Various carboxylic acid substitution patterns on the 1,3,5-triphenylbenzene nucleus were explored, and their influence on the symmetry of the resulting two-dimensional (2D) crystal structures was assessed. The symmetry of 1,3,5-benzenetribenzoic acid (H3BTB) was reduced by modifying the substitution pattern of the arene and/or adding an additional carboxylic acid. Four analogues belonging to various point groups were studied. Comparison of the monolayers of the analogues to that of H3BTB shows that plane group symmetry and molecular symmetry are not correlated: H3BTB and its analogues exhibit the same plane group p2 at the heptanoic acid/graphite interface. The 2D crystal structure of the H3BTB analogues is more strongly controlled by the geometry of hydrogen-bonding interactions rather than molecular symmetry. Other significant observations in this study include porosity, uncommon hydrogen-bonding motifs, and an unusually high number of inquivalent molecules (Z' = 3) present in the 2D crystal of the lowest symmetry analogue. This research demonstrates that reduction of molecular symmetry based on geometric modification of noncovalent interactions allows for control over porosity of the 2D crystals (close-packed structures to nanoporous networks) without changing the core shape of the molecule.