Crystal structures of an imidazo[1,5-a]pyridinium-based ligand and its (C13H12N3)2[CdI4] hybrid salt

The monocation product of the oxidative condensation-cyclization between two molecules of pyridine-2-carbaldehyde and one molecule of CH3NH2 center dot HCl in methanol, 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium, was isolated in the presence of metal ions as bis[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] tetraiodocadmate, (C13H12N3)(2)[CdI4], (I), and the mixed chloride/nitrate salt, bis[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] 1.5-chloride 0.5-nitrate trihydrate, 2C(13)H(12)N(3)(+)center dot 1.5Cl(-)center dot 0.5NO(3)(-)center dot 3H(2)O, (II). Hybrid salt (I) crystallizes in the space group P2(1)/n with two [L](2)[CdI4] molecules in the asymmetric unit related by pseudosymmetry. In the crystal of (I), layers of organic cations and of tetrahalometallate anions are stacked parallel to the ab plane. Antiparallel L+ cations disposed in a herring-bone pattern form pi-bonded chains through aromatic stacking. In the inorganic layer, adjacent tetrahedral CdI4 units have no connectivity but demonstrate close packing of iodide anions. In the crystal lattice of (II), the cations are arranged in stacks propagating along the a axis; the one-dimensional hydrogen-bonded polymer built of chloride ions and water molecules runs parallel to a column of stacked cations.