Figure shows the crystal structure of triclinic NbSe 2 I 2 , and Figure in Supporting Information shows the crystal structure of the monoclinic C2/m phase as a comparison. In Figure (a), it is obvious that NbSe 2 I 2 crystal has parallel ab-plane sheets bonded by van der Waals interactions. Figure (b) shows the ab-plane of triclinic NbSe 2 I 2 . Here it can be seen that loops form in the ab-plane which consists of 6 Nb 4+ ions in total. The iodine ions are all bonded to niobium, and the Nb-I distance ranges from 2.9644 Å to 2.9764 Å. This distance range confirms the Nb-I bonding, which is seen in some but not all Nb-Se-I compounds. Figure in Supporting Information shows the visualization of Nb-I distance comparison. All the selenium ions are dimerized, forming Se 2 2-dimers between niobium ions. Given the fact that all iodine and selenium ions have a 1-valence, we know from charge counting that all the niobium has a valence of 4+, leaving one unpaired 4d electron for each Nb . Looking closer at the ab-plane structure, it can be seen that the Nb-Nb distance through two Se Considering the complicated triclinic crystal structure with very low symmetry and the balanced charge without free electrons for further modulation, especially one-dimensional modulation, charge density wave (CDW) is not expected for triclinic P 1 NbSe 2 I 2 , unlike Nb-Se-I phases with intermediate Nb 4+/5+ valence, such as (TaSe 4 ) 2 I, (NbSe 4 ) 2 I, and (NbSe 4 ) 3.33 I. One interesting feature of the crystal structure is the ab-plane crystallographic angle γ = 61.3 • , which can be seen from the unit cell in Figure (b). This non-special number is, however, very close to 60 • , thus making the crystals look very much like a hexagonal one with 120 • angles, shown in the bottom right part of the SEM image in Figure (b). If NbSe 2 I 2 crystals can be exfoliated and if the exfoliated crystals can maintain environmental stability, then it may be an excellent candidate to for the construction of Moiré superlattice heterostructures with hexagonal van der Waals materials.