Molecular arrangement in the chiral smectic phases of the glassforming (S)-4'-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]benzoate is investigated by X-ray diffraction. An increased correlation length of the positional short-range order in the supercooled state agrees with the previous assumption of the hexatic smectic phase. However, the registered X-ray diffraction patterns are not typical for the hexatic phases. Comparison of the smectic layer spacing and optical tilt angle indicates a strongly non-linear shape of molecules, which enables choice of the molecular models obtained by DFT calculations, used subsequently to interpret the infra-red spectra. The presumption of the hexatic smectic F