From Zero- to Three-Dimensional Thioantimonates: [Ni(aepa)₂]₃Sb₆S₁₂ (aepa = C₅H₁₅N₃ = N-(aminoethyl)-1,3-propandiamine), Containing the Unique [Sb₆S₁₂]^6– Cyclic Anion, [Ni(aepa)₂]₆(Sb₃S₆)₂(SO₄)₃·2H₂O, with Isolated [Sb₃S₆]^3– anions and [Ni(aepa)₂]Sb₄S

Abstract

Thioantimonate chemistry is characterized by a fascinating structural and chemical diversity. 1 One intriguing structural feature is that for a given Sb/S ratio the dimensionality of the thioantimonate anion may range from zero-dimensional (0D) isolated anions to three-dimensional (3D) networks. Analyzing the thioantimonate(III) structures containing charge compensating cations of different sizes and charges, only a moderate influence on the dimensionality could be identified. For instance, 0D Ni 2+ containing thioantimonates(III) were obtained with diethylenetriamine (dien) as solvent; one-dimensional (1D) chains with ethylenediamine (en), dien, and tris(2-aminoethyl)amine (tren); two-dimensional (2D) layers with 1,2-diaminopropane (1,2-dap), dien, and tren; and 3D networks with en, dien, and 1,4,8,11-tetraazacyclotetradecane (cyclam). This clearly demonstrates that the choice of the size/charge of the solvent/structure director has no effect on the dimensionality of the inorganic part of the compounds. There are no general rules allowing prediction of the chemical composition and/or crystal structure of thioantimonates formed under solvothermal conditions. Thiometallate compound formation was investigated by us applying in situ X-ray scattering and X-ray absorption techniques demonstrating the complexity of the reactions occurring under solvothermal conditions. 2À5 Concerning the structural chemistry of thioantimonates containing Ni-amine complexes as structure directing and charge balancing agents, two compounds are 0D, namely, [Ni (dien) 2 ]-Sb 4 S 8 6 and [Ni(dien) 2 ] 3 (Sb 3 S 6 ) 2 . 7 In the former compound, four SbS 3 moieties share common corners to form the [Sb 4 S 8 ] 4À heterocycle. 6 The [Sb 3 S 6 ] 3À anion 7 is constructed by three vertex-linked SbS 3 pyramids. Several isolated thioantimonate(V) anions could also be isolated like [Ni(en) 3 ] 3 (SbS 4 )(NO 3 ), 8 [Ni-(dien) 2 ] 3 (SbS 4 ) 2 , 9 (paH)[Ni(tren)SbS 4 ], 10 [Ni(chxn) 3 ] 3 (SbS 4 ) 2 3 4H 2 O 11 and [Ni(en) 3 (enH)]SbS 4 . 12 Only in (paH)[Ni(tren)-SbS 4 ] 10 the Ni 2+ ion is octahedrally surrounded by four N atoms of the amine and by two S atoms of the [SbS 4 ] 3À anion. 1D chain anions are found in [Ni(tren)]Sb 2 S 4 , 13 [Ni(dien) 2 ]Sb 4 S 9 , 14 [Ni(tren)Sb 4 S 7 ], 15 [Ni(en) 3 ]Sb 2 S 4 , and [Ni(en) 3 ]Sb 4 S 7 . 16 The compound [Ni(tren)]Sb 2 S 4 13 is a rare example where the Ni 2+ ion is incorporated in the thioantimonate network via NiÀS bonds. ABSTRACT: The new thioantimonates [Ni(aepa) 2 ] 3 Sb 6 S 12 (1), [Ni(aepa) 2 ] 6 -(Sb 3 S 6 ) 2 (SO 4 ) 3 3 2H 2 O (2), and [Ni(aepa) 2 ]Sb 4 S 7 (3) (aepa = C 5 H 15 N 3 = N-(aminoethyl)-1,3-propandiamine) were obtained under solvothermal conditions by slightly varying the reaction conditions. In all compounds the [Ni(aepa) 2 ] 2+ complexes were formed in situ during the chemical reactions. Compound 1 features the new unique [Sb 6 S 12 ] 6À cyclic anion composed by vertex-linked SbS 3 trigonal pyramids. This [Sb 6 S 12 ] 6À cyclic anion represents the largest isolated thioantimon...

Effect of lanthanide contraction on the Ln/Sb/Se/dien system: solvothermal syntheses and characterizations of lanthanide(III)-selenidoantimonate complexes with diethylenetriamine as a co-ligand

“…[15], and [Ni(aepa) 2 ] 3 Sb 6 S 12 , [Ni(aepa) 2 ]Sb 4 S 7 (aepa = N-(aminoethyl)-1,3-propandiamine) [16], as recent examples.…”

The Two‐Dimensional Anion [Sb6Se10]2–: Solvothermal Synthesis, Crystal Structure, and Properties of an Iron ­Selenidoantimonate(III) [Fe(phen)3]Sb6Se10

“…Sb Q 3 and Sb Q 4 ( Q = S, Se) are the primary building units (PBUs) of condensed multinuclear chalcogenidoantimonates [Sb x Q y ] n – . The high tendency for condensation of the SbS 3 and SbS 4 PBUs by corner‐ or edge‐sharing had led to a series of binary thioantimonates with different compositions and structures ranging from discrete anions,4 1D chains,5–9 2D sheets,10–12 to 3D frameworks13,14,16,20 with TM complex counter cations. However the SbSe 3 and SbSe 4 PBUs seem to be less facile in the formation of binary polymeric anion [Sb x Q y ] n – in the presence of transition metal complexes.…”

“…A large number of TM ‐thioantimonates(III) with a variety of structure patterns have been prepared in different ethylene polyamines using solvothermal methods 4–14. The recent notable examples of thioantimonates(III) of the TM /Sb/S family are [Ni(tren) 2 ] 2 [Ni(tren)(en)] 2 (Sb 4 S 8 ) 2 · 0.25H 2 O,15 [Ni(en)(tren)] 4 Sb 14 S 25 (en = ethylendiamine, tren = tris(2­aminoethyl)amine),16 [Ni(dien) 2 ]CuSb 3 S 6 ,17 [Co(dien) 2 ] 4 [CoSb 6 S 14 ] (dien = diethylenetriamine),18 [Mn(1, 2‐chxn) 2 SbS 3 H] (chxn = 1, 2‐diaminocyclohexane),19 [Ni(aepa) 2 ] 3 Sb 6 S 12 , [Ni(aepa) 2 ]Sb 4 S 7 (aepa = N ‐(aminoethyl)‐1, 3‐propandiamine),20 (trien)Mn 3 Sb 2 S 6 (trien = triethylenetetramine),21 (dienH 3 )[(dienH)MnSb 8 S 15 ] · H 2 O,22 and [Mn(tepa)Sb 6 S 10 ] (tepa = tetraethylenepentamine) 23…”

[N,N-Bis(2-aminoethyl)ethane-1,2-diamine](ethane-1,2-diamine)nickel(II) thiosulfate trihydrate

“…The structure of the title compound was determined within a project on the synthesis, structure determination and investigation of the properties of new thioantimonates (Seidlhofer et al, 2011;Lühmann et al, 2011). The crystals were obtained accidentally by the reaction of [Ni(en) 3 ]Cl 2 with Sb and S in tris(2-aminoethyl)amine.…”

“…For background of this work, see: Lü hmann et al (2011); Seidlhofer et al (2011). For related thiosulfate crystal structures, see: Nardelli & Coghi (1958); Varand et al (1967); Freire et al (2000); Díaz de Vivar et al (2007).…”