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Unexpectedly Complex Crystalline Phases in the MSO 3 F–Ag(SO 3 F) 2 Phase Diagram (M = Na, K, Rb, Cs)
Author(s) -
Michałowski T.,
Mazej Z.,
Budzianowski A.,
Jagličić Z.,
Leszczyński P. J.,
Grochala W.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402948
Subject(s) - monoclinic crystal system , chemistry , orthorhombic crystal system , triclinic crystal system , crystallography , isostructural , raman spectroscopy , octahedron , phase diagram , crystal structure , stereochemistry , phase (matter) , organic chemistry , physics , optics
The syntheses and characterizations of mixed‐cation fluorosulfates containing Ag II ions are reported and add to the moderately well‐known chemistry of Ag II compounds. The compounds synthesized mostly show different structures and compositions. The mixed sodium–silver fluorosulfate is isostructural with Ag 3 (SO 3 F) 4 (monoclinic P 2 1 / c , a = 5.2812 Å, b = 13.0473 Å, c = 19.3557 Å, and β = 100.970°) and has the composition (Ag 0.05 Na 0.95 )(Ag 0.65 Na 0.35 )Ag II (SO 3 F) 4 . The mixed potassium–silver fluorosulfate does not correspond to K I 2 Ag II (SO 3 F) 4 but rather to KAg I 2 Ag II (SO 3 F) 5 [orthorhombic P 222 1 , 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 RbAg I 2 Ag II (SO 3 F) 5 [orthorhombic P 222 1 , a = 6.4828(6) Å, b = 7.3551(7) Å, c = 18.0262(17) Å], and the other corresponds to RbAg II (SO 3 F) 3 [monoclinic P 2 1 / 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 CsAg II (SO 3 F) 3 salt [triclinic P $\bar {1}$ , 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 MAg I 2 Ag II (SO 3 F) 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(SO 3 F) 3 derivatives (M = Rb, Cs).