Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS₄]^3— Anion Acting as a Monodentate Ligand: [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ and [Mn(C₆H₁₄N₂)₃]₂[Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O

Abstract

Abstract The two novel thioantimonate(V) compounds [Mn(C 6 H 18 N 4 )(C 6 H 19 N 4 )]SbS 4 ( I ) and [Mn(C 6 H 14 N 2 ) 3 ] [Mn(C 6 H 14 N 2 ) 2 (SbS 4 ) 2 ]·6H 2 O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn ( trans ‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P 1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)Å 3 , Z = 2, and II in the monoclinic space group C 2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)Å 3 , Z = 4. In I the Mn 2+ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS 4 ] 3— anion yielding a distorted octahedral environment. In II one unique Mn 2+ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn 2+ ion is coordinated by two chxn ligands and two monodentate [SbS 4 ] 3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.