The distances between bismuth and iodine are 3.4382(5) Å (I1A) and 3.5226(5) (I1B), i.e. significantly below the sum of the respective van der Waals radii (∑vdWBiI = 4.05 Å), and corresponding to RXB values of 0.849 and 0.870. Interestingly, the pnictogen-iodine distances are similar or even shorter than in adducts of Ph3As•C6I3F3 (3.4211(3) Å), Ph3Sb•C6I3F3 (3.5747(3) Å) or Me3Sb•C6F5I (3.4951(4) Å. With regards to the C-I bond lengths (C1A-I1A 2.171(3) Å and C1B-I1B 2.147(4) Å), a significant increase is observed when compared with free C6H3(CF3)2I (2.100(5) A), consistent with population of the σ*(C-I) orbital. In addition to the electron-withdrawing effect of the CF3 groups, we hoped that their placement in the ortho-positions would additionally provide the possibility for weak H … F contacts with the tert-butyl groups of the bismuthinidene to augment the halogen bonded assembly. However, the crystal structure shows that these moieties are, in the main, too far away from each other: only one such contact (F2B-H14A: 2.607(3) Å) is observed. Instead, intermolecular H … F contacts between the CF3 groups and the hydrogen atoms of the tert-butyl groups (F2A-H15B 2.587(2) Å) and the aryl ring of the bismuthinidene are observed (H3- We have examined the potential halogen bonds present in the bismuthinidene•2,6-bis(trifluoromethyl)iodobenzene adduct 3 using Density Functional Theory (DFT) calculations. Initially, we compared the geometry of the halogen-bonded (HaB) adduct in the solid state with its optimized counterparts (Figure , ESI). Specifically, two DFT geometry optimizations were undertaken: one for the isolated adduct in the gas phase and another employing Periodic Boundary Conditions (PBC) to account for packing effects. Notably, the gas phase geometry closely resembles both the experimental and PBC geometries, with the latter two being nearly identical regarding the relative orientation of the crystal conformers (Figure ). Importantly, the I•••Bi halogen bonds persist in the gas phase with analogous distances (3.456 and 3.459 Å). This observation underscores the structure-directing capability of the halogen bonds and refutes any notion that they could be manifested merely due to packing effects. The primary variance between the gas phase and the experimental/PBC configurations is evident in the I-Bi-I angle. In the gas phase, this angle is calculated to be 147.9°, compared to 161.6° for PBC and 160.6° for the X-ray study. This reduced angle in the gas phase arises as the isolated adduct attempts to maximize intramolecular interactions. Figure presents the non-covalent interaction plot (NCIplot) of the trinuclear assembly. The Reduced Density Gradient (RDG) isosurfaces provide a visual representation of interactions in real space. Dual disk-shaped RDG isosurfaces are observed between the Bi and I-atoms, corroborating the presence of halogen bonds. Additionally, the NCIplot highlights (in green) RDG iso-surfaces between the methyltrifluoromethyl groups and between the methyl-iodine atoms, signifying weak van der Waals (vdW) interactions (Figure ). When examining the formation energy of the trinuclear assembly against isolated monomers, values of -24.6 kcal/mol (experimental geometry) and -24.3 kcal/mol (DFT-optimized, isolated adduct) have been calculated. This finding further affirms the assertion that packing effects are not the primary force behind adduct formation. The Natural Bond Orbital (NBO) analysis has been used to probe the significance of orbital donor-acceptor interactions within the halogen bonds. This analysis reveals that the two bismuth LPs reside in the 6s and 6p atomic orbitals. The LP within the 6p orbital participates in electron donation from bismuth to the antibonding σ*(C-I) orbitals (Figure ). The LP(Bi)→σ*(C-I) charge transfer energies (21 and 16.5 kcal/mol), further underscore the idea of predominant system stabilization arising from the HaB formation. To evaluate the HaB energies independent of the influence of vdW interactions, we also modelled a mutated adduct, substituting tert-butyl groups with H-atoms. This effectively eliminates the CF3•••H3C and CH3•••I interactions. Figure depicts this model, integrating both the quantum theory of atoms-in-molecules (QTAIM) and NCIPlot analyses. These methods confirm the exclusive establishment of HaBs in the mutated adduct, each characterized by a Bond Critical Point (BCPs) and bond path linking the I and Bi-atoms. The electron density values at the BCPs are consistent with strong halogen bonds. The interaction energy diminishes to -19.4 kcal/mol, relative to a value of -24.6 kcal/mol for the "full" system. Such findings underscore the assertion that the formation energy is predominantly attributed to the I•••Bi interactions, aligning with the pronounced and negative MEP value observed at the Bi-atom, as visualized in The two-dimensional (2D) electron localization function (ELF) plot of the trimeric assembly is depicted in Figure , offering further insight into the role(s) of the σ-holes in the interactions. This figure provides a sectional view of the ELF 2D map, focusing on the plane demarcated by the Bi-atom and its two interacting iodine counterparts. Through this ELF visualization, it becomes evident that the σ-holes on the iodine atoms are oriented towards the LP of the bismuth atom. Indeed, the bond path connecting I to Bi passes through both the iodine σ-hole and bismuth LP. This specific electron localization in the I-Bi-I plane at the Bi-atom aligns well with the findings from the NBO analysis, particularly emphasizing the involvement of the LP located at the atomic 6p orbital.