The crystal of ZZ-1S′ contained two crystallographically independent molecules (molecules A and B), as shown in Figures and, respectively. The selected structural parameters are listed in Table . The key difference between molecules A and B lies in the conformational arrangements of the two terminal thiophenes at opposite ends of the trithiophene backbone: a syn-conformation, in which the sulfur atoms of the adjacent thiophenes face each other, and an anti-conformation, in which they face away. Molecule A exhibited a fixed syn/anti conformation, whereas molecule B exhibited a conformational disorder between syn/syn (86% occupancy) and syn/anti (14% occupancy). Both molecules maintained near planarity with only slight deviations. In the syn conformation, the S1•••S2 distances were 3.0419(7) and 3.047(1) Å for molecules A and B, respectively, which are shorter than the sum of the van der Waals radii of sulfur atoms. This suggests the presence of chalcogen bonding interactions. These interactions are characteristically directional, with an ideal C-S•••S angle exceeding 170°. The 171° angle observed in our structures supports the presence of such interactions. For 1O, the initial crystallization yielded only needle-like crystal bundles of the EZ isomer (confirmed by NMR analysis), which were unsuitable for X-ray analyses. However, subsequent crystallization of the mother liquor after the removal of the needle crystals produced single crystals that were successfully characterized by X-ray diffraction. The crystal contained two crystallographically independent molecules, both of which were EE isomers with nearly identical structures (Figure ). The structure shows three nearly coplanar furan rings.