Inorganic–organic hybrid salts of diaminobenzenes and related cations

Abstract

We describe ten new inorganic–organic hybrid ionic crystal structures containing isomers of diaminobenzene dication as well as related moieties such as N,N-substituted ions, benzotriazol or diamino pyridinium cations. Each of the structures contains complex inorganic metal-halide anions. We also used structural data retrieved from the CSD for 32 salts containing metal halide complexes. In order to compare the arrangements of moieties we proposed criteria defining the final architecture of such systems. Twenty-eight structures—including seven with anions polymerized in sheets—can be treated as of 2-D type and eleven—including two with anions polymerized in rods—as of 1-D type, while the remaining three as having 0-D final crystal architecture. We have defined several structural parameters describing 2-D and/or 1-D densities of packing of ions (ρ_2-D and ρ_1-D, respectively), properties and orientation of cations in the crystal lattice, namely the inter-stack/row distance (s), distance between the mean planes passing through complex anions (d), angle defining the tilt between the N–N axis of the cation with respect to the layers passing through complex anions (τ), and angle describing the relative, average distortion of the N–N axis of the cations in one stack (φ). We have found several significant relationships for them. Among others, it appears that ρ_2-D correlates with ρ_1-D, s and τ. We discuss details of these and others structural relationships.