Crystal structures and Hirshfeld surface analyses of methyl 4-{2,2-di-chloro-1-[(E)-phenyl-diazen-yl]eth-enyl}benzoate, methyl 4-{2,2-di-chloro-1-[(E)-(4-methyl-phen-yl)diazen-yl]ethen-yl}benzoate and methyl 4-{2,2-di-chloro-1-[(E)-(3,4-di-methyl-phen-yl)diazen-yl]ethen-yl}benzoate.

The crystal structures and Hirshfeld surface analyses of three similar azo compounds are reported. Methyl 4-{2,2-di-chloro-1-[(E)-phenyl-diazen-yl]ethen-yl}benzoate, C16H12Cl2N2O2, (I), and methyl 4-{2,2-di-chloro-1-[(E)-(4-methyl-phen-yl)diazen-yl]ethen-yl}benzoate, C17H14Cl2N2O2, (II), crystallize in the space group P21/c with Z = 4, and methyl 4-{2,2-di-chloro-1-[(E)-(3,4-di-methyl-phen-yl)diazen-yl]ethen-yl}benzoate, C18H16Cl2N2O2, (III), in the space group P with Z = 2. In the crystal of (I), mol-ecules are linked by C-H⋯N hydrogen bonds, forming chains with C(6) motifs parallel to the b axis. Short inter-molecular Cl⋯O contacts of 2.8421 (16) Šand weak van der Waals inter-actions between these chains stabilize the crystal structure. In (II), mol-ecules are linked by C-H⋯O hydrogen bonds and C-Cl⋯π inter-actions, forming layers parallel to (010). Weak van der Waals inter-actions between these layers consolidate the mol-ecular packing. In (III), mol-ecules are linked by C-H⋯π and C-Cl⋯π inter-actions forming chains parallel to [011]. Furthermore, these chains are connected by C-Cl⋯π inter-actions parallel to the a axis, forming (01) layers. The stability of the mol-ecular packing is ensured by van der Waals forces between these layers.

Crystal structure and Hirshfeld surface analysis of 4-azido-2-(3,5-di-methyl-phen-yl)-5-(4-nitro-phen-yl)-2H-1,2,3-triazole.

In the title compound, C16H13N7O2, the 3,5-di-methyl-phenyl and 4-nitro-phenyl rings are inclined to the central 2H-1,2,3-triazole ring by 1.80 (7) and 1.79 (7)°, respectively, and to one another by 2.16 (7)°. In the crystal, the mol-ecules are linked by C-H⋯N hydrogen bonds and π-π stacking inter-actions [centroid-to-centroid distances = 3.7295 (9) and 3.7971 (9) Å], forming ribbons along the b-axis direction. These ribbons are connected to each other by weak van der Waals inter-actions and the stability of the crystal structure is ensured. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (31.5%), N⋯H/H⋯N (19.2%), O⋯H/H⋯O (14.5%), N⋯C/C⋯C (10.9%) and C⋯H/H⋯C (10.2%) contacts.

Crystal structures and Hirshfeld surface analyses of (E)-1-[1-(4-tert-butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-phenyl-diazene, (E)-1-[1-(4-tert-butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-(4-methyl-phen-yl)diazene, (E)-1-[1-(4-tert-butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-(4-meth-oxy-phen-yl)diazene and (E)-1-[1-(4-tert-butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-(3-methyl-phen-yl)diazene.

