3-(4-Pyridyl)-2,4-pentanedione – a bridge between coordinative, halogen, and hydrogen bonds

Merkens, Carina; Pan, Fangfang; Englert, Ulli

doi:10.1039/c3ce41306c

Cited by 56 publications

(46 citation statements)

References 37 publications

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“…[Symmetry codes: The iodine substituents in the TFDIB residue are suitable halogen-bond donors towards nucleophiles such as the terminal S atom from the isothiocyanate ligands. TFDIB has been used successfully as an electrophilic component in short halogen bonds with pyridine derivatives (Roper et al, 2010;Sgarbossa et al, 2012;Merkens et al, 2013).…”

Section: Research Papersmentioning

confidence: 99%

“…Tetrafluorodiiodobenzene (TFDIB) meets the requirements for a good halogen-bond donor through its iodo substituents towards nucleophiles such as the S atom of an isothiocyanate ligand. Our group has used TFDIB for the construction of cocrystals in which hydrogen and halogen bonds of different strengths co-exist with coordinative bonds (Merkens et al, 2013).…”

Section: Introductionmentioning

confidence: 99%

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Halogen bonds on demand: I...S contacts in cocrystals oftrans-bis(thiocyanato-κN)tetrakis(4-vinylpyridine-κN)nickel(II) and 2,3,5,6-tetrafluoro-1,4-diiodobenzene

et al. 2015

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Hydrogen bonds are considered a powerful organizing force in designing supramolecular architectures because they are directional, selective and reversible at room temperature. trans-Dithiocyanatotetrakis(4-vinylpyridine)nickel(II) is a popular host for the inclusion of small molecules and 2,3,5,6-tetrafluoro-1,4-diiodobenzene (TFDIB) represents a strong halogen-bond donor. These constituents cocrystallize in a 1:1 stoichiometry, [Ni(NCS)2(C7H7N)4]·C6F4I2, in the tetragonal space group I4₁/a. Both residues occupy special positions, i.e. the pseudo-octahedral Ni(II) complex is located on a twofold axis and the TFDIB molecule sits about a crystallographic centre of inversion. The components interact via a short S···I contact of 3.2891 (12) Å between the thiocyanate S atom of the host and the iodine substituent at the perhalogenated aromatic ring of the smaller guest molecule. This interaction meets the commonly accepted criteria for a halogen bond. Such halogen bonds to sulfur are significantly less common than to smaller electronegative atoms.

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Section: Research Papersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Halogen bonds on demand: I...S contacts in cocrystals oftrans-bis(thiocyanato-κN)tetrakis(4-vinylpyridine-κN)nickel(II) and 2,3,5,6-tetrafluoro-1,4-diiodobenzene

et al. 2015

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“…The neutral molecule may act as a substituted pyridine; in its deprotonated form, acacPy À has been used as an O,O 0 chelating ligand towards divalent and trivalent cations (M) and as a ditopic ligand for the construction of oligo-or polynuclear binary coordination compounds (Mackay et al, 1995;Vreshch et al, 2003Vreshch et al, , 2004Vreshch et al, , 2005Chen et al, 2004;Zhang et al, 2008;Knight et al, 2008;Knight & McCusker, 2010;Li et al, 2011;Merkens et al, 2014;Truong et al, 2017a). In addition, the uncoordinated N atom in the pyridyl ring in [M(acacPy) 3 ] may provide electron density towards the hole in the strong halogen-bond partner 1,4diiodotetrafluorobenzene (Merkens et al, 2013). Despite these many structurally characterized derivatives, the structure of uncoordinated HacacPy itself has not yet been reported, to the best of our knowledge.…”

Section: Introductionmentioning

confidence: 99%

Phase transition and proton ordering at 50 K in 3-(pyridin-4-yl)pentane-2,4-dione

