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The iron sulfate Na 3 Fe(SO 4 ) 3  studied here has been obtained as a high-temperature (HT) product (-400 °C) from the thermal decomposition of sideronatrite from Sierra Gorda (Chile) having composition Na 2 Fe(SO 4 ) 2 (OH)⋅3H 2 O. The structure determination was carried out using synchrotron X‑ray powder diffraction. Structural data refined by the Rietveld method, up to R p  = 11.95%, are: space group R3̅, lattice parameters a = b = 13.6231(1) Å and c = 9.0698(1) Å, V = 1457.76(2) Å 3 , and Z = 6. The structure of Na 3 Fe(SO 4 ) 3  can be described in terms of FeO 6  octahedra connected to sulfate tetrahedra by corner-sharing to form infinite chains [Fe(SO 4 ) 3 ] ∞ , running along c. These chains are joined together by Na atoms to build up a three-dimensional network of strong (Fe-O-S) and weak (Na-O) bonds. The topological relationships of Na 3 Fe(SO 4 ) 3  to the structure of some analog minerals are also discussed.

Crystal structure of Na 3 Fe(SO 4 ) 3 : A high-temperature product (∼400 °C) of sideronatrite [Na 2 Fe(SO 4 ) 2 OH⋅3H 2 O]