Two isostructural complexes of Ni(ii) and Zn(ii) with violurate and pyridine: a detailed structural, theoretical, magnetic, and NMR investigation
文献信息
Susital Mal, Rupak Banik, Subrata Das, Ľubor Dlháň, Ján Titiš, Roman Boča, Alexander M. Kirillov, Paul Hazendonk, Ray J. Butcher, Antonio Bauza, Antonio Frontera
Two new metal(II) complexes [M(dmv)2(py)2]·3H2O {M = Ni (1), Zn (2)} were self-assembled from a metal(II) chloride salt, N,N′-dimethylvioluric acid (Hdmv), and pyridine (py). They were isolated as stable crystalline solids and characterized, including by single crystal X-ray diffraction. Structures 1 and 2 are composed of discrete [M(dmv)2(py)2] blocks in which the six-coordinate metal(II) atoms show a slightly distorted {MN4O2} octahedral geometry. The adjacent [M(dmv)2(py)2] units are hydrogen bonded with an involvement of disordered water clusters into 1D H-bonded chains. DFT calculations were used to analyse the unconventional anti-parallel CO⋯CO interaction observed between the monomeric units in 1 and 2. Complex 1 also refers to an elongated tetragonal bipyramid for which a positive zero-field splitting is confirmed by magnetic studies. The complex matches the magnetostructural D-correlation for hexacoordinate Ni(II) complexes with moderate structural and magnetic anisotropy with Dstr = +7.45 pm, and Dmag = +5.11 cm−1. Solution state NMR spectroscopy reveals a slow isomerization process related to the bidentate-N,O and bidentate-O,O coordination of dimethylviolurate in 2, with the barrier ranging from 76.4 to 77.9 kJ mol−1. The 1H NMR spectra confirm the presence of three water molecules which exhibit significant chemical shift dependence on temperature indicating strong binding to the complex in solution phase.
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CrystEngComm

CrystEngComm is the forum for the design and understanding of crystalline materials. We welcome studies on the investigation of molecular behaviour within crystals, control of nucleation and crystal growth, engineering of crystal structures, and construction of crystalline materials with tuneable properties and functions. We publish hypothesis-driven research into… how crystal design affects thermodynamics, phase transitional behaviours, polymorphism, morphology control, solid state reactivity (crystal-crystal solution-crystal, and gas-crystal reactions), optoelectronics, ferroelectric materials, non-linear optics, molecular and bulk magnetism, conductivity and quantum computing, catalysis, absorption and desorption, and mechanical properties. Using Techniques and methods including… Single crystal and powder X-ray, electron, and neutron diffraction, solid-state spectroscopy, spectrometry, and microscopy, modelling and data mining, and empirical, semi-empirical and ab-initio theoretical evaluations. On crystalline and solid-state materials. We particularly welcome work on MOFs, coordination polymers, nanocrystals, host-guest and multi-component molecular materials. We also accept work on peptides and liquid crystals. All papers should involve the use or development of a design or optimisation strategy. Routine structural reports or crystal morphology descriptions, even when combined with an analysis of properties or potential applications, are generally considered to be outside the scope of the journal and are unlikely to be accepted.