This methodology is illustrated using a previously unreported co-crystal (FSPA) formed between furosemide (FS) and picolinamide (PA). H solid-state NMR and molecular dynamics simulations are used to probe the behavior of FSPA with acetone and ethanol as the solvent guest. The direct prediction of the NMR data from MD simulation, combined with a complementary principal componenttype analysis, allows the overall molecular behavior to be understood in terms of the local site symmetry. This methodology can be readily applied to other solid systems in which guest molecules are moving within cavities.