Novel and elegant modes of SbF3 coordination in the complexes with azacrown ethers

Synthesis and single-crystal X-ray structures are recorded for three adducts of SbF₃ with different azacrown ethers. [SbF₃·H₂O·L₁], 1, (L₁ = 12,13-benz-1,10-di(azamethyl)-4,7-dioxacyclotetradecane-1,14-dione), triclinic, , a = 11.234(2), b = 11.691(2), c = 8.869(2) Å, = 94.66(3), = 113.12(3), = 67.82(3)°, Z = 2. [SbF₃Cl·H₂O·(HL₂)], 2, (L₂ = monoaza-18-crown-6), orthorhombic, P2₁2₁2₁, a = 8.763(2), b = 13.003(3), a = 16.836(3) Å, Z = 4. [(SbF₃)₂Cl₂·(H₂L₃)], 3, (L₃ = 1,10-diaza-18-crown-6), triclinic, , a = 8.284(2), b = 9.016(2), c = 9.134(2) Å, = 82.92(3), = 65.24(3), = 63.38(3)°, Z = 1. All three structures include SbF₃ neutral molecules in the pyramidal mode and the antimony second coordination sphere is completed up to six in different fashions. In 1 the dimeric (SbF₃)₂ adducts are made up due to the involvement of the symmetry-related fluorine atom in coordination. The distorted octahedron is then completed by water molecule and carbonyl oxygen of L₁. The neutral molecules are joined by coordination and hydrogen bonds in the infinite ribbons. 2 and 3 are both comprised of neutral and charged species also bounded via coordination and hydrogen bonds. L₂ and L₃ in the complexes adopt the form of single and double-charged cations, respectively. The inorganic backbone unites the neutral SbF₃ molecules and chloride anions in the alternative mode. The sixth coordination site in the antimony polyhedron is completed by the water molecule in 2 and the ethereal oxygen atom in 3. Alignment of the inorganic entities within the structures of 2 and 3 is strikingly similar. Hydrogen bonding patterns are discussed.