The packing behavior in the neat films were investigated by two-dimensional grazing incidence wide-angle X-ray scattering (2D-GIWAXS). As shown in Figures 1c and 1d, the neat film ofTz-H exhibited a bi-modal packing as supported by the (010) π–π stacking peaks (d ₀₁₀ = 3.61 Å) along both the out-of-plane (OOP) and the in-plane (IP) directions. In contrast, a dominant (010) π–π stacking peak in the OOP direction (q _z = 1.75 Å⁻¹,d ₀₁₀ = 3.58 Å) was observed in the Tz-Clthin film, indicating a predominantly face-on orientation. Besides, the crystal coherence lengths (CCLs) for (010) diffraction peaks along the OOP direction were 1.65 and 1.82 nm for Tz-H andTz-Cl , respectively, as determined by the Scherrer equation. The reduced π–π stacking distance and enhanced CCLs in the neat film ofTz-Cl indicated a more compact and ordered packing, which may be attributed to the improved backbone coplanarity by the simultaneous incorporation of S···N and S···Cl NoCLs.