Colourless single crystals of Ba[SnF6], a hitherto unknown representative of the K[OsF6] type as well Ba[TiF6] (Ba[SiF6] type) have been obtained. Ba[SnF6] ("Sealed copper tube"; 28 d; 750-degrees-C; BaF2/met. Sn/CuF2 with Ba:Sn:Cu = 1:1:2) crystalizes in SPCG. R3BAR with a = 742.79(9) pm and c = 741.8(2) pm, (Four-circle diffractometer, Siemens AED 2, MoK-alpha-BAR, R = 3.64% and R(w) = 3.79%, 344 of 2047 I(o)(hkl). Ba[TiF6] ("Sealed copper tube"; 35 d; 650-degrees-C; BaF2/met. Ti/CuF2 with Ba:Ti:Cu = 1:1:2) crystalizes in the space group R3BARm with a = 736.76(9) pm and c = 725.2(1) pm, (Four-circle diffractometer, Siemens AED 2, MoK-alpha-BAR, R = 2.33% and R(w) = 2.31%, 202 of 2004 I(o)(hkl). BaSnF6 which is characterized by single crystal data is the first representative of the K[OsF6] type. Its structure is compared with that of Ba[TiF6], a fellow of the Ba[SiF6] type. The Madelung Part of Lattice Energy, MAPLE, "Mean Fictive Ionic Radii, MEFIR", and "Effective Coordination Numbers, ECoN", as well as the Charge Distribution, "CHARDI", are calculated and discussed.