Truong

Merkens

Meven

et al. 2017

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Single-crystal neutron diffraction experiments at 100 and 2.5 K have been performed to determine the structure of 3-(pyridin-4-yl)pentane-2,4-dione (HacacPy) with respect to its protonation pattern and to monitor a lowtemperature phase transition. Solid HacacPy exists as the enol tautomer with a short intramolecular hydrogen bond. At 100 K, its donorÁÁÁacceptor distance is 2.450 (8) Å and the compound adopts space group C2/c, with the N and para-C atoms of the pyridyl ring and the central C of the acetylacetone substituent on the twofold crystallographic axis. As a consequence of the axial symmetry, the bridging hydrogen is disordered over two symmetrically equivalent positions, and the carbon-oxygen bond distances adopt intermediate values between single and double bonds. Upon cooling, a structural phase transition to the t 2 subgroup P " 1 1 occurs; the resulting twins show an ordered acetylacetone moiety. The phase transition is fully reversible but associated with an appreciable hysteresis in the large single crystal under study: transition to the lowtemperature phase requires several hours at 2.5 K and heating to 80 K is required to revert the transformation. No significant hysteresis is observed in a powder sample, in agreement with the second-order nature of the phase transition.

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“…1; Burrows et al, 2007;Kondracka & Englert, 2008;Merkens & Englert, 2012a;Merkens et al, 2012b], or 3-(pyridin-4-yl)acetylacetone, HacacPy [see (b) in Fig. 1; Chen et al, 2004;Li et al, 2011;Mackay et al, 1995;Merkens et al, 2013Merkens et al, , 2014Truong et al, 2017a;Vreshch et al, 2003Vreshch et al, , 2004Vreshch et al, , 2005Zhang et al, 2008], have been used to assemble the extended structures. Keto-enol equilibria in the uncoordinated species depend on the individual molecule, state of aggregation and solvent polarity (Truong et al, 2017c).…”

Section: Introductionmentioning

confidence: 99%

3-(Pyridin-4-yl)acetylacetone: a donor ligand towards mercury(II) halides and a versatile linker for complex materials

Truong

Merkens

Englert

2017

Acta Crystallogr Sect B

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The ditopic organic molecule 3-(pyridin-4-yl)acetylacetone (HacacPy) acts as a pyridine-type ligand towards HgX (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, namely a ligand-rich mononuclear complex, HgCl(HacacPy), and a ligand-deficient one-dimensional chain polymer, [Hg(μ-Cl)(HacacPy)], with five-coordinated Hg cations. Two compounds are also observed for HgBr, a molecular complex isomorphous to the chloride derivative and a chain polymer with the composition [Hg(μ-Br)Br(HacacPy)], 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 does not depend on the ligand-to-cation ratio but corresponds to [Hg(μ-I)I(HacacPy)], 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) and Al(acacPy) complexes in the first step. These mononuclear building blocks act as bridging poly(pyridine) ligands towards Hg 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 halides acting as linkers. In the alternative unprecedented product, both the tris(ligand) complexes and the [HgX(μ-X)HgX] groups act as equivalent triconnected nodes. They form a uninodal two-dimensional coordination network with vertex symbol 4.8 and fes topology.

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3-(4-Pyridyl)-2,4-pentanedione – a bridge between coordinative, halogen, and hydrogen bonds

Cited by 56 publications

References 37 publications

Halogen bonds on demand: I...S contacts in cocrystals oftrans-bis(thiocyanato-κN)tetrakis(4-vinylpyridine-κN)nickel(II) and 2,3,5,6-tetrafluoro-1,4-diiodobenzene

Halogen bonds on demand: I...S contacts in cocrystals oftrans-bis(thiocyanato-κN)tetrakis(4-vinylpyridine-κN)nickel(II) and 2,3,5,6-tetrafluoro-1,4-diiodobenzene

Phase transition and proton ordering at 50 K in 3-(pyridin-4-yl)pentane-2,4-dione

3-(Pyridin-4-yl)acetylacetone: a donor ligand towards mercury(II) halides and a versatile linker for complex materials

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