Structural features in Tutton's salts K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn

Bosi, Ferdinando; Belardi, Girolamo; Ballirano, Paolo

doi:10.2138/am.2009.2898

Cited by 46 publications

(27 citation statements)

References 20 publications

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“…Tutton's salts are double sulphates with the general formula A 2 M(RO 4 ) 2 Á6H 2 O, where A = NH 4 , K, Rb_, M = Co, Ni, Zn, Mg, Fe, Cu, Mn_ and R = S and Se. They crystallize in the monoclinic point group 2/m (Bosi et al, 2009) and are shaped by a predominating prism {110} and pinacoid {001}, and faces with subordinate {201}, {011} and {010} faces (Fig. 1a).…”

Section: Methodsmentioning

confidence: 99%

Effect of crystal composition and growth rate on sector zoning in solid solutions grown from aqueous solutions

2009

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Sector zoning in solid solutions of Tutton’s salts (NH4)2M(SO4)2.6H2O (M = Co, Ni, Zn, Mg) and nitrates of divalent metals Me(NO3)2 (Me = Sr, Pb, Ba) grown from low-T aqueous solutions under controlled conditions is studied. The effect of crystal composition and growth rate (supersaturation) on the intersector difference in concentrations of isomorphic components is examined experimentally and modelled theoretically based on the phenomenological approach to crystallization in a ‘solid solution—aqueous solution’ system. Calculations show a predominating contribution of the selective adsorption phenomena in the formation of a sector-zoned crystal with usually minor, but sometimes a major contribution of growth kinetics.

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Section: Methodsmentioning

confidence: 99%

Effect of crystal composition and growth rate on sector zoning in solid solutions grown from aqueous solutions

2009

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“…Tutton salts with the general formula A 2 [M(H 2 O) 6 ](XO 4 ) 2 , where A is an alkali metal or ammonium cation, M is a firstrow transition metal, and X is sulfur or selenium, continue to generate interest due to the opportunity to study systematic variations in an extensive series of isotypic structures (Cotton et al, 1993;Bosi et al, 2009). Of particular interest are the copper salts due to the interaction of the cooperative Jahn-Teller distortion (Falvello, 1997;Halcrow, 2013) with the lattice (Hitchman et al, 1999).…”

Section: Introductionmentioning

confidence: 99%

Neutron and X-ray investigations of the Jahn–Teller switch in partially deuterated ammonium copper Tutton salt, (NH₄)₂[Cu(H₂O)₆](SO₄)₂

Jørgensen

Piccoli

Hathwar

et al. 2017

Acta Crystallogr Sect B

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The structural phase transition accompanied by a Jahn-Teller switch has been studied over a range of H/D ratios in (NH 4 ) 2 [Cu(H 2 O) 6 ](SO 4 ) 2 (ACTS). In particular, single-crystal neutron diffraction investigations of crystals with deuteration in the range 50 to 82% are shown to be consistent with previous electron paramagnetic resonance (EPR) experiments exhibiting a phase boundary at 50% deuteration under ambient pressure. Polycrystalline samples show that the two phases can co-exist. In addition, single-crystal neutron and polycrystalline X-ray diffraction pressure experiments show a shift to lower pressure at 60% deuteration versus previous measurements at 100% deuteration.

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“…On the other hand, the Fe 2 (SO 4 ) 3 structure type does not seem to be flexible enough to allow the accommodation of Mg at the M site. Investigations of kieserite-, blödite-, and Tutton-type sulfates [25][26][27][28]…”

Section: Resultsmentioning

confidence: 99%

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

2019

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The novel compounds M 2+ Zr(SO 4) 3 with M = Mg, Mn, Co, Ni, Zn, and Cd as well as (Fe 3+,2+ ,Zr) 2 (SO 4) 3 were synthesized at mild hydrothermal conditions (Teflon-lined stainless steel vessels, 220 °C) from the mixtures of Zr 2 O 2 (CO 3)(OH) 2 , the respective M 2+ (SO 4)•nH 2 O hydrated salts, H 2 SO 4 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 Fe 2 (SO 4) 3 ; they are either isotypic in space group P2 1 /n (No. 14), Z = 4, i.e. M 2+ Zr(SO 4) 3 with M = Mn, Co, Ni, Zn, and Cd as well as the mixed valence sulfate (Fe 3+,2+ ,Zr) 2 (SO 4) 3 or in the case of MgZr(SO 4) 3 , closely related but with a larger unit cell, in space group Pc and Z = 8. The framework of the monoclinic Fe 2 (SO 4) 3 structure is characterized by two types of isolated Fe 3+ O 6 octahedra, corner-linked with three types of sulfate groups. In the isotypic M 2+ Zr(SO 4) 3 series, the Fe 3+ atom on the Fe(1) position is substituted by Zr 4+ while M 2+ 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 M 2+-O distances) are generally rather short, but still within the range reported in literature.

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Structural features in Tutton's salts K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn

Cited by 46 publications

References 20 publications

Effect of crystal composition and growth rate on sector zoning in solid solutions grown from aqueous solutions

Effect of crystal composition and growth rate on sector zoning in solid solutions grown from aqueous solutions

Neutron and X-ray investigations of the Jahn–Teller switch in partially deuterated ammonium copper Tutton salt, (NH₄)₂[Cu(H₂O)₆](SO₄)₂

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

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Structural features in Tutton's salts K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn

Cited by 46 publications

References 20 publications

Effect of crystal composition and growth rate on sector zoning in solid solutions grown from aqueous solutions

Effect of crystal composition and growth rate on sector zoning in solid solutions grown from aqueous solutions

Neutron and X-ray investigations of the Jahn–Teller switch in partially deuterated ammonium copper Tutton salt, (NH4)2[Cu(H2O)6](SO4)2

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

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Neutron and X-ray investigations of the Jahn–Teller switch in partially deuterated ammonium copper Tutton salt, (NH₄)₂[Cu(H₂O)₆](SO₄)₂