Sodium Thioether Macrocyclic Chemistry: Remarkable Homoleptic Octathia Coordination to Na+

Unprecedented homoleptic octathioether macrocyclic coordination to Na+ in [Na([24]­aneS8)]+ has been achieved by using Na­[B­{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) Å. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.