N,N-dimethyl-N'-(2-methylbenzoyl)thiourea, C11H14N2SO (HL1), N,N-dibutyl-N'-(2-methylbenzoyl) thiourea, C17H26N2SO (HL2), and N,N-dihexyl-N'-(2-methylbenzoyl) thiourea, C21H34N2SO (HL3) were synthesized and characterized by elemental analysis, spectroscopic methods (FT-IR, NMR), and single crystal X-ray diffraction. Compound HL1 crystallizes in the monoclinic system, space group P2(1)/c, Z = 4. Compound HL3 also crystallizes in the monoclinic system, space group P2(1)/n, Z = 8 with 2 independent molecules in the asymmetric unit. Compound HL2 crystallizes in the orthorhombic system, space group Penn, Z = 8. In all compounds, molecules form dimers through the strong intermolecular N-H center dot center dot center dot S hydrogen bonds. Moreover, there are different types of intra-and inter-molecular interactions in the crystal structures, and so the molecules of the 3 compounds also pack differently.