The structural properties of dichlorodiazadienes synthesized based on 4-methylbenzaldehyde

Dichlorodiazadienes were synthesized based on 4-methylbenzaldehyde, the structures of some compounds were confirmed via the X-ray method and a series of crystallographic properties, the role of non-covalent interactions in the forming of crystal, and (using Hirshfeld surface analysis) intermolecular interactions were studied. It was determined that as the result of the impact of nitro-group on the direction of the reactions of (E)-1-(4-methylbenzylydene)-2-(4-nitrophenyl)-hidrazone with CCl4 and CBr4, reaction by-products E)-1-(4-nitrophenyl)-2-(1,1,1-trichloro-2-methylpropan-2-yl)diazene, (Z)-4-methyl-N-(4nitrophenyl)benzohydra-zonoyl chloride and (Z)-4-methyl-N-(4-nitrophenyl)benzohydrazonoylbromide had been formed. While (E)-1-(2,2-dichloro-1-(p-tolyl)vinyl)-2-(3,4-dimethylphenyl)diazene crystallizes in the monoclinic P21/n space group with Z = 4, (E)-4-((2,2-dichloro-1-(p-tolyl)vinyl)diazenyl) benzonitrile crystallizes in the monoclinic Cc space group with four independent molecules (I, II, III and IV) in the asymmetric unit (Z = 16), and (E)-1-(4-nitrophenyl)-2-(1,1,1-trichloro-2-methylpropan-2-yl)diazene and (Z)-4-methyl-N-(4-nitrophenyl)benzohydrazonoylbromide crystallize in the monoclinic P21/c space group with Z = 4. The molecules in the crystal of (E)-1-(2,2-dichloro-1-(p-tolyl)vinyl)-2-(3,4-dimethylphenyl)diazene are linked into infinite three-dimensional network by C−H···N of hydrogen bonds, C---H…π and C---Cl…π interaction. In the crystal of the (E)-4-((2,2-dichloro-1-(p-tolyl)vinyl)diazenyl) benzonitrile, while molecules are linked in layers parallel to the (200) plane by intermolecular C---H…N hydrogen bonds and C---H…π interactions, in the crystal of the (E)-1-(4-nitrophenyl)-2-(1,1,1-trichloro-2-methylpropan-2-yl)diazene, the molecules are connected in layers parallel to the (10-2) plane by intermolecular C---H…O hydrogen bonds, C---Cl… π and π-π interactions, and in the crystal of the (Z)-4-methyl-N-(4 nitrophenyl)benzohydrazonoylbromide, the molecules are connected in layers parallel to the (020) plane by intermolecular C---H…O and N---H…O hydrogen bonds and C--O…π interactions. These layers bond with van der Waals interactions, strengthening the crystal structure. © 2025 Elsevier B.V., All rights reserved.