The crystal structures and Hirshfeld surface analyses of four similar azo compounds are reported. (E)-1-[1-(4-tert-Butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-phenyl-diazene, C18H18Cl2N2, (I), and (E)-1-[1-(4-tert-butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-(4-methyl-phen-yl)diazene, C19H20Cl2N2, (II), crystallize in the monoclinic space group C2/c with Z = 8, and (E)-1-[1-(4-tert-butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-(4-meth-oxy-phen-yl)diazene, C19H20Cl2N2O, (III), in the monoclinic space group P21/c with Z = 4. (E)-1-[1-(4-tert-Butyl-phen-yl)-2,2-di-chloro-ethen-yl]-2-(3-methyl-phen-yl)diazene, C19H20Cl2N2, (IV), crystallizes in the triclinic space group P with Z = 4 and comprises two mol-ecules (A and B) in the asymmetric unit. In the crystal structures of (I) and (II), mol-ecules are linked by C-H⋯π and C-Cl⋯π inter-actions, forming layers parallel to (02), while mol-ecules of (III) are linked by C-H⋯O contacts, C-H⋯π and C-Cl⋯π inter-actions forming layers parallel to (02). The stability of the mol-ecular packing is ensured by van der Waals forces between these layers. In the crystal structure of (IV), mol-ecules are linked by C-H⋯π and C-Cl⋯π inter-actions, forming a tri-periodic network.

Crystal structure and Hirshfeld surface analysis of a new polymorph of (E)-2-(4-bromo-phen-yl)-1-[2,2-di-bromo-1-(3-nitro-phen-yl)ethen-yl]diazene.

A new polymorph of the title compound, C14H8Br3N3O2, (form-2) was obtained in the same manner as the previously reported form-1 [Akkurt et al. (2022 ▸). Acta Cryst. E78, 732-736]. The structure of the new polymorph is stabilized by a C-H⋯O hydrogen bond that links mol-ecules into chains. These chains are linked by face-to-face π-π stacking inter-actions, resulting in a layered structure. Short inter-mol-ecular Br⋯O contacts and van der Waals inter-actions between the layers aid in the cohesion of the crystal packing. In the previously reported form-1, C-H⋯Br inter-actions connect mol-ecules into zigzag chains, which are linked by C-Br⋯π inter-actions into layers, whereas the van der Waals inter-actions between the layers stabilize the crystal packing of form-2. Hirshfeld mol-ecular surface analysis was used to compare the inter-molecular inter-actions of the polymorphs.

Crystal structure and Hirshfeld surface analysis of (E)-2-(4-bromo-phen-yl)-1-[2,2-di-bromo-1-(4-nitro-phen-yl)ethen-yl]diazene.

The mol-ecule of the title compound, C14H8Br3N3O2, consists of three almost planar groups: the central di-bromo-ethenyldiazene fragment and two attached aromatic rings. The mean planes of these rings form dihedral angles with the plane of the central fragment of 26.35 (15) and 72.57 (14)° for bromine- and nitro-substituted rings, respectively. In the crystal, C-H⋯Br inter-actions connect mol-ecules, generating zigzag C(8) chains along the [100] direction. These chains are linked by C-Br⋯π inter-actions into layers parallel to (001). van der Waals inter-actions between the layers aid in the cohesion of the crystal packing. The most substantial contributions to crystal packing, according to a Hirshfeld surface analysis, are from Br⋯H/H⋯Br (20.9%), C⋯H/H⋯C (15.2%), O⋯H/H⋯O (12.6%) and H⋯H (11.7%) contacts.

Crystal structure and Hirshfeld surface analysis of (E)-1-[2,2-di-bromo-1-(4-nitro-phen-yl)ethen-yl]-2-(4-fluoro-phen-yl)diazene.

In the title compound, C14H8Br2FN3O2, the 4-fluoro-phenyl ring and the nitro-substituted phenyl ring form a dihedral angle of 64.37 (10)°. Mol-ecules in the crystal are connected by C-H⋯O and C-H⋯F hydrogen bonds into layers parallel to (011). The crystal packing is consolidated by C-Br⋯π and C-F⋯π inter-actions, as well as by π-π stacking inter-actions. According to a Hirshfeld surface analysis of the crystal structure, the most significant contributions to the crystal packing are from O⋯H/H⋯O (15.0%), H⋯H (14.3%), Br⋯H/H⋯Br (14.2%), C⋯H/H⋯C (10.1%), F⋯H/H⋯F (7.9%), Br⋯Br (7.2%) and Br⋯C/C⋯Br (5.8%) contacts.

