“…The [XeF 5 ] + cations of compounds 1 and 3 – 6 interact with their respective anions through Xe‐ ‐ ‐F secondary bonding interactions (Tables S2–S6, Supporting Information) that are significantly less than the sum of the Xe and F van der Waals radii (3.61 Å, 3.52 Å) . Each [XeF 5 ] + cation of structure 4 also interacts with the fluorine atom of a HF molecule through a Xe‐ ‐ ‐F (H) contact (2.7985(9) Å) that is significantly less than those of [XeF 5 ] 2 [H 2 F] ⋅ HF (Xe‐ ‐ ‐F (H) , 3.006(5)–3.096(6) Å) . With the exception of [Xe 2 F 11 ][AuF 6 ], which has a Xe coordination number of 7, the common coordination numbers of Xe in [XeF 5 ] + and [Xe 2 F 11 ] + salts are CN=8: e.g., [XeF 5 ] 2 [PdF 6 ], [XeF 5 ][AsF 6 ], [XeF 5 ] 2 [NiF 6 ], and [XeF 5 ][OsO 3 F 3 ], and CN=9: e.g., [XeF 5 ][SbF 6 ] ⋅ XeOF 4 , [XeF 5 ][PtF 6 ], [XeF 5 ][AgF 4 ], [XeF 5 ][μ‐F(OsO 3 F 2 ) 2 ], [Xe 2 F 11 ][OsO 3 F 3 ], and [Xe 2 F 11 ] 2 [NiF 6 ] …”