Long chain alkane (C31H64) and alcohol (C30H61OH) crystals relevant to the composition of IW layers in plant leaves have been prepared in two orientations for the examination of crystals along and across the chain axis by electron and atomic force microscopy. The orientation and possible unit cell assignments were evaluated using SAED. AFM height and adhesion mapping showed alternate packing of terminal alcohol groups in C30H61OH. Low-dose SED revealed a hierarchical tilted grain microstructure in C31H64, containing ordered lamellar domains as well as nematic phases and dynamical disorder along the chain axis. Grain microstructure was absent in C30H61OH crystals and no lamellar ordering was observed. These observations suggest significant staggered or disordered alignment of chain ends as described in nematic phase packing, possible in β-form C30H61OH, or ordered staircase packing typical of γ-form C30H61OH. Experimental evidence of grain microstructure, mis-aligned chain ends and nematic phases co-existing with lamellar ordering, and dynamical disorder suggest the unit cell descriptions serve as guideposts only for the 'endmember' structural motifs in what is otherwise a complex, nanoscale landscape comprising a distribution of structures at the nanoscale.