Contributions to the stereochemistry of zirconium oxysalts\u2014part III: syntheses and crystal structures of M2+Zr(SO4)3 with M\u2009=\u2009Mg, Mn, Co, Ni, Zn and Cd, and a note on (Fe3+,2+,Zr)2(SO4)3 and Fe2(SO4)3

Gerald Giester,Manfred Wildner,Dominik Talla

doi:10.1007/s00706-019-02496-2

Gerald Giester, Manfred Wildner + Show 1 more

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https://doi.org/10.1007/s00706-019-02496-2

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Abstract

The novel compounds M2+Zr(SO4)3 with M = Mg, Mn, Co, Ni, Zn, and Cd as well as (Fe3+,2+,Zr)2(SO4)3 were synthesized at mild hydrothermal conditions (Teflon-lined stainless steel vessels, 220 °C) from the mixtures of Zr2O2(CO3)(OH)2, the respective M2+(SO4)·nH2O hydrated salts, H2SO4 and a minor amount of water. Crystals up to several tenths of a mm in size were obtained within a few days and studied at 200 K by single-crystal X-ray diffraction techniques. All these compounds belong to the structure type of monoclinic Fe2(SO4)3; they are either isotypic in space group P21/n (No. 14), Z = 4, i.e. M2+Zr(SO4)3 with M = Mn, Co, Ni, Zn, and Cd as well as the mixed valence sulfate (Fe3+,2+,Zr)2(SO4)3 or in the case of MgZr(SO4)3, closely related but with a larger unit cell, in space group Pc and Z = 8. The framework of the monoclinic Fe2(SO4)3 structure is characterized by two types of isolated Fe3+O6 octahedra, corner-linked with three types of sulfate groups. In the isotypic M2+Zr(SO4)3 series, the Fe3+ atom on the Fe(1) position is substituted by Zr4+ while M2+ ions occupy the Fe(2) site in the ferric sulfate structure type. Mean cation-oxygen bond lengths (S[4]: 1.462–1.472 Å; Zr[6]: 2.053–2.060 Å as well as M2+–O distances) are generally rather short, but still within the range reported in literature.Graphic abstract

Highlights

We recently have initiated a study on the crystal chemistry of novel zirconium oxysalts synthesized under mild hydrothermal conditions
All compounds presented belong or are related to the structure type of monoclinic Fe2(SO4)3; they are either isotypic in space group P21/n (No 14), Z = 4, i.e. MZr with M = Mn, Co, Ni, Zn, and Cd as well as the mixed valence sulfate (Fe3+,2+,Zr)2(SO4)3, or, in the case of MgZr, closely related but with a larger unit cell and space group Pc, Z = 8
1 0/1 0 0), the unit cell of AlFe(MoO4)3 [a = 15.509 Å, b = 9.132 Å, c = 18.021 Å, β = 125.31°, V = 2082.9 Å3, Z = 8, space group P21/a] turns into [a = 15.564 Å, A series of novel M2+Zr(SO4)3 compounds with M = Mg, Mn, Co, Ni, Zn, and Cd as well as ( Fe3+,2+,Zr)2(SO4)3 were obtained at mild hydrothermal conditions by the reaction of Zr2O2(CO3)(OH)2 with M2+(SO4)·nH2O, H2SO4 and H2O

Summary

Introduction

We recently have initiated a study on the crystal chemistry of novel zirconium oxysalts synthesized under mild hydrothermal conditions. For the compound MgZr a larger monoclinic unit cell with Z = 8 was obtained.

Results

Conclusion