RESUMO
We report a [3+2] cycloaddition using 3,6-bis-propargyloxy-1,2,4,5-tetrazine and azides to synthesize energetic polymers containing 1,2,4,5-tetrazine within the scaffold. This work also includes [3+2] cycloaddition to crosslink azide containing glycidyl azide polymer (GAP). These reactions provide pathways for incorporation of 1,2,4,5-tetrazine into novel energetic materials using click-chemistry and provide an alternative polymer curing approach.
RESUMO
The reaction of 3,4-dinitropyrazole, 5-nitrotetrazole, or 4-nitro-1,2,3-triazole with 1,2,4,5-tetrazines substituted with 3,5-dimethylpyrazolyl (dmp) groups results in energetic cocrystals after 1 minute of reflux and cooling to room temperature in yields of 89-92 %. Hydrogen-bonding between the dmp group to the N-H of the energetic heterocycles are the predominant interaction that stabilizes the new cocrystals. Each cocrystal packs in a different lattice structure and the cocrystals with sheet-like and herring-bone crystal packing orientations are less sensitive than the cocrystal with the interlocked structure. Electrostatic potential mapping helps rationalize why dmp-substituted tetrazines readily form cocrystals, whereas more electron-deficient pyrazolyl tetrazines do not. The calculated energetic performance of the new cocrystals approaches that of 2,4,6-trinitrotoluene (TNT) and importantly, these materials will aid in the rational design of new cocrystalline energetic materials.
RESUMO
In the mol-ecule of neutral bis-[(1H-tetra-zol-5-yl)meth-yl]nitramide, (I), C4H6N10O2, there are two intra-molecular N-Hâ¯O hydrogen bonds. In the crystal, N-Hâ¯N hydrogen bonds link mol-ecules, forming a two-dimensional network parallel to (-201) and weak C-Hâ¯O, C-Hâ¯N hydrogen bonds, and inter-molecular π-π stacking completes the three-dimensional network. The anion in the molecular salt, tri-amino-guanidinium 5-({[(1H-tetra-zol-5-yl)meth-yl](nitro)-amino}-meth-yl)tetra-zol-1-ide, (II), CH9N6+·C4H5N10O2-, displays intra-molecular π-π stacking and in the crystal, N-Hâ¯N and N-Hâ¯O hydrogen bonds link the components of the structure, forming a three-dimensional network. In the crystal of di-ammonium bis-[(tetra-zol-1-id-5-yl)meth-yl]nitramide monohydrate, (III), 2NH4+·C4H4N10O22-·H2O, O-Hâ¯N, N-Hâ¯N, and N-Hâ¯O hydrogen bonds link the components of the structure into a three-dimensional network. In addition, there is inter-molecular π-π stacking. In all three structures, the central N atom of the nitramide is mainly sp2-hybridized. Bond lengths indicate delocalization of charges on the tetra-zole rings for all three compounds. Compound (II) was found to be a non-merohedral twin and was solved and refined in the major component.
RESUMO
In the title compound, C5HN7, the nitrile and azido substituents are close to being coplanar with the central ring. Mol-ecules in the crystal are linked via an N-Hâ¯N hydrogen bond to a nitrile acceptor, forming a chain extending along the c-axis direction.
RESUMO
The title compound, C3H2N4O4, forms crystals with two mol-ecules in the asymmetric unit which are conformationally similar. With the exception of the O atoms of the nitro groups, the mol-ecules are essentially planar. In the crystal, adjacent mol-ecules are associated by N-Hâ¯N hydrogen bonds involving the imidazole N-H donors and N-atom acceptors of the unsaturated nitro-gen of neighboring rings, forming layers parallel to (010).
RESUMO
In the title compound, C5N6, all the atoms are approximately coplanar. In the crystal, mol-ecules are packed with short contact distances of 2.885â (2) (between the diazo N atom connected to the ring and a cyano N atom on a neighboring mol-ecule) and 3.012â (2)â Å (between the terminal diazo N atom and an N atom of a neighboring imidazole ring).
RESUMO
Hexaferrocenylbenzene has been synthesized by six-fold Negishi type ferrocenylation of hexabromo- or hexaiodobenzene.