The simple system of tetraammonium octafluorouranate is employed to derive a fundamental understanding of the uranium-fluorine interaction. The structure is composed of isolated molecules, enabling a detailed examination of the U4+ (f(2)) ion. Characterization of single-crystals by X-ray diffraction, absorption spectroscopy, and magnetic analysis up to 45 T is combined with extensive theoretical treatment by CASSCF. The influence of different active spaces and representations of the structure is examined in the context of the experimental evidence. The Interacting Quantum Atoms method (IQA) is used to examine the nature of the U-F bond, concluding that there is a non-negligible degree of covalent character (9% of the total bond energy) in [UF8](4-). For the structural and theoretical reasons discussed herein, it is proposed that the structure of (NH4)(4)UF8 may be appropriately employed as a benchmark compound for future theoretical characterization of U(IV).