Unexpectedly Complex Crystalline Phases in the MSO3F–Ag(SO3F)2 Phase Diagram (M = Na, K, Rb, Cs)

Tomasz Michałowski, Zoran Mazej, Armand Budzianowski, Zvonko Jagličić, Piotr J. Leszczyński, and Wojciech Grochala

European Journal of Inorganic Chemistry
Volume 2015, Issue 2, Pages 324-332.

EurJIC (2015). 2015, 324-332 [10.1002/ejic.201402948]

This work is dedicated to Professor Michał Ksawery Cyrański on the occasion of his birthday.

Abstract

The syntheses and characterizations of mixed-cation fluorosulfates containing AgII ions are reported and add to the moderately well-known chemistry of AgII compounds. The compounds synthesized mostly show different structures and compositions. The mixed sodium–silver fluorosulfate is isostructural with Ag3(SO3F)4 (monoclinic P21/c, a = 5.2812 Å, b = 13.0473 Å, c = 19.3557 Å, and β = 100.970°) and has the composition (Ag0.05Na0.95)(Ag0.65Na0.35)AgII(SO3F)4. The mixed potassium–silver fluorosulfate does not correspond to KI2AgII(SO3F)4 but rather to KAgI2AgII(SO3F)5 [orthorhombic P2221, a = 6.4736(3) Å, b = 7.3915(4) Å, and c = 17.7736(10) Å]. Two rubidium–silver fluorosulfates form as a mixture, one corresponds to RbAgI2AgII(SO3F)5 [orthorhombic P2221, a = 6.4828(6) Å, b = 7.3551(7) Å, c = 18.0262(17) Å], and the other corresponds to RbAgII(SO3F)3 [monoclinic P21/m, a = 15.8152(14) Å, b = 15.4861(13) Å, c = 17.0211(14) Å, and β = 101.513(5)°]. The cesium fluorosulfate/silver(II) fluorosulfate phase diagram is exemplified by the CsAgII(SO3F)3 salt [triclinic Pequation image, a = 14.9241(5) Å, b = 9.7046(3) Å, c = 17.8465(7) Å, α = 109.116(2)°, β = 84.655(3)°, and γ = 119.171(3)°]. The IR and Raman spectra of the compounds were measured, and their thermal stability and magnetic properties have been determined. The MAgI2AgII(SO3F)5 systems show antiferromagnetic behavior with absolute superexchange constants of up to 19.1 meV for M = K, and ferromagnetism can be observed below 20–40 K for the MAg(SO3F)3 derivatives (M = Rb, Cs).

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