation　embedded　in　a　deformable{[Ni(NCS)6]4-}∞　supramolecular　framework　are　in-depth　investigated　by　variable-temperature　tests　of　single-crystal　X-ray　diffraction,dielectric　measurement,and　MD　simulation.Interestingly,it　is　found　that　the　confined　swinging　or　flipping　of　the(i-PrNHMe2)+cation　as　a　whole　is　assisted　by　a　synergistic　change　of　its　torsion　angle.This　research　provides　a　helpful　insight　into　the　solid-state　MD　of　moderate-sized　quasi-spherical　molecules/ions　that　feature　a　flexible　inner　core.