The [Sn₂S₆]^4– Anion Acting as Tetradentate Linker: ­Solvothermal Synthesis and Selected Properties of {[TM(phen)₂]₂Sn₂S₆} and {[TM(phen)₂]₂Sn₂S₆}·phen·H₂O (TM = Fe, Co)

Crystal Structures and Selected Properties of CoII Containing Thiostannates prepared by a New Room Temperature Route

“…Such compounds are known and were recently reported by us with, e.g. phenanthroline . This is further supported by an IR spectrum of the residue obtained at 110 °C, which shows that all absorptions of the ligand are present, indicating that it remains stable upon heating (Figure S10, top, Supporting Information).…”

Transition Metal Complexes with Linkage to the Thiostannate Units Forced by Suitable Amine Molecules

“…One may speculate that the size matching is essential for generation of π–π interactions and if the aromatic molecules are too large or exhibit the “wrong” shape these are not integrated into a crystalline product. Nevertheless compound 2 {[Ni(phen) 2 ] 2 [Sn 2 S 6 ]} · phen · H 2 O crystallized in the presence of naphthalene, anthracene, phenanthrene, or p ‐terphenyl and the analogous syntheses with Mn, Fe, Co lead to the formation of {[TM(phen) 2 ] 2 [Sn 2 S 6 ]} and {[TM(phen) 2 ] 2 [Sn 2 S 6 ]} · phen · H 2 O (TM = Mn, Fe, Co) , …”

“…Especially the S term –Sn–S term angles in compounds 1 , 2 , and 5 show deviations up to 10° from ideal tetrahedral arrangement of a free [Sn 2 S 6 ] 4– ion [S term –Sn–S term : 100.25(3)–103.69(9)°; S term –Sn–(μ‐S): 113.31(3)–120.43(3)°; (μ‐S)–Sn–(μ‐S): 92.15(3)–92.89(3)°], whereas the anions in 3 and 4 are less distorted [S term –Sn–S term : 113.44(3)–117.28(2)°; S term –Sn–(μ‐S): 110.54(3)–114.03(3)°; (μ‐S)–Sn–(μ‐S): 93.17(3)–93.83(2)°]. The distinct deviation of these angles in compounds 1 , 2 , and 5 is caused by the fixed position of the terminal S atoms by the bonds to the bridging TM 2+ cation, but all values are still comparable to literature data of similar compounds , …”

“…The charge compensation in these compounds can be achieved in different ways: (a) inorganic cations, (b) inorganic‐organic hybrid compounds with protonated amine molecules as counterions, (c) compounds with integrated transition metal ions (TM) in the thiostannate unit and protonated amines as counterions, and finally (d) compounds containing [TM(amine) n ] m + or [ Ln (amine) n ] m + complexes for charge compensation as summarized in several review articles , , . In the latter group mainly the [Sn 2 S 6 ] 4– unit is observed, whereas the [SnS 4 ] 4– anion is less common , , , . Other thiostannate ions like for example [Sn 3 S 7 ] 2– , [Sn 4 S 9 ] 2– ,, [Sn 5 S 12 ] 4– , [Sn 3 S 9 ] 6– , or [Sn 4 S 10 ] 4– are only found in pure inorganic or inorganic‐organic hybrid compounds so far.…”

“…using amines like tetraethylenepentamine (tepa) in {[Ni(tepa)] 2 [Sn 2 S 6 ]}, or tris(2‐aminoethyl)amine (tren) in {[Ni(tren)] 2 [Sn 2 S 6 ]} n , which cannot saturate the coordination sphere of the central metal atom. Aromatic or cyclic amines with rigid positions of the amine groups like 1,10‐phenanthroline (phen) in {[TM(phen) 2 ] 2 [Sn 2 S 6 ]} · (TM = Fe, Co), and {[Ni(phen) 2 ] 2 [Sn 2 S 6 ]} · amine (amine = 2,2′‐bipyridine (2,2′‐bipy), 4,4′‐bipyridine (4,4′‐bipy)) and 1,2‐diaminocyclohexane (1,2‐dach) in the related class of thioantimonates in {[Fe(1,2‐dach) 2 ][Sb 6 S 10 ]} seem to be exceptions: in principal these amine ligands could satisfy the coordination requirements of the central TM 2+ atoms, but interestingly TM–S bonds have been observed, even with Fe 2+ and Co 2+ which normally prefer bonds to N donor ligands. A further observation is that only few [TM(amine) n ] 2+ containing tin‐sulfur compounds exhibit a dimensionality larger than zero.…”