[Fe(C 6 H 14 N 2 ) 2 ][Sb 6 S 10 ] – Using a Transition Metal Complex Acting as a Pillar for the Generation of a Three‐dimensional Thioantimonate(III) Network

The new three‐dimensional thioantimonate [Fe(C 6 H 14 N 2 ) 2 ][Sb 6 S 10 ] was obtained under solvothermal conditions. The compound crystallizes in space group P $\bar{1}$ with a = 6.174(4), b = 9.679(2), c = 12.772(3) Å, α = 72.08(3), β = 88.15(3), γ = 89.51(3)°, Z = 2. Trigonal pyramidal [SbS 3 ] units and [SbS 4 ] groups are joined to form a two‐dimensional [Sb 6 S 10 ] 2– layer. The in‐situ formed [Fe(C 6 H 14 N 2 ) 2 ] 2+ complexes act like pillars joining the layers into a three‐dimensional framework through Fe–S bonds. The Fe–S bond lengths are long which may be caused by a pronounced Jahn–Teller distortion. The optical bandgap of 2.0 eV is in agreement with the brownish color of the compound. The Mössbauer spectrum shows a doublet with an isomer shift typical for Fe 2+ in the high spin state. In the Raman spectrum the Sb–S stretching modes of the [SbS 3 ] and [SbS 4 ] groups can be distinguished. Upon heating in nitogen the compound is decomposed in one step yielding Sb 2 S 3 and FeSb 2 S 4 .