Liquid crystal n-(alkyloxybenzilidene)-n'-toluidines R-O-C6H4-CH = N-C6H4-CH3 (R = C9H20 1 and C10H21 2) have been investigated by single crystal X-ray structural analysis. The investigation of 2 has been performed at different temperatures (120, 295, 320, and 333 K). Both compounds undergo the crystal-smectic-nematic-isotropic phase transitions. Crystal packing of the compounds consists of alternating loosely packed aliphatic and closely packed aromatic areas that involve weak directional ... stacking interactions and weak O...H-C hydrogen bonds. A possible mechanism of the phase transitions in these compounds based on peculiarities of their crystal packings is discussed.