We report the synthesis, characterization and structural studies of the higher homologues ofN(4-n-pentyloxybenzylidene)4-n-alkylaniline compounds, viz. 5O.12, 5O.14 and 5O.16 by thermal microscopy, differential scanning calorimetry and X-ray diffraction. The compounds exhibit N–SA–SB, N–SA–SBand N–SAphase sequence variants, respectively. The X-ray results reveal the existence of an interdigitated smectic A phase in 5O.16 and smectic B phase in 5O.14. Results are discussed in light of the available data on thenO.mseries