Abstract Click to copy section linkSection link copied! Five novel heterometallic bismuth-bearing cluster salts within two structural families, monoclinic P21/c α-[M2Bi14Cl4][TrCl4]4 and triclinic P1̅ [M2Bi14Cl2][AlCl4]6 (M = Ru, Os; Tr = Al, Ga), have been discovered via Lewis acidic ionic liquid (LAIL)-assisted synthesis at 180 °C.