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Persistent URL http://purl.org/net/epubs/work/36239
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Record Id 36239
Title Stoichiometry-dependent structures: an X-ray and neutron single-crystal diffraction study of the effect of reaction stoichiometry on the crystalline products formed in the potassium-cyanurate system
Abstract Reaction of cyanuric acid (C3H3N3O3; neutral form CYH3; anionic form CYH 2 ; dianionic form CYH2 ) with K2CO3 or KOH in aqueous solution gave three different crystalline products, according to the reaction stoichiometry used. The structures of two products were easily determined by singlecrystal X-ray diffraction: [K(CYH2)(H2O)], (1), of which the crystal structure is already known [Marsh, R. E. et al. (2002). Acta Cryst. B58, 62?77], and [K2(CYH)], (2), a highly symmetrical and dense structure. Further stoichiometric variation produced another new complex, (3), and reaction of Rb2CO3 with CYH3 yielded a further product, (4), which was found to be isostructural with (3). Determination of the structures of (3) and (4) by X-ray diffraction gave a result that was chemically unreasonable owing to a charge imbalance, with the asymmetric unit apparently containing 2 against 1.5+ (partial charges as the result of crystallographic mirror symmetry). A single-crystal neutron diffraction analysis carried out on a fully deuterated sample of (3) revealed the presence of a supercell, with the c axis doubled compared with the X-ray result. Subsequent refinement of the structure with this supercell showed that it is the result of just two D atoms breaking crystallographically imposed mirror symmetry, which is otherwise essentially observed by the rest of the structure. This minor deviation from pseudo-symmetry could not be identified by X-ray diffraction. Thus, single-crystal neutron diffraction data revealed that the true chemical formula of the structure of (3) [and presumably also of the isostructural (4) with Rb instead of K and H instead of D], is [K3(C3D2N3O3)3(C3D3N3O3)(D2O)4], the deuterated form of [K3(CYH2)3(CYH3)(H2O)4].
Organisation CCLRC , ISIS , ISIS-SXD
Keywords ISIS 2006 , Chemistry , neutron diffraction
Funding Information
Related Research Object(s): 10.5517/ccnyq09
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Language English (EN)
Type Details URI(s) Local file(s) Year
Journal Article Acta Crystallogr B 62 (2006): 798-807. doi:10.1107/S0108768106025171 2006