Silver-europium double sulfate AgEu(SO) was obtained by solid-phase reaction between AgSO and Eu(SO). The crystal structure of AgEu(SO) was determined by Monte Carlo method with simulated annealing, and after that, it was refined by the Rietveld method from X-ray powder diffraction data. The compound crystallizes in the triclinic symmetry, space group P1̅ ( a = 0.632929(4), b = 0.690705(4), c = 0.705467(4) nm, α = 98.9614(4), β = 84.5501(4), γ = 88.8201(4)°, V = 0.303069(3) nm). Two types of sulfate tetrahedra were found in the structure, which significantly affects the spectroscopic properties in the IR-range. In the temperature range of 143-703 K, the average linear thermal expansion coefficients of cell parameters a, b, and c are very similar, (1.11-1.67) × 10 K in magnitude, and therefore, AgEu(SO) expands almost isotropically. Upon heating in argon flow, AgEu(SO) is stable up to 1053 K. The luminescence spectra in the region of ultranarrow D-F transition contain a single narrow and symmetric line at 579.5 nm that is evidence of good crystalline quality of AgEu(SO) and uniform local environment of Eu ions in the structure. Distribution of luminescence bands is determined by the environment of Eu ions in the structure. Influence of Ag ions on the electron density distribution at Eu sites is detected.
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