In:
Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, International Union of Crystallography (IUCr), Vol. 73, No. 5 ( 2017-10-01), p. 981-991
Abstract:
The ditopic organic molecule 3-(pyridin-4-yl)acetylacetone (HacacPy) acts as a pyridine-type ligand towards Hg X 2 ( X = Cl, Br, I). The nature of the anion and the ligand-to-cation ratio dominate the outcome of the reaction. Two different coordination compounds form with HgCl 2 , namely a ligand-rich mononuclear complex, HgCl 2 (HacacPy) 2 , and a ligand-deficient one-dimensional chain polymer, [Hg( μ -Cl) 2 (HacacPy)] 1 ∞ , with five-coordinated Hg II cations. Two compounds are also observed for HgBr 2 , a molecular complex isomorphous to the chloride derivative and a chain polymer with the composition [Hg( μ -Br)Br(HacacPy)] 1 ∞ , in which the cations are four-coordinated. The ligand-rich mononuclear and ligand-deficient polymeric chloride and bromide complexes may be interconverted via thermal degradation and mechanochemical synthesis. In contrast to the chloride and bromide compounds, the reaction product with HgI 2 does not depend on the ligand-to-cation ratio but corresponds to [Hg( μ -I)I(HacacPy)] 1 ∞ , isomorphous to the bromide derivative. The N -coordinated HacacPy complexes could not be deprotonated and further crosslinked with a second cation. Synthesis of mixed-metal products could be achieved, however, by deprotonation of the acetylacetone moiety in HacacPy and formation of tris-chelated Fe(acacPy) 3 and Al(acacPy) 3 complexes in the first step. These mononuclear building blocks act as bridging poly(pyridine) ligands towards Hg II halides and form two structure types. The first represents a one-dimensional ladder, with the tris(ligand) complexes acting as triconnected nodes and the Hg II halides acting as linkers. In the alternative unprecedented product, both the tris(ligand) complexes and the [Hg X 2 ( μ - X )Hg X ] groups act as equivalent triconnected nodes. They form a uninodal two-dimensional coordination network with vertex symbol 4.8 2 and fes topology.
Type of Medium:
Online Resource
ISSN:
2052-5206
DOI:
10.1107/S2052520617011118
DOI:
10.1107/S2052520617011118/bm5094sup1.cif
DOI:
10.1107/S2052520617011118/bm50941asup2.hkl
DOI:
10.1107/S2052520617011118/bm50941bsup3.hkl
DOI:
10.1107/S2052520617011118/bm50942sup4.hkl
DOI:
10.1107/S2052520617011118/bm50942bsup5.hkl
DOI:
10.1107/S2052520617011118/bm50943sup6.hkl
DOI:
10.1107/S2052520617011118/bm50946csup7.hkl
DOI:
10.1107/S2052520617011118/bm50949dsup8.hkl
DOI:
10.1107/S2052520617011118/bm5094sup9.pdf
Language:
Unknown
Publisher:
International Union of Crystallography (IUCr)
Publication Date:
2017
detail.hit.zdb_id:
2020841-8
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