magnified image Six pyrazolo[1,5‐a]pyrimidines bearing a 7‐trifluoromethyl (three compounds), a 7‐trichloromethyl (two compounds), and a 7‐ethoxycarbonyl (one compound) have been structurally characterized. The new X‐ray structures of 2‐methyl‐5‐(p‐bromophenyl)‐7‐trifluoromethylpyrazolo[1,5‐a]pyrimidine (3) and 2‐methyl‐7‐trichloromethylpyrazolo[1,5‐a]pyrimidine (4) are reported. The combined use of GIAO/B3LYP/6‐311++G(d,p) calculations with NMR spectroscopy in solution and in the solid state allows to establish some general rules that can be useful for characterizing related compounds. Compounds 3 and 4 present in the solid‐state interesting intra‐ and intermolecular halogen bonds. J. Heterocyclic Chem., (2010).