Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes
Mailman, A., Puttreddy, R., Lahtinen, M., Svahn, N., & Rissanen, K. (2020). Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes. Chemistry, 2(3), 700-713. https://doi.org/10.3390/chemistry2030045
DisciplineOrgaaninen kemiaSoveltavan kemian yksikköEpäorgaaninen ja analyyttinen kemiaOrganic ChemistryThe Unit of Applied ChemistryInorganic and Analytical Chemistry
© 2020 by the authors. Licensee MDPI, Basel, Switzerland
A new class of six mono- (1; 3-Cl-, 2; 5-Cl-, 3; 6-Cl-) and di-(4; 3,6-Cl, 5; 5,6-Cl-, 6; 3,5-Cl-) chloro-substituted pyrazin-2-amine ligands (1–6) form complexes with copper (I) bromide, to give 1D and 2D coordination polymers through a combination of halogen and hydrogen bonding that were characterized by X-ray diffraction analysis. These Cu(I) complexes were prepared indirectly from the ligands and CuBr2 via an in situ redox process in moderate to high yields. Four of the pyrazine ligands, 1, 4–6 were found to favor a monodentate mode of coordination to one CuI ion. The absence of a C6-chloro substituent in ligands 1, 2 and 6 supported N1–Cu coordination over the alternative N4–Cu coordination mode evidenced for ligands 4 and 5. These monodentate systems afforded predominantly hydrogen bond (HB) networks containing a catenated (μ3-bromo)-CuI ‘staircase’ motif, with a network of ‘cooperative’ halogen bonds (XB), leading to infinite polymeric structures. Alternatively, ligands 2 and 3 preferred a μ2-N,N’ bridging mode leading to three different polymeric structures. These adopt the (μ3-bromo)-CuI ‘staircase’ motif observed in the monodentate ligands, a unique single (μ2-bromo)-CuI chain, or a discrete Cu2Br2 rhomboid (μ2-bromo)-CuI dimer. Two main HB patterns afforded by self-complimentary dimerization of the amino pyrazines described by the graph set notation R22(8) and non-cyclic intermolecular N–H∙∙∙N’ or N–H∙∙∙Br–Cu leading to infinite polymeric structures are discussed. The cooperative halogen bonding between C–Cl∙∙∙Cl–C and the C–Cl∙∙∙Br–Cu XB contacts are less than the sum of the van der Waals radii of participating atoms, with the latter ranging from 3.4178(14) to 3.582(15) Å. In all cases, the mode of coordination and pyrazine ring substituents affect the pattern of HBs and XBs in these supramolecular structures. ...
Publication in research information system
MetadataShow full item record
Related funder(s)European Commission; Academy of Finland
Funding program(s)Postdoctoral Researcher, AoF; Academy Project, AoF
The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
Additional information about fundingThis work was financially supported by the Academy of Finland (projects 298817 and 289172), the University of Jyväskylä, and in part by the European Union’s H2020 program, under the Marie Skłodowska-Curie grant agreement 659123 for A.M.
Showing items with similar title or keywords.
von Essen, C.; Rissanen, K.; Puttreddy, R. (MDPI, 2019)Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the ...
Kramer, Eric; Yu, Shilin; Ward, Jas S.; Rissanen, Kari (Royal Society of Chemistry (RSC), 2021)Four bis(O–I–N) compounds have been synthesised from various dihypoiodites and 4-ethylpyridine. The compounds were characterised in both the solution and solid states by NMR spectroscopy (1H, 15N), X-ray diffraction, and ...
Valkonen, Arto; Chukhlieb, Maryna; Moilanen, Jani; Tuononen, Heikki; Rissanen, Kari (American Chemical Society, 2013)Three derivatives of 5-iodouracil were prepared, and their complexation properties, supplemented by 5-iodouracil under the same conditions, were studied with and without halogen bond acceptors in N,N-dimethylformamide, ...
Cocrystal trimorphism as a consequence of the orthogonality of halogen- and hydrogen-bonds synthons Topić, Filip; Lisac, Katarina; Arhangelskis, Mihails; Rissanen, Kari; Cinčić, Dominik; Friščić, Tomislav (Royal Society of Chemistry, 2019)True trimorphic cocrystals, i.e. multi-component molecular crystals of identical composition that exhibit three polymorphic structures, are exceedingly rare and so far no halogen-bonded cocrystal system has been reported ...
Puttreddy, Rakesh; Rautiainen, Mikko; Mäkelä, Toni; Rissanen, Kari (Wiley-VCH Verlag, 2019)A detailed study of the strong N−X⋯−O−N+ (X = I, Br) halogen bonding interactions in solution and in the solid‐state reports 2×27 donor×acceptor complexes of N‐halosaccharins and pyridine N‐oxides (PyNO). Density Functional ...