Synthesis and crystal structures of silver thianthrene complexes with weakly coordinating anions

Two novel silver complexes with thianthrene (TA) as a ligand have been synthesized in the poorly coordinating solvent liquid sulfur dioxide, using silver salts with weakly coordinating anions [BF₄]^- and [SbF₆]^-. Both colorless compounds contain discrete molecular entities and SO₂ molecules included in the crystal structure. Selection of crystals and the diffraction data collection were performed at low temperatures (123 K). The tris(μ-thianthrene- κ²S)disilver(I) bis(hexafluoroantimonate) sulfur dioxide solvate [Ag₂(TA)₃][SbF₆]₂ · 5SO₂ (1) (monoclinic, P2₁/c, a = 21.644(3), b = 12.4216(4), c = 21.934(3) Å, β = 115.04(1)°, Z = 4) is made up of complexes bearing three TA units acting as bridging ligands with both S atoms towards two Ag⁺ ions with d(Ag⁺-Ag⁺) = 2.911 Å giving the [Ag₂(TA)₃J²⁺ unit approximately D_3h molecular symmetry. The bis(μ-thianthrene- κ²5)disilver(I) bis(tetrafluoroborate) sulfur dioxide solvate [Ag₂(TA)₂][BF₄]₂ -3SO₂ (2) (monoclinic, C2/c, a = 21.0045(6), b = 7.4553(2), c = 22.6024(6) Å, β= 109.65(0)°, Z = 4) is made up of [Ag₂(TA) ₂]²⁺ units with two bridging TA units coordinating two Ag⁺ ions with d(Ag⁺-Ag⁺) = 2.925 Å giving the complexes approximately D_2h molecular symmetry. Weak, secondary bonds between Ag⁺ and the F atoms of the anions, such as Ag⋯F-SbF₅ = 2.862(4) Å in 1 or Ag⋯F-BF ₃ = 2.773(2) Å in 2, and with O atoms of SO₂ molecules link the complexes with the anions and the solvate molecules, respectively.