Comparison of hydrogen bonds and diverse weak interactions of the nitro group in 2-methyl-4-nitroanilinium nitrate, bisulfate and two hexafluoridosilicates: elementary graph-set approach

Crystal structures of (H2m4na)NO₃ (1), (H2m4na)HSO₄ (2), (H2m4na)₂SiF₆ (3) and (H2m4na)₂SiF₆·2H₂O (4), where 2m4na = 2-methyl-4-nitroaniline, are presented. Two layers of interactions occur in the structures, N-H...O/F hydrogen bonds and interactions with the nitro group. Although diverse, hydrogen-bonding patterns are compared with each other by means of interrelations among elementary graph-set descriptors and descriptors of hydrogen-bonding patterns. Using mathematical relations, the gradual expansion of the ring patterns was shown in the crystal structures. Parallel and perpendicular arranged nitro groups form weak π(N)_NO2...π(O)_NO2 and π(N)_NO2...O_NO2 interactions, respectively. The π_NO2...π_ring interaction has an impact to the stabilization of parallel oriented nitro groups. Generally, weak interactions constructed by the nitro group occur in the studied crystals as follows: π(N)_NO2...π(O)_NO2, π_ring...π_ring, C-H...O (1); π(N)_NO2...π(O)_NO2, π(N)_NO2...O_NO2 (2); π(N)_NO2...π(O)_NO2, π(N)_NO2...O_NO2 (3); C-H...O (4).