A family of isostructural, chiral supramolecular networks have been obtained in the solid state by exploiting second sphere coordination interactions in the self-assembly of achiral tris amines L₁ and L₂ with tetrahalometallate and halide ions. Quantum-Mechanical (QM) calculations specific for solid phases provided additional insights into the intramolecular and packing interactions which determine chirality, pointing to a direct effect of the methyl groups of the central benzene ring.