Issue 16, 2015

Varied forms of lamellar [Sn3Se7]n2n anion: the competitive and synergistic structure-directing effects of metal–amine complex and imidazolium cations

Abstract

Presented are the syntheses, characterizations and properties of a series of selenidostannate compounds directed by metal–amine complex (MAC) cations and/or [Bmmim]+ (Bmmim = 1-butyl-2,3-dimethylimidazolium). Mixtures of the ionic liquid (IL) (Bmmim)Cl and amines, such as ethylenediamine (en) and diethylenetriamine (dien), in various ratios were used to ionothermally/solvothermally prepare four selenidostannates, namely, [Mn(en)3]Sn3Se7 (1), [Mn(dien)2]Sn3Se7·H2O (2), (Bmmim)3[Mn(en)3]2[Sn9Se21]Cl (3) and (Bmmim)6[Mn(dien)2]2Sn15Se35 (4). Single-crystal X-ray diffraction analyses revealed that these compounds exhibit lamellar anionic [Sn3Se7]n2n structures. [Sn3Se7]n2n layers in all 1–4 possess a {63} net, considering [Sn3Se10] semi-cube unit as a 3-connected node; however, diverse multi-membered rings exist there. In compounds 1 and 2, all the [Sn3Se10] units are 3-connected nodes interlinking with each other via edge-sharing two Se atoms to produce six-membered rings. However, in compound 3, the insertion of two [Sn3Se9] units into a six-membered ring results in a novel eight-membered heart-shaped ring, which has never been observed before in the family of chalcogenidostannates. More interestingly, the [Sn3Se7]n2n layer in compound 4 consists of mixed six- and eight-membered rings. The phase composition is strongly dependent on the ratio of IL to MAC in the syntheses, e.g., 1 and 2 were obtained with IL : MAC ratios less than 3 : 1 and 4 : 1, while 3 and 4 were obtained when the ratios were increased to 4 : 1 and 5 : 1, respectively. The structural variation from 1 to 4 clearly indicates the competitive and synergistic effects between MAC and IL cation on the formation of lamellar selenidostannates. A synthetic approach via varying the ratio of IL to MAC cation as solvent and structure-directing agent will be attractive in the synthesis of novel chalcogenidometallates.

Graphical abstract: Varied forms of lamellar [Sn3Se7]n2n− anion: the competitive and synergistic structure-directing effects of metal–amine complex and imidazolium cations

Supplementary files

Article information

Article type
Paper
Submitted
11 Feb 2015
Accepted
09 Mar 2015
First published
09 Mar 2015

Dalton Trans., 2015,44, 7364-7372

Author version available

Varied forms of lamellar [Sn3Se7]n2n anion: the competitive and synergistic structure-directing effects of metal–amine complex and imidazolium cations

C. Du, J. Li, M. Feng, G. Zou, N. Shen and X. Huang, Dalton Trans., 2015, 44, 7364 DOI: 10.1039/C5DT00620A

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