Comparative exploration of the nanometer-scale atomic structure of K
xFe
2−yCh2 (
Ch = S, Se) was performed using neutron total scattering-based atomic pair distribution function (PDF) analysis of 5 K powder diffraction data in relation to physical properties. Whereas
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Comparative exploration of the nanometer-scale atomic structure of K
xFe
2−yCh2 (
Ch = S, Se) was performed using neutron total scattering-based atomic pair distribution function (PDF) analysis of 5 K powder diffraction data in relation to physical properties. Whereas K
xFe
2−ySe
2 is a superconductor with a transition temperature of about 32 K, the isostructural sulphide analogue is not, which instead displays a spin glass semiconducting behavior at low temperatures. The PDF analysis explores phase separated and disordered structural models as candidate descriptors of the low temperature data. For both materials, the nanoscale structure is well described by the iron (Fe)-vacancy-disordered K
2Fe
5−yCh5 (
I4/
m) model containing excess Fe. An equally good description of the data is achieved by using a phase separated model comprised of
I4/
m vacancy-ordered and
I4/
mmm components. The
I4/
mmm component appears as a minority phase in the structure of both K
xFe
2−ySe
2 and K
xFe
2−yS
2, and with similar contribution, implying that the phase ratio is not a decisive factor influencing the lack of superconductivity in the latter. Comparison of structural parameters of the Fe-vacancy-disordered model indicates that the replacement of selenium (Se) by sulphur (S) results in an appreciable reduction in the Fe-
Ch interatomic distances and anion heights, while simultaneously increasing the irregularity of Fe
Ch4 tetrahedra, suggesting the more significant influence of these factors. Structural features are also compared to the non-intercalated FeSe and FeS parent phases, providing further information for the discussion about the influence of the lattice degrees of freedom on the observed properties in layered iron chalcogenides.
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