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In this Article, we explore how the chemical pressure (CP) features of an intermetallic phase may provide opportunities to couple perturbations in electron count with the stabilization of the underlying geometrical structure. AuCu3‐type LnGa3 (Ln = lanthanide or group 3 metal) phases contain octahedral cavities of negative CP held open by overly compressed Ln–Ga interactions, leading to a series of transition metal‐stuffed derivatives. We present new additions to this family with the synthesis and crystal structures of Dy4T1−xGa12 with (T, x) = (Ag, 0.29) and (Ir, 0.15), adopting Y4PdGa12‐type superstructures of the AuCu3‐type. Density Functional Theory (DFT)‐CP calculations, when adjusted to avoid dipolar CP features, affirm that T atom incorporation provides a mechanism for the relief of packing tensions, while electronic density of states distributions illustrate that the T atoms serve largely as electron or hole donors to the band structure, as needed for them to attain d10 configurations. The maximum obtainable value for x may be limited by a mismatch between the Fermi energy and pseudogap, in line with the balance of factors envisioned by the frustrated and allowed structural transitions principle. Trends in resistivity measurements on T = Ir, Pd, and Ag compounds are interpretable in terms of the varying degrees of disorder arising from x< 1.0. 

Like many complex intermetallic phases, the crystal structures of REZn_5+xcompounds (RE = lanthanide or Group 3 element) based on the EuMg₅type have gradually unfolded. The original reports described a complex hexagonal structure with an unusual combination of tetrahedrally close-packed regions and open spaces, as well as observations of superstructure reflections. More recently, we reinvestigated the structure of YZn₅, reclassifying it as the EuMg_5+x-type compound YZn_5+x(x ≃ 0.2), in which disordered channels run alongcthrough the spaces formerly considered open. In addition, DFT-chemical pressure (DFT-CP) analysis of ordered models of YZn_5+xhighlighted paths for communication between neighboring channels setting the stage for superstructure formation. Herein, the experimental elucidation of this effect is presented with the synthesis and structure determination of a modulated form of YZn_5+x. By slow-cooling samples of YZn_5+xfrom the annealing temperature, crystals were obtained that exhibit satellite reflections with the modulation wavevectorq= {1\over 3}a*+ {1\over 3}b*+ 0.3041c*. Structure solution and refinement using a (3+1)D model in superspace groupP31c({1\over 3}\,\!{1\over 3}σ₃)00sreveals incommensurate order in the structure's channels. Here, two Zn sites associated with the channels are present, each with discontinuous atomic domains that are slanted in thex₃x₄plane. Their slanting corresponds to adjustments along thecaxis for the presence or absence of close neighbors along that axis, while the occupation patterns of neighboring channels are shifted by {1\over 3} of the modulation period. These features follow earlier predictions from CP analysis, highlighting how this approach can be used predictively in search of new phenomena.