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Complexes of Thiourea with alkali metal bromides and iodides: Structural properties, mixed-halide and mixed-metal materials, and halide exchange processes

Charalampopoulos, Vasileios G., Kariuki, Benson and Harris, Kenneth David Maclean 2017. Complexes of Thiourea with alkali metal bromides and iodides: Structural properties, mixed-halide and mixed-metal materials, and halide exchange processes. Crystal Growth and Design 17 (2) , pp. 786-793. 10.1021/acs.cgd.6b01644

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Abstract

We report the preparation and structural properties of complexes of metal halides and thiourea with composition MX[thiourea]4 (MX = KBr, KI, RbI, CsI), together with the mixed-halide materials KBrnI1–n[thiourea]4 (0 < n < 1) and the mixed-metal materials KnCs1–nI[thiourea]4 (0 < n < 1). These materials are isostructural, with a tetragonal structure (space group P4/mnc) characterized by M+[thiourea]4 coordination columns along the 4-fold axis and halide anions located in channels in the region of space between adjacent columns and running parallel to the columns. For the mixed-halide materials, the stoichiometry KBrnI1–n[thiourea]4 depends on the bromide/iodide ratio in the crystallization solution; the crystalline complexes have a higher bromide/iodide ratio than the crystallization solution, indicating preferential incorporation of bromide within the complex. Soaking crystals of KBr0.61I0.39[thiourea]4 in iodide containing solutions leads to halide exchange, with the iodide to bromide ratio increasing relative to the parent crystal. Further experiments produced no evidence that these thiourea complexes can accommodate extended polyiodide networks.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 1528-7483
Date of First Compliant Deposit: 9 January 2017
Date of Acceptance: 22 December 2016
Last Modified: 24 Dec 2017 12:57
URI: http://orca-mwe.cf.ac.uk/id/eprint/97281

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