Based on rotational dynamics measurements carried out with isomorphic co-crystals formed by halogen-bonding (XB) between tritylacetylene halides (TrX) and diazabicyclo[2.2.2]octane (dabco), we were able to distinguish the sources of the enthalpic and entropic components in the rotational free energy barrier. We describe the formation of the 1:1 co-crystals (TrX center dot center dot center dot N(R)(3)N) obtained from 1 equiv of dabco and 1 equiv of either TrI or TrBr, respectively, to give 4a and 4b instead of the potential 2:1 complexes. The co-crystals were prepared by solvent evaporation and mechanochemical synthesis. No co-crystal with TrCl was obtained, reflecting the weaker nature of the TrCl center dot center dot center dot NR3 interaction. Single-crystal X-ray diffraction confirmed structures that resemble a spinning top on a tripod and revealed that the two XB co-crystals are isomorphous, with slightly different C-X center dot center dot center dot NR3 (X = I, Br) distances and packing interactions. Quadrupolar-echo H-2 NMR experiments with H-2-labeled samples showed that fast rotation of dabco in these co-crystals follows a six-fold potential energy surface with three lowest energy minima. Variable-temperature H-1 NMR spin lattice relaxation (VT H-1 T-1) data revealed rotational dynamics with indistinguishable pre-exponential factors and small but distinguishable activation energies. The activation energy of 4b (E-a = 0.71 kcal mol(-1)) is the lowest reported in the field of amphidynamic crystals. Using the Eyring equation, we established that their activation entropy for rotation is small but negative (Delta S double dagger = -3.0 cal mol(-1) K-1), while there is almost a 2-fold difference in activation enthalpies, with 4a having a higher barrier (Delta H double dagger = 0.95 kcal mol(-1)) than 4b (Delta H double dagger = 0.54 kcal mol(-1)). Analysis of the rotator cavity in the two co-crystals revealed subtle differences in steric interactions that account for their different activation energies.