Protonated melonate Ca[HC6N7(NCN)3]·7H2O – synthesis, crystal structure, and thermal properties

Calcium hydrogenmelonate heptahydrate Ca[HC6N7(NCN)3]·7H2O was obtained by metathesis reaction in aqueous solution. The structure of the molecular salt was elucidated by single-crystal X-ray diffraction. The crystal structure consists of alternating layers of planar monopronated melonate ions, Ca2+ and crystal water molecules. The anions of adjacent layers are staggered so that no π–π stacking occurs. The melonate entities are interconnected by hydrogen bonds within and between the layers. Ca[HC6N7(NCN)3]·7H2O was investigated by solid-state NMR and FTIR spectroscopy, TG and DTA measurements.

Poly(triazine imide) with intercalation of Lithium and ChlorideiIons [(C3N3)2(NHxLi1−x)3⋅LiCl]: A Crystalline 2D Carbon Nitride network

Poly(triazine imide) with intercalation of lithium and chloride ions (PTI/Li+Cl−) was synthesized by temperature-induced condensation of dicyandiamide in a eutectic mixture of lithium chloride and potassium chloride as solvent. By using this ionothermal approach the well-known problem of insufficient crystallinity of carbon nitride (CN) condensation products could be overcome. The structural characterization of PTI/Li+Cl− resulted from a complementary approach using spectroscopic methods as well as different diffraction techniques. Due to the high crystallinity of PTI/Li+Cl− a structure solution from both powder X-ray and electron diffraction patterns using direct methods was possible; this yielded a triazine-based structure model, in contrast to the proposed fully condensed heptazine-based structure that has been reported recently. Further information from solid-state NMR and FTIR spectroscopy as well as high-resolution TEM investigations was used for Rietveld refinement with a goodness-of-fit (χ2) of 5.035 and wRp=0.05937. PTI/Li+Cl− (P63cm (no. 185); a=846.82(10), c=675.02(9) pm) is a 2D network composed of essentially planar layers made up from imide-bridged triazine units. Voids in these layers are stacked upon each other forming channels running parallel to [001], filled with Li+ and Cl− ions. The presence of salt ions in the nanocrystallites as well as the existence of sp2-hybridized carbon and nitrogen atoms typical of graphitic structures was confirmed by electron energy-loss spectroscopy (EELS) measurements. Solid-state NMR spectroscopy investigations using 15N-labeled PTI/Li+Cl− proved the absence of heptazine building blocks and NH2 groups and corroborated the highly condensed, triazine-based structure model.