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

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 ] 2 -[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 P1, a ϭ 9.578(2), b ϭ 11.541(2), c ϭ 12.297(2) Å , α ϭ 62.55(1), β ϭ 85.75(1), γ ϭ 89.44(1)°, V ϭ 1202.6(4) Å 3 , Z ϭ 2, and II in the monoclinic space group C2/c, a ϭ 32.611(2), b ϭ 13.680(1), c ϭ 19.997(1) Å , β ϭ 117.237(5)°, V ϭ 7931.7(8) Å 3 , Z ϭ 4. In I the Mn 2ϩ cation is surrounded by one tetradentate tren molecule, one

2,2′,2′′-Nitrilotris(ethylammonium) tetrathioantimonate

“…A mixture of 0.5 mmol MnSb 2 S 4 , 0.5 mmol (NH 4 ) 2 MoS 4 , 3 mmol S and 5 ml concentrated tris(2-aminoethyl)amine were heated at 413 K for 7 d followed by cooling to room temperature. The product was identified by X-ray powder diffraction and contained two different phases in approximately equivalent amount: red crystals of [Mn(tren)(trenH)]SbS 4 (tren = tris(2-ethyl)amine) (Schaefer et al, 2003), and yellow crystals of the title compound.…”

“…× 6 H 2 O and [Mn(tren)(trenH)]SbS 4 (tren = tris(2-ethyl)amine) (Schaefer et al, 2003), [Ni(en) 3 (enH)]SbS 4 (Jia et al, 2004), [Sm(en) 4 ]SbS 4 × 0.5 en (Jia, Zhu et al, 2005), [Ln(en)…”

A Coordination Polymer based on Interconnection of Thioantimonate(III) and [Mn(terpy)]2+ Complexes: Synthesis, Crystal Structure, and Properties of {[(Mn(terpy))2Sb4S8]·0.5H2O}n

“…For thioantimonates(V) a regular [SbS 4 ] 3– tetrahedron is observed as structural motif, which is either isolated or joined via covalent bonds to transition metal (TM) or rare earth cations , . The occurrence of mixed‐valent thioantimonates(III/V) is rare and less than a handful examples were reported , .…”

“…[25,26] For thioantimonates(V) a regular [SbS 4 ] 3tetrahedron is observed as structural motif, which is either isolated [27][28][29][30][31][32] or joined via covalent bonds to transition metal (TM) or rare earth cations. [21,[33][34][35][36][37] The occurrence of mixed-valent thioantimonates(III/V) is rare and less than a handful examples were reported. [19,[38][39][40] Many thioantimonates were solvothermally prepared with transition metal centered complexes in the presence of the metal, metal sulfide, Sb or Sb 2 S 3 and/or S in aqueous amine or hydrazine solutions.…”

“…[19,[38][39][40] Many thioantimonates were solvothermally prepared with transition metal centered complexes in the presence of the metal, metal sulfide, Sb or Sb 2 S 3 and/or S in aqueous amine or hydrazine solutions. Analyzing the TM complex containing thioantimonate compounds an interesting observation is that Mn 2+ can be easily integrated into the anionic network via Mn-S bond formation , [21,37,[41][42][43][44][45][46][47][48][49][50][51][52] which indicates that this cation has a similar affinity to N and S atoms.…”