Dalton Transactions
Varied forms of lamellar [Sn3Se7]n2n− anion: the competitive and synergistic structure-directing effects of metal–amine complex and imidazolium cations
Cheng-Feng Du,ab Jian-Rong Li,*a Mei-Ling Feng,a Guo-Dong Zou,c Nan-Nan Shenab and Xiao-Ying Huanga
a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, People's Republic of China
E-mail: jrli@fjirsm.ac.cn
Tel: +86 0591 63173146
b University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China
c College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, China
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.
Crystal structure data CIF (200K)
The article was received on 11 Feb 2015, accepted on 09 Mar 2015 and first published on 09 Mar 2015
DOI: 10.1039/C5DT00620A
Author version
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Download Citation: Dalton Trans., 2015,44, 7364-7372
C. Du, J. Li, M. Feng, G. Zou, N. Shen and X. Huang, Dalton Trans., 2015, 44, 7364
Cheng-Feng Du
Jian-Rong Li
Mei-Ling Feng
Guo-Dong Zou
Nan-Nan Shen
Xiao-Ying Huang