KAgF3, K2AgF4 and K3Ag2F7: important steps towards a layered antiferromagnetic fluoroargentate(II),
Crystal structure and magnetic properties of K2AgF4, related to recently studied Cs2AgF4, have been scrutinized. It crystallizes orthorhombic (Cmca No.64) with a = 6.182(3) Å, b = 12.632(5) Å, c = 6.436(3) Å (Z = 4, V = 502.6(7) Å3). K2AgF4 exhibits slightly puckered [AgF2] sheets and a compressed octahedral coordination of Ag(II) and it is not isostructural to related Cs2AgF4. Violet–coloured K2AgF4 orders ferromagnetically below 26 K. The DFT calculations reproduce semiconducting properties and ferromagnetism of K2AgF4 at the LSDA + U level but only if substantial values of Mott–Hubbard on-site electron–electron repulsion energies for Ag and F are used in calculations. We have also succeeded to solve the crystal structure of a brown KAgF3 (1D antiferromagnet below 64 K; GdFeO3–type, PnmaNo. 62, a = 6.2689(2) Å, b = 8.3015(2) Å, c = 6.1844(2) Å, Z = 4, V = 321.84(2) Å3) and to prepare K3Ag2F7, a novel KAgF3/K2AgF4 intergrowth phase and a member of the Ruddlsden–Popper KnAgFn+2 series (n = 1.5). Dark brown K3Ag2F7 crystallizes orthorhombic (K3Cu2Cl7-type, CccaNo. 68, setting 2) with a = 20.8119(14) Å, b = 6.3402(4) Å, c = 6.2134(4) Å (Z = 4, V = 819.87(9) Å3).