Polar and Non-Polar Polymorphs of (PhO, F)-Azine Are Reported. Both Polymorphs Feature Identical 2-D Perfectly Parallel-Aligned Beloamphiphile Monolayers (PBAMs). the Striking Contrast between the Polymorphs is the Stacking of the PBAMs in the Third Dimension. the Difference in Stacking Demonstrates the Subtle Role of Weak Non-Covalent Interlayer Interactions and Unit Cell Polarity in Affecting the Crystal Architecture.