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

Abstract

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, $$P\bar 1$$ , a = 11.234(2), b = 11.691(2), c = 8.869(2) A, α = 94.66(3), β = 113.12(3), γ = 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) A, Z = 4. [(SbF3)2Cl2·(H2L3)], 3, (L3 = 1,10-diaza-18-crown-6), triclinic, $$P\bar 1$$ , a = 8.284(2), b = 9.016(2), c = 9.134(2) A, α = 82.92(3), β = 65.24(3), γ = 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.