Syntheses, Crystal Structures, and Reactivity of [enH]4[Sn2Se6]·en, [enH]4[Sn2Te6]·en and [enH]4[Sn2S6]: Known Anions within Novel Coordination Spheres obtained by Novel Synthesis Routes

Abstract

The hexachalcogenodistannates K 6 [Sn III 2 Se 6 ] or Li 4 [Sn IV 2 Te 6 ]·8en were recently reported to simultaneously act as mild oxidants and chalcogenide sources in reactions with CoCl 2 / LiCp* (Cp* ϭ pentamethylcyclopentadienide) while the SnϪE (E ϭ Se, Te) fragment is not kept in the products, e.g. [(Cp*Co) 3 (µ 3 -Se) 2 ], [(Cp*Co) 3 (µ 3 -Se) 2 ][Cl 2 Co(µ 2 -Cl) 2 Li(thf) 2 ] or [(Cp*Co) 4 (µ 3 -Te) 4 ]. In search of related reagents with possibly different reaction behavior, we isolated and crystallographically characterized isotypic compounds [enH] 4 [Sn IV 2 Se 6 ]·en (1), and [enH] 4 [Sn IV 2 Te 6 ]·en (2) (en ϭ 1,2-diaminoethane), that result from an uncommon disproportion/re-arrangement reaction: distannate(III) K 6 [Sn 2 E 6 ] (E ϭ Se, Te) was reacted with en·2HCl to yield 1 or 2 under disproportion of Sn III to Sn II and Sn IV . Another pathway was necessary to synthesize the respective but solvent-free thiostannate [enH] 4 -

Solvothermal Syntheses, Crystal Structures, and Thermal Properties of the First Example of Selenidostannates with Mixed Ethylene Polyamine‐Coordinated Transition Metal Complexes as Counterions

“…In 1 , all terminal selenium atoms of [Sn 2 Se 6 ] 4– are involved in the intermolecular N–H ··· Se hydrogen bonding with the adjacent [Ni(en) 3 ] 2+ cations. Each [Sn 2 Se 6 ] 4– anion contacts with six [Ni(en) 3 ] 2+ cations by hydrogen bonds (Figure 3) with N ··· Se separations varying from 3.454(8) to 3.629(8) Å and the N–H ··· Se angles varying from 157.2 to 167.5° (Table 3), which are consistent with the values reported in the literature 8. The intermolecular hydrogen bonding contacts lead to a 3D network of the [Ni(en) 3 ] 2+ and [Sn 2 Se 6 ] 4– ions.…”

Ultrasound and solvent-induced reversible chromism in a luminescent chalcogenidostannate

“…The H···Se bond lengths fall in the range of 2.62-2.93 Å and N-H···Se angles range from 145°to 173°, respectively (table S2 of the Supplementary material). The H···Se lengths and N-H···Se angles are consistent with values in the literature[33][34][35].In contrast to the structure of 1, Co(II) of 2 shows squeezed octahedral geometry, in which the equatorial Co1-N (N=N2, N3, N5, N6) bond lengths slightly stretch 0.007 Å, the axial Co1-N (N=N1, N4) bond lengths are contracted by 0.009 Å. The largest change in bond angles of 2 is a value of 0.35°observed in the N(2)-Co(1)-N(1) angle of [Co (dien) 2 ] 2+ .…”

Solvothermal Syntheses and Characterization of Thiostannates [M(en)3]2Sn2S6 (M = Mn, Co, Zn), the Influence of Metal Ions on the Crystal Structure

“…In the case of sulfur, a dark brown color is developed immediately when the sulfur reacts with en. The species of Q 2Ϫ , Q m 2Ϫ and (enH) ϩ have been confirmed by the products, such as (enH) 4 [Sn 2 Se 6 ]·en, (enH) 4 [Sn 2 Te 6 ]·en [12] and [Mn(en) 3 ]Te 4 [26]. The oxidized products of amine are still unclear.…”