The crystal structures of 2,4,6-triisopropylbenzenesulfonamide and the 1:1 adduct of hexamethylenetetramine and 1,2,3-trihydroxybenzene have been solved from synchrotron and laboratory X-ray powder diffraction data respectively. The structures were solved by application of a direct space structure solution approach using the Monte Carlo method and confirmed by Rietveld refinement. In the sulfonamide. the molecules are linked by N-H . . .O hydrogen bonds into two-dimensional sheets built from alternating eight and twenty-membered rings. In the cocrystal the molecules are linked by O-H . . .N hydrogen bonds to form puckered molecular ribbons that are in rum linked into a continuous 3D framework by C-H . . . pi (arene) interactions.