Abstract
In weakly bound materials such as water, one of the three primitive Frank-Kasper (FK) phases, the Z phase, is long absent due to the relatively unstable framework. The Z phase in clathrate hydrate, which is known as the HS-I structure, has now been discovered by precise tuning of the molecular guest structure. In the crystal structure, the never stabilized combination water cage of two 15-hedra and two 14-hedra formed with its original symmetries, providing sufficient gas capacity to the 12-hedral cages. With the discovery of the final FK clathrate hydrate, guest design now enables engineering of weak interactions in any mix of the three, illuminating how to leverage properties of clathrates in the broadest sense.