Methanolothermal Syntheses, Crystal Structures and Optical Properties of Binuclear Transition Metal Complexes Involving the Bidentate S-Donor Ligand μ-Sn2S6

One-Dimensional Vanadium(III) Chalcogenidostannates Incorporating [V(tepa)]3+ Complexes as Bridging Groups

“…Two [SnQ 4 ] tetrahedra are connected by two Q bridges, forming a dimeric anion, [Sn 2 Q 6 ] 4– . The Sn–Q bond lengths [2.326(5)–2.457(4) Å for Sn–S and 2.438(2)–2.577(2) Å for Sn–Se] are in agreement with those in other [Sn 2 Q 6 ] 4– . The V 3+ ion is coordinated by five N atoms of one tepa ligand and two Q atoms from two [Sn 2 Q 6 ] 4– anions (Figure a,b), generating a [VN 5 Q 2 ] pentagonal-bipyramidal geometry (Figure c), whose polyhedra are slightly distorted and Q–V–Q [168.5(2)° for 1 and 168.08(14)° for 2 ] angles deviate evidently from the ideal value of 180°.…”

“…Two-dimensional (2D) SnQ (Q = Se, Te) monolayers constructed by [SnQ 3 ] trigonal pyramids show high thermoelectric properties. , The 2D organic hybrid thiostannate (Me 2 NH 2 ) 1.33 (Me 3 NH) 0.66 Sn 3 S 7 ·1.25H 2 O containing [SnS 5 ] can be applied for [UO 2 ] 2+ ion exchange . The incorporation of other transition-metal (TM) ions into the chalcogenidostannate frameworks might result in a new class of multinary chalcogenidostannates, which can not only increase their structural diversities but also alter their physicochemical properties for different applications. − The chalcophilic TM ions, as exemplified by Cu + , Ag + , and Hg 2+ , are encapsulated entirely within chalcogenidostannate anions via TM–Q bonds in amine solvents, while other TM ions, including trivalent Cr 3+ ion and some divalent Zn 2+ , Mn 2+ , Fe 2+ , Co 2+ , and Ni 2+ ions, generally generate unsaturated TM amine complexes, which can further interact with chalcogenidostannate anions to give new organic hybrid chalcogenidostannates with various structures. , Unexpectedly, no organic hybrid chalcogenidostannates incorporating vanadium­(III) amine complexes had emerged until now, mainly because the oxyphilic V 3+ ion has difficulty bonding to the chalcogen atoms of chalcogenidostannates under solvothermal conditions.…”

“…In order to achieve vanadium­(III) chalcogenidostannates with useful properties, we began to explore the system Sn/Q/V/tepa (Q = S, Se) under solvothermal conditions and successfully prepared two new vanadium­(III) chalcogenidostannates, [H 2 tepa] 0.5 n [V III (tepa)­(μ-Sn 2 Q 6 )] n [Q = S ( 1 ; CCDC 2046539), Se ( 2 ; CCDC 2046540)]. Because the TM ion generally prefers a coordination number of 6 within the chalcogenidometalates, the pentadentate tepa ligand chelates the TM ion to form an unsaturated [TM­(tepa)] n + complex with one free coordination site of the TM ion, which only acts as a decorating group, as exemplified by {[TM­(tepa)] 2 (μ 2 -A 2 Q 6 )} (TM = Mn, Fe, Co, Ni, Zn; A = Sn, Ge; Q = S, Se), , [Mn­(tepa)­Sn 3 Se 7 ] n , {[Mn­(tepa)] 8 Sn 4 Ga 4 Zn 2 Se 20 }, {[Ni­(tepa)] 2 SO 4 }­[Ni­(tepa)­(Ga 4 S 6 (SH) 4 )], and {[Ni­(tepa)] 2 In 4 S 7 (SH) 2 }·H 2 O, but no [TM­(tepa)] n + complexes as bridging groups have been applied in the formation of various polymeric chalcogenidometalates, to the best of our knowledge. Therefore, both 1 and 2 present the first examples of 1D vanadium­(III) chalcogenidostannates based on [V­(tepa)] 3+ complexes as bridging groups.…”

“…The V–S [2.487(5) Å] and V–Se [2.619(3)–2.620(3) Å] bond lengths are compared with the corresponding values [2.324(2)–2.496(2) Å for V–S and 2.4932(8)–2.6361(8) Å for V–Se] in other vanadium­(III) complexes containing chalcogen atoms . The tepa ligand shows a rare coplanar configuration, whose five N atoms lie in the equatorial locations of the pentagonal bipyramid because the reported tepa ligand chelating the TM ion usually adopts the enfoldment-like configuration, in which four N atoms seat at the equatorial locations of the octahedron and one N atom situates at the axial location. , According to bond valence sums, the oxidation state of the V atom (∑ s = 2.789 for 1 and 2.809 for 2 ) is 3+. The usual valences of S (or Se) and Sn are 2– and 4+, respectively, the [V III (tepa)­(μ-Sn 2 Q 6 )] fragment brings a charge of 1–, and its negative charge can be balanced by half of a protonated H 2 tepa 2+ cation.…”

“…More interestingly, 1 and 2 show some unique structural characteristics. First, the [Sn 2 Q 6 ] 4– anions adopt generally a trans-bridging mode (Figure S1a); for instance, the [Sn 2 Q 6 ] 4– anions bridge two unsaturated [TM­(tepa)] 2+ (TM = Mn, Fe, Co, Ni, Zn) or [TM­(tren)] 2+ [tren = tris­(2-aminoethyl)­amine; TM = Mn, Co, Ni, Zn] ,, complexes by trans -Q t (t = terminal) atoms to create the neutral {[M­(tepa)] 2 (μ 2 -Sn 2 Q 6 )} or {[M­(tepa)] 2 (μ 2 -Sn 2 Q 6 )} molecules, whose [Sn 2 Q 6 ] 4– anions are situated at the center of inversion. The unsaturated [Mn­(en) 2 ] 2+ (en = ethylenediamine) complexes are alternately bridged by trans -[Sn 2 S 6 ] 4– anions and linear en ligands to form the 1D [Mn 2 (en) 4 (μ-en)­(μ-Sn 2 S 6 )] n chains .…”