1,4,8,11-Tetraazacyclotetradecane antimony(III) sulfide

Zeitschrift anorg allge chemie

2009

The two new one-dimensional polymeric compounds [Ce(C 4 N 3 H 13 ) 2 (μ 3 -SbS 4 )] n (1) and [La(C 4 N 3 H 13 ) 2 (μ 4 -Sb 2 S 5 )(μ 3 -SO 4 )] n (2) were synthesized under solvothermal conditions. In the first compound, the unique Ce 3+ cation is surrounded by six nitrogen atoms of the amine ligands and by three sulfur atoms of the thioantimonate(V) anion. The CeN 6 S 3 polyhedron may be described as a distorted tricapped trigonal prism. The prisms are interconnected by [SbS 4 ] 3anions, which act in a μ 3 -binding mode yielding a chain running along [100]. An extended hydrogen-bonding network leads to the formation

Section: Introductionmentioning

confidence: 99%

Solvothermal Syntheses and Crystal Structures of the Two New Polymeric Compounds [Ce(C₄N₃H₁₃)₂(μ₃‐SbS₄)]_n and [La(C₄N₃H₁₃)₂(μ₄‐Sb₂S₅)(μ₃‐SO₄)]_n

Lichte

Näther

Zeitschrift anorg allge chemie

2009

“…Compound 3 contains a unique network topology and represents the first thioantimonate with a [Sb 10 S 17 ] 4– anion; i.e., it is the first compound with a Sb:S ratio of 1:1.7. Compounds with the next lowest ratio 1:1.67 are thioantimonates with the [Sb 6 S 10 ] 2– anion such as [Ni(dien) 2 ][Sb 6 S 10 ]·0.43 H 2 O, [Co(dien) 2 ][Sb 6 S 10 ]·0.46 H 2 O, (aep)Sb 6 S 10 (aep = 1-(2-aminoethyl)-piperazine), the isotypic compounds (cyclam)[Sb 6 S 10 ] (cyclam = 1,4,8,11-tetraazacyclotetradecane), (dachH 2 )(dach)[Sb 6 S 10 ], [Ni(bipy) 3 ][Sb 6 S 10 ], and [Fe(bipy) 3 ][Sb 6 S 10 ] and [Ni(dibipy) 3 ][Sb 6 S 10 ] (dibipy = 4,4′-dimethyl-2,2′-bipyridine) . The same ratio is observed in the [Sb 9 S 15 ] 3– anion like, e.g., in (dbnH) 3 [Sb 9 S 15 ] (dbn = 1,5-diazabicyclo[4.3.0]non-5-ene) and in the [Sb 3 S 5 ] − anion of ( trans -1,2-dachH)[Sb 3 S 5 ]·H 2 O, ( trans -1,4-dachH)[Sb 3 S 5 ], (tma)[Sb 3 S 5 ] (tma = tetramethylammonium) and (tpa)[Sb 3 S 5 ] (tpa = tetrapropylammonium) .…”

Section: Resultsmentioning

confidence: 99%

Fast Preparation of Dimorphic Thioantimonates and a Thioantimonate with a Hitherto Unknown Network Topology Applying a New Synthesis Approach

Anderer

Näther

Crystal Growth & Design

2016

The reaction of an aqueous solution of Na3SbS3 with [Ni(terpy)2]2+ (terpy = 2,2′:6′,2″-terpyridine) afforded crystallization of three new thioantimonates in short reaction times. Two polymorphic compounds, [Ni(terpy)2][Sb4S7]·H2O (1, 2), were obtained simultaneously under identical reaction conditions, while an increase of the reaction temperature led to formation of the third compound [Ni(terpy)2]2[Sb10S17] (3). In 1 the anion consists of a [Sb4S7]2– chain, whereas 2 is composed of a layered [Sb4S7]2– anion. Form 2 disappeared at longer reaction times, and therefore modification 1 might represent the thermodynamically stable form at this temperature despite the lower density compared to 2. Storing modification 1 at elevated temperatures the water can partly be removed in a topotactic reaction leading to the compound [Ni(terpy)2][Sb4S7]·0.25 H2O (1A). Compound 3 exhibits a unique Sb:S ratio, and a never before observed network topology significantly enhancing the structural diversity of thioantimonates(III).

“…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]. The layered [Sb 6 S 10 ] 2− anion in (cyclamH 2 )Sb 6 S 10 represents different structural motifs constructed by condensation of Sb 2 S 2 , Sb 4 S 4 and Sb 7 S 7 heterocycles [71].…”

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

Zeitschrift Für Naturforschung B

2010

138

112

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.