The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes

Lees, Rachel J. E.; Powell, Anthony V.; Chippindale, Ann M.

doi:10.1016/j.jpcs.2006.12.010

Cited by 29 publications

(27 citation statements)

References 17 publications

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“…For the thioantimonate anion [Sb 3 S 5 ] − onedimensional chains are observed in (Pr 4 N)Sb 3 S 5 [55] while (PPh 4 ) 2 Sb 6 S 10 contains the [Sb 6 S 10 ] 2− anion [64]. Interestingly, in both compounds a Sb 5 S 5 [65,69] is relatively complex and may be described as chains generated by linking the [SbS 3 ] and [SbS 4 ] moieties to form Sb 2 S 2 , Sb 4 S 4 , and Sb 5 S 5 heterocycles. The chains are then joined by condensation of the rings in the order Sb 4 S 4 -Sb 5 S 5 -Sb 2 S 2 -Sb 5 S 5 -Sb 4 S 4 into large 32-membered Sb 16 S 16 rings [65].…”

Section: Approaches To a Structural Classification For Thioantimonatementioning

confidence: 98%

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Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Seidlhofer

Pienack

Bensch

2010

Zeitschrift Für Naturforschung B

138

112

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A rich variety of inorganic-organic hybrid thioantimonates and thiostannates were prepared during the last few years under solvothermal conditions applying organic amine molecules or transition metal complexes as structure directors. In this review synthetic approaches to and structural features of these thiometallates are discussed. For thioantimonates(III) the structures range from well isolated thioanions to three-dimensional networks, whereas the structural chemistry of thiostannates(IV) is strongly dominated by the [Sn 2 S 6 ] 4− anion, and no three-dimensional thiostannate has been reported so far. In the structures of thioantimonates(III) several primary building units like the [SbS 3 ] trigonal pyramid, the [SbS 4 ] unit or even the [SbS 5 ] moiety are joined by vertex-and/or edge-linkages to form building blocks of higher structural hierarchy like [Sb 3 S 4 ] semi-cubes or Sb x S x heterocycles. A pronounced difference between thioantimonate and thiostannate chemistry is the tendency of Sb(III) to enhance the coordination geometry via so-called secondary bonds. In most cases the environment of Sb(III) is better described as a 3 + n polyhedron with n = 1 -3. The thioantimonate(V) structural chemistry is less rich than that of thioantimonates(III), and the [SbS 4 ] 3− anion shows no tendency for further condensation. By applying suitable multidentate amine molecules, transition metal cations which normally prefer bonding to the N atoms of the amines can be incorporated into the thiometallate frameworks.

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Section: Approaches To a Structural Classification For Thioantimonatementioning

confidence: 98%

“…The three-dimensional [Sb 8 S 13 ] 2− anion in (maH) 2 Sb 8 S 13 [74]. [69], whereas a more round-shaped Sb 18 S 18 pore with diameter 11.9 × 11.2Å occurs in (pyrH) 2 Sb 8 S 13 [75] (see Fig. 10).…”

Section: Approaches To a Structural Classification For Thioantimonatementioning

confidence: 99%

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Seidlhofer

Pienack

Bensch

2010

Zeitschrift Für Naturforschung B

138

112

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“…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 19 SbS 3 and SbS 4 units share corners and edges and form Sb 2 S 2 , Sb 3 S 7 , and Sb 6 S 12 secondary building units and they are connected to the final 3D framework.…”

Section: ' Introductionmentioning

confidence: 99%

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

Seidlhofer

Djamil

Näther

et al. 2011

Crystal Growth & Design

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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...

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“…This synthetic method continues to generate unusual and original structural motifs, as shown by the new phases presented in this paper. However, the crystallization process is sensitive to subtle changes in reaction conditions as demonstrated by the fact that the compound [Co(dien) 2 ]{Sb 18 S 30 [Co(dien)] 2 } ( 3 ) is formed at 463 K from a reagent mixture of the same composition as that used previously to prepare [Co(dien) 2 ]Sb 6 S 10 · 0.46H 2 O at 438 K. The structure of the latter consists of Sb 6 S 10 2– layers separated by isolated [Co(dien) 2 ] 2+ cations. Such a dramatic change in crystal structure between the two cobalt‐antimony‐sulfide compounds suggests that over 25 K, the crystallization pathway alters significantly.…”

Section: Discussionmentioning

confidence: 99%

Transition‐Metal Linkage of Antimony‐Sulfide Chains in [M(dien)₂]{Sb₁₈S₃₀[M(dien)]₂} (M = Mn, Fe, Co)

Lees

Powell

Chippindale

2016

Zeitschrift anorg allge chemie

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Three new isostructural transition‐metal thioantimonates [M(dien)2]{Sb18S30[M(dien)]2} [M = Mn (1), Fe (2), Co (3)] were prepared under solvothermal conditions in the presence of diethylenetriamine (dien). The compounds were characterized by single‐crystal X‐ray diffraction, thermogravimetry, elemental analysis, magnetic susceptibility measurements, and UV/Vis reflectance spectroscopy. The materials crystallize in the space group P1 and adopt a structure, in which complex Sb18S306– chains are cross‐linked into layers through transition‐metal‐dimer bridges, [M2S2], directly bonded to the thioantimonate layers. The layers contain pores, those in successive layers being aligned to generate a channel structure. Additional [M(dien)2]2+ cations are located within these channels in the interlayer space.

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The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes

Cited by 29 publications

References 17 publications

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Transition‐Metal Linkage of Antimony‐Sulfide Chains in [M(dien)₂]{Sb₁₈S₃₀[M(dien)]₂} (M = Mn, Fe, Co)

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The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes

Cited by 29 publications

References 17 publications

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

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

Transition‐Metal Linkage of Antimony‐Sulfide Chains in [M(dien)2]{Sb18S30[M(dien)]2} (M = Mn, Fe, Co)

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Transition‐Metal Linkage of Antimony‐Sulfide Chains in [M(dien)₂]{Sb₁₈S₃₀[M(dien)]₂} (M = Mn, Fe, Co)