PREPARATION AND STRUCTURAL AND MAGNETIC-PROPERTIES OF AGF(-) (M=IR, RU, SB, BI) AND AG2+(BIF6-)(2)()MF(6)()

AgFMF(6) salts (M = Ir, Ru, Sb, Bi) have been prepared by the action o f elemental F-2 in AHF on AgMF(6), and for AgFBiF6, also by interactio n of Ag(BiF6)(2) with KBF4 or KPF6 in AHF. Three structure types have been identified. AgFlrF(6) {orthorhombic Pnma, a = 7.628(2) Angstrom, b = 7.067(2) Angstrom, c = 10.253(4) Angstrom, V = 552.7(3) Angstrom(3 ), and Z = 4, with R = 0.026 and R(w) = 0.030 for 531 observed reflect ions and 50 parameters refined by full-matrix least squares, Mo K alph a radiation at 298 K} is isostructural with AgFAsF6 and AgFAuF6, the o ne dimensional cation (Ag-F)(n)(n+), showing Ag(II) linearly coordinat ed to two F ligands with Ag-F = 1.977(9) and 2.014(9) Angstrom and Ag- F-Ag = 146.0(5)degrees. In AgFRuF6 {monoclinic P2(1)/n, a = 8.3432(13) Angstrom, b = 5.4933(8) Angstrom, c = 11.9286(22) Angstrom, beta = 10 8.36(1)degrees, V = 518.9(3) Angstrom(3), and Z = 4, with R = 0.027 an d R(w) = 0.028 for 1511 observed reflections and 83 parameters refined by full matrix least squares, Mo K alpha radiation at 298 K} the Ag(I I) is nearly square coordinated by four F; two cis F, each shared near ly equally with another Ag(II) {Ag-F = 2.007(3) and 2.018(2) Angstrom, Ag-F-Ag 155.9(2)degrees} give the cation a ribbonlike polymeric chara cter. The other two F ligands of the square array {Ag-F = 2.140(3) and 2.158(3) Angstrom} are each associated with a different RuF6-, each o f which is so linked to two Ag(II) moieties. AgFMF(6) (M = Sb, Bi) bel ong to a third structure type. The cation chains of the AgF(+)MF(6)(-) salts have approximate temperature independence of magnetic susceptib ility, akin to that of metallic systems. In contrast, Ag(BiF6)(2) {tri clinic P $($) over bar$$ 1, a = 5.218(2) Angstrom, b = 5.579(1) Angstr om, c = 8.934(2) Angstrom, alpha = 76.08(2)degrees, beta = 88.93(2)deg rees, gamma = 65.08(2)degrees, V = 228.0(1) Angstrom(3) and Z = 1, wit h R = 0.055 and R(w) = 0.067 for 1327 observed reflections and 41 para meters refined by full-matrix least squares, Mo K alpha radiation at 2 98 K}, which is isostructural with Ag(SbF6)(2), shows approximate obed ience to the Curie-Weiss law. AgRuF6BiF6 appears to be similar. In the structure of Ag(BiF6)(2), each Ag(II) is linked in nearly square arra y to four F ligands of four surrounding BiF6- ions {Ag-F = 2.096(9) An gstrom x 2 and 2.122(9) Angstrom x 2}, two other anions making contact normal to that plane, with Ag-F = 2.440(10) Angstrom.