Premium
Crystalline Intermediates during Polycondensation Reactions in the C–N–Cl System – The Paddle‐Wheel Molecule N(C 6 N 7 Cl 2 ) 3
Author(s) -
Tragl Sonja,
Gibson Katharina,
Glaser Jochen,
Heydenrych Greta,
Frenking Gernot,
Duppel Viola,
Simon Arndt,
Meyer H.Jürgen
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200800092
Subject(s) - chemistry , cyanuric chloride , crystallinity , alkali metal , salt metathesis reaction , inorganic chemistry , lithium (medication) , molecule , crystallography , nitride , metathesis , polymer chemistry , organic chemistry , medicine , layer (electronics) , polymerization , endocrinology , polymer
Solid state metathesis reactions between cyanuric chloride and C–N–H or alkali metal–(B–)C–N compounds, respectively, were carried out in the temperature range between 150 °C to 500 °C, studying intermediate stages of reactions and targeting the formation of carbon nitride materials by elimination of HCl or alkali metal chlorides. Although cyanuric chloride was reacted with quite a number of different reaction partners such as melamine, cyanamide, lithium nitride, lithium or sodium carbodiimide, lithium nitridoborate or sodium dicyandiamide, always the same intermediate compounds appeared in the reactions mixtures. Colorless, needle‐shaped crystals of the tertiary amine N(C 3 N 3 Cl 2 ) 3 ( 1 ) were obtained at temperatures around 200–250 °C. Temperatures as high as 400 °C yielded yellow, plate‐like crystals of the heptazine compound C 6 N 7 Cl 3 ( 2 ). At even higher temperatures, the reaction products were of poorer crystallinity, but evidence of the formation of another crystalline intermediate was given by X‐ray powder diffraction and electron diffraction experiments. This third intermediate is assumed to be a tertiary amine, quite similar to 1 , however, having heptazine ligands instead of triazine ligands and is assigned with the formula N(C 6 N 7 Cl 2 ) 3 ( 3 ). Theoretical calculations were performed for the structures and the vibrational spectra of 1 and 3 . Theoretical calculations and a structure refinement based of X‐ray powder diffraction data yielded a plausible structural model for compound 3 .