The crystal and molecular structure of 4-n-hexylphenyl-4′-n-butyloxythiolbenzoate (4S6) has been determined using single crystal X-ray diffraction data. The crystals belong to the monoclinic system with space group P21/c,a= 15.726 (7) ǎ,b =8.317 (4) ǎ,c= 17.709 (9) ǎ, β = 108.25 (2)°, Z = 4. The structure of4S6 has been solved by direct methods and refined to R-value of 0.0973(Rw=0.0725). The molecules are arranged parallel to each other and lie perpendicular to [010] alternating withy ∼ 1/4andy ∼ 3/4in a head-to-tail configuration. Two types of layers are discussed in the crystalline state. No dipole-dipole contacts are found.