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Cs2.91Na1.34Fe3+0.25[Fe3O(SO4)6(H2O)3]·5H2O, a member of the Maus's salt family

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The title compound, tricaesium sodium iron(III) μ3‐oxido‐hexa‐μ2‐sulfato‐tris[aquairon(III)] pentahydrate, Cs2.91Na1.34Fe3+ 0.25[Fe3O(SO4)6(H2O)3]·5H2O, belongs to the family of Maus's salts, K5[Fe3O(SO4)6(H2O)3]·6H2O, which is based on the triaqua‐μ3‐oxido‐hexa‐μ‐sulfato‐triferrate(III) anion, [Fe3O(SO4)6(H2O)3]5−, with Fe in a characteristically distorted octahedral coordination environment, sharing a common corner via an oxide O atom. Cs in four different cation sites, Na in three different cation sites and five water molecules link the anions in three dimensions and set up a crystal structure in which those parts parallel to (001) and within 0.05 < z < 0.95 have a distinct trigonal pseudosymmetry, whereas the cation arrangement and bonding near z∼ 0 generate a clear‐cut noncentrosymmetric polar edifice with the monoclinic space group C2. The structure shows some cation disorder in the region near z ∼ , where one Na atom in octahedral coordination is partly substituted by Fe3+, and a Cs atom is substituted by small amounts of Na on a separate nearby site. One Na atom, located on a twofold axis at z = 0 and tetrahedrally coordinated by four sulfate O atoms of two [Fe3O(SO4)6(H2O)3]5− units, plays a key role in generating the noncentrosymmetric structure. Three of the seven different cation sites are on twofold axes (one Na+ site and two Cs+ sites), and all other atoms of the structure are in general positions.
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Document Type: Research Article

Affiliations: Institute of Chemical Technology and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria

Publication date: October 15, 2013

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