The CTH(-A) structure adopted herein, never observed as a pure ordered material in the experiments, is an ordered member of the disordered framework structure family denoted as * CTH, or also known as an intergrowth family CIT-13, which are a set of polymorphs that differ in the connectivity pattern between CFI layers and a row of D4R units. The Ge-rich (Si/Ge ≈ 4) samples of the intergrowth * CTH were reported to undergo the ADORtype transformation, leading to the formation of daughter zeolites with CFI layers connected by S4R or direct O-linkages . However, a significantly increased efficacy of the alkaline-based delamination was noted in some of these studies, hinting at the presence of the Si-O-Si connections between the CFI layers within the D4R units. This partially counters the previous PXRDbased structure refinement for mildly higher Si/Ge = 5.6 that places the most Ge atoms (≈ 80 %) into D4R units, i.e., about four Ge atoms per D4R unit at this Si/Ge ratio. These seemingly contrasting observations may be interpreted as a consequence of the heterogeneity in D4R occupations, which we also observe in our simulations (Figure ). However, our computational predictions (Figure ) seem to moderately underestimate the germanium population of the D4R units around this Si/Ge ratio (≈ 50 %) at the expense of increased population of the T sites inside the CFI layers, which may be related the effect of fluoride/OSDA.