Extending the Time: Solvothermal Syntheses, Crystal Structures, and Properties of Two Non-isostructural Thioantimonates with the Composition [Mn(tren)]Sb2S4
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- 作者：Michael Schaefer ; Daniel Kurowski ; Arno Pfitzner ; Christian Nä ; ther ; Zomaje Rejai ; Karina Mö ; ller ; Nancy Ziegler ; and Wolfgang Bensch
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：May 1, 2006
- 年：2006
- 卷：45
- 期：9
- 页码：3726 - 3731
- 全文大小：399K
- 年卷期：v.45,no.9(May 1, 2006)
- ISSN：1520-510X
文摘
The two novel compounds, [Mn(tren)]Sb2S4 (1 and 2), were obtained by the reaction of elemental Mn, Sb, and Sin aqueous solutions of tren (tren = tris(2-aminoethyl)amine, C6H18N4) after different reaction times. Compound 1is formed up to a reaction time of 13 d, and an extension of the reaction time leads to the formation of 2. Bothcompounds crystallize in monoclinic space groups (1, P21/c; 2, C2/c). In 1, the two unique SbS3 trigonal pyramidsshare a common S atom to form a Sb2S5 unit. Two S atoms of this group have a bond to Mn2+ yielding a MnSb2S3heteroring in the boat conformation. The Sb2S5 moieties are joined via common corners into the final undulated
[Sb2S4]2- anion which is directed along [001]. The structure of 2 contains the [Mn(tren)]2+ ion, one SbS3 pyramid,and a SbS4 unit. Two symmetry-related SbS4 groups share an edge, forming a Sb2S6 group containing a Sb2S2ring. This group is joined via corners to two SbS3 pyramids on both sides producing a Sb4S4 ring. The Sb2S2 andSb4S4 rings are condensed into the final 
[Sb2S4]2- anion which runs along [010]. The [Mn(tren)] groups are boundto the thioantimonate(III) backbone on opposite sides of the Sb4S4 ring, and a small MnSbS2 ring is formed. In bothstructures, weak S···H bonds are found which may contribute to the stability of the materials. The two compoundsdecompose in one step upon heating, and only MnS and Sb2S3 could be identified as the crystalline part of thedecomposition products. Both compounds can also be prepared under solvothermal conditions using MnSb2S4 asstarting material. Compounds 1 and 2 are obtained from this ternary material in a high yield.
[Sb2S4]2- anion which is directed along [001]. The structure of 2 contains the [Mn(tren)]2+ ion, one SbS3 pyramid,and a SbS4 unit. Two symmetry-related SbS4 groups share an edge, forming a Sb2S6 group containing a Sb2S2ring. This group is joined via corners to two SbS3 pyramids on both sides producing a Sb4S4 ring. The Sb2S2 andSb4S4 rings are condensed into the final [Sb2S4]2- anion which runs along [010]. The [Mn(tren)] groups are boundto the thioantimonate(III) backbone on opposite sides of the Sb4S4 ring, and a small MnSbS2 ring is formed. In bothstructures, weak S···H bonds are found which may contribute to the stability of the materials. The two compoundsdecompose in one step upon heating, and only MnS and Sb2S3 could be identified as the crystalline part of thedecomposition products. Both compounds can also be prepared under solvothermal conditions using MnSb2S4 asstarting material. Compounds 1 and 2 are obtained from this ternary material in a high yield.