Atoms and molecules <0.9 nm in diameter can be incorporated in the cages formed by hydrogen-bonded water molecules making up the crystalline solid clathrate hydrates. For these materials crystallographic structures generally fall into 3 categories, which are 2 cubic forms and a hexagonal form. A unique clathrate hydrate structure, previously known only hypothetically, has been synthesized at high pressure and recovered at 77 K and ambient pressure in these experiments. These samples contain Xe as a guest atom and the details of this previously unobserved structure are described here, most notably the host-guest ratio is similar to the cubic Xe clathrate starting material. After pressure quench recovery to 1 atmosphere the structure shows considerable metastability with increasing temperature (T <160 K) before reverting back to the cubic form. This evidence of structural complexity in compositionally similar clathrate compounds indicates that the reaction path may be an important determinant of the structure, and impacts upon the structures that might be encountered in nature.