Melem (2,5,8-triamino-tri-s-triazine), an important intermediate during condensation of melamine rings to graphitic carbon nitride:: Synthesis, structure determination by X-ray powder diffractometry, solid-state NMR, and theoretical studies

Single-phase melem (2,5,8-triamino-tri-s-triazine) C6N7(NH2)(3) was obtained as a crystalline powder by thermal treatment of different less condensed C-N-H compounds (e.g., melamine C3N3(NH2)(3), dicyandiamide H4C2N4, ammonium dicyanamide NH4[N(CN)(2)], or cyanamide H2CN2, respectively) at temperatures up to 450 degreesC in sealed glass ampules. The crystal structure was determined ab initio by X-ray powder diffractometry (Cu Kalpha(1): P2(1)/c (No. 14), a = 739.92(1) pm, b = 865.28(3) pm, c = 1338.16(4) pm, beta = 99.912(2)degrees, and Z = 4). In the solid, melem consists of nearly planar C6N7(NH2)(3) molecules which are arranged into parallel layers with an interplanar distance of 327 pm. Detailed C-13 and N-15 MAS NMR investigations were performed. The presence of the triamino form instead of other possible tautomers was confirmed by a CPPI (cross-polarization combined with polarization inversion) experiment. Furthermore, the compound was characterized using mass spectrometry, vibrational (IR, Raman), and photoluminescence spectroscopy. The structural and vibrational properties of molecular melem were theoretically studied on both the B3LYP and the MP2 level. A structural optimization in the extended state was performed employing density functional methods utilizing LDA and GGA. A good agreement was found between the observed and calculated structural parameters and also for the vibrational frequencies of melem. According to temperature-dependent X-ray powder diffractometry investigations above 560 degreesC, melem transforms into a graphite-like C-N material.