The thioantimonate anion SbS33− acting as ligand: Syntheses, crystal structures and selected properties of [Mn(1,2-chxn)2SbS3H] and [Cr(1,3-dap)2SbS3]

Two new isolated thioantimonates [Mn(1,2-chxn)2SbS3H] (1) (1,2-chxn=1,2-diaminocyclohexane) and [Cr(1,3-dap)2SbS3] (2) (1,3-dap=1,3-diaminopropane) were synthesized under solvothermal conditions. The crystal structures of 1 and 2 consist of neutral Mn2+ or Cr3+ complexes with the transition metal cations being in a distorted octahedral environment of four nitrogen atoms of 1,2-chxn resp. 1,3-dap and two sulphur atoms of the bidentate SbS33− unit. Compound 1 is remarkable because charge neutrality is achieved by the presence of Mn2+ and a SH group which was never observed before. In both compounds intermolecular S⋯H bonding interactions connect the complexes into higher dimensionality. Compound 1 crystallizes in the monoclinic space group P21/c with a=21.5440(16) Å, b=6.9295(3) Å, c=13.9276(10) Å and β=102.692(8)°. Compound 2 crystallizes in the orthorhombic space group Pbca with a=8.5999(2), b=15.9741(4) and c=21.6770(7) Å. - Graphical Abstract: The two new compounds [Mn(1,2-chxn)2SbS3H] and [Cr(1,3-dap)2SbS3] contain the SbS33− anion acting as bidentate ligand. Highlights: ► New isolated thioantimonates(III) with SbS33− anion acting as a bidentate ligand. ► Charge neutrality through protonated sulphur atom. ► First neutral Mn2+ complex chelated by bidentate amines and SbS33− pyramid.