Lorenz Volker, Liebing Phil, Müller Matthias, Hilfert Liane, Feneberg Martin, Kluth Elias, Kühling Marcel, Buchner Magnus R, Goldhahn Rüdiger, Edelmann Frank T
Chemisches Institut, Otto-von-Guericke-Universität Magdeburg, Universitätsplatz 2, 39106 Magdeburg, Germany.
Institut für Anorganische und Analytische Chemie, Humboldtstr. 8, 07743 Jena, Germany.
Dalton Trans. 2022 May 24;51(20):7975-7985. doi: 10.1039/d2dt00606e.
A series of brightly colored alkaline earth metal 1,3-dimethylviolurates M(MeVio) have been prepared and fully characterized. The title compounds AE(MeVio)·HO (AE = Mg, = 6 (3); AE = Ca, = 8 (4), AE = Sr, = 6 (5); AE = Ba, = 4 (6)) were obtained by neutralizing 1,3-dimethylvioluric acid monohydrate (=H(MeVio)·HO; 2) with 0.5 equiv. of the corresponding metal dihydroxides AE(OH). The hair-like appearance of the Sr derivative 5 prevented the growth of single-crystals. This problem could be solved by crystallizing the crown ether derivative Sr(MeVio)(18-crown-6) (5a). The isolated salts exhibit intense colors ranging from red to purple. Various attempts to prepare the beryllium derivative Be(MeVio) failed. Instead, work-up of the reaction mixtures provided pink crystals of a new modification of 2 formulated as [HO][MeVio] (2b) as shown by an X-ray diffraction study. An unexpected oxidation reaction of the barium salt Ba(MeVio) led to formation of the novel mixed-anion salt Ba(MeVio)(MeNOBarb)·2HO (8, MeNOBarb = 1,3-dimethyl-5-nitrobarbiturate anion). Compound 8 could also be synthesized deliberately by treatment of Ba(OH) with a 1 : 1 mixture of 2 and 1,3-dimethyl-5-nitrobarbituric acid (7, =H(MeNOBarb)·HO). All new compounds were fully characterized by their IR, Raman, NMR (H, C{H}) and UV-vis spectra as well as elemental analyses. Single-crystal X-ray diffraction studies revealed that the solid-state structures of compounds 3, 4, 5a and 6 are governed by the typical coordination behavior of the alkaline-earth metals, increasing coordination numbers and a decreasing degree of hydration when going from Mg to Ba. The dimensions of the structures range from hydrogen-bonded ions (3) over monomeric, neutral complex molecules (4, 5a), to polymeric networks (6). The successful isolation of the mixed-anion barium salt 8 adds a new facet to the coordination chemistry of violurate and related ligands.
