High-resolution F-19 magic angle spinning (MAS) NMR spectroscopy is used to study disorder and bonding in a crystalline solid. F-19 MAS NMR reveals four distinct F sites in a 50% fluorine-substituted deuterated hydrous magnesium silicate (clinohumite, 4Mg(2)SiO(4)center dot Mg(OD1-xFx)(2) with x = 0.5), indicating extensive structural disorder. The four F-19 peaks can be assigned using density functional theory (DFT) calculations of NMR parameters for a number of structural models with a range of possible local F environments generated by F-/OH-substitution. These assignments are supported by two-dimensional F-19 double-quantum MAS NMR experiments that correlate F sites based on either spatial proximity (via dipolar couplings) or through-bond connectivity (via scalar, or J, couplings). The observation of F-19-F-19 J couplings is unexpected as the fluorines coordinate Mg atoms and the Mg-F interaction is normally considered to be ionic in character (i.e., there is no formal F-Mg-F covalent bonding arrangement). However, DFT calculations predict significant F-19-F-19 J couplings, and these are in good agreement with the splittings observed in a F-19 J-resolved MAS NMR experiment. The existence of these J couplings is discussed in relation to both the nature of bonding in the solid state and the occurrence of so-called "through-space" F-19-F-19 J couplings in solution. Finally, we note that we have found similar structural disorder and spin spin interactions in both synthetic and naturally occurring clinohumite samples.