Crystal structure and Hirshfeld surface analysis of (E)-1-[2,2-di-bromo-1-(2-nitro-phen-yl)ethen-yl]-2-(4-fluoro-phen-yl)diazene.

In the title compound, C14H8Br2FN3O2, the nitro-substituted benzene ring and the 4-fluoro-phenyl ring form a dihedral angle of 65.73 (7)°. In the crystal, mol-ecules are linked into chains by C-H⋯O hydrogen bonds running parallel to the c-axis direction. The crystal packing is consolidated by C-F⋯π inter-actions and π-π stacking inter-actions, and short Br⋯O [2.9828 (13) Å] contacts are observed. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (17.4%), O⋯H/H⋯O (16.3%), Br⋯H/H⋯Br (15.5%), Br⋯C/C⋯Br (10.1%) and F⋯H/H⋯F (8.1%) contacts.

Crystal structure and Hirshfeld surface analysis of (E)-1-[2,2-di-chloro-1-(4-fluoro-phen-yl)ethen-yl]-2-(2,4-di-chloro-phen-yl)diazene.

In the title compound, C14H7Cl4FN2, the dihedral angle between the 4-fluoro-phenyl ring and the 2,4-di-chloro-phenyl ring is 46.03 (19)°. In the crystal, the mol-ecules are linked by C-H⋯N inter-actions along the a-axis direction, forming a C(6) chain. The mol-ecules are further connected by C-Cl⋯π inter-actions and face-to-face π-π stacking inter-actions, forming ribbons along the a-axis direction. Hirshfeld surface analysis indicates that the greatest contributions to the crystal packing are from Cl⋯H/H⋯Cl (35.1%), H⋯H (10.6%), C⋯C (9.7%), Cl⋯Cl (9.4%) and C⋯H/H⋯C (9.2%) inter-actions.

Crystal structure and Hirshfeld surface analysis of 3-[2-(3,5-di-methyl-phen-yl)hydrazinyl-idene]benzo-furan-2(3H)-one.

In the title compound, C16H14N2O2, the 2,3-di-hydro-1-benzo-furan ring system is essentially planar and makes a dihedral angle of 3.69 (7)° with the di-methyl-phenyl ring. The mol-ecular conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond with an S(6) ring motif. In the crystal, mol-ecules are connected by C-H⋯π and π-π stacking inter-actions, forming a layer lying parallel to the (11) plane. One methyl group is disordered over two orientations, with occupancies of 0.67 (4) and 0.33 (4). Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (51.2%), O⋯H/H⋯O (17.9%), C⋯H/H⋯C (15.2%) and C⋯C (8.1%) contacts.

Crystal structure and Hirshfeld surface analysis of (E)-4-({2,2-di-chloro-1-[4-(di-methyl-amino)-phen-yl]ethenyl}diazen-yl)benzo-nitrile.

In the title compound, C17H14Cl2N4, the dihedral angle between the aromatic rings is 50.09 (9)°. The central -N=N- unit shows an E configuration. In the crystal, C-H⋯N inter-actions, C-Cl⋯π and π-π stacking inter-actions [centroid-to-centroid distance = 3.7719 (14) Å] link the mol-ecules, forming mol-ecular layers approximately parallel to the (002) plane. Additional weak van der Waals inter-actions between the layers consolidate the three-dimensional packing. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (33.6%), N⋯H/ H⋯N (17.2%), Cl⋯H/H⋯Cl (14.1%) and C⋯H/H⋯C (14.1%) contacts.

Crystal structure and Hirshfeld surface analysis of (E)-1-[2,2-di-chloro-1-(4-methyl-phen-yl)ethen-yl]-2-(4-meth-oxy-phen-yl)diazene.

The asymmetric unit of the title compound, C16H14Cl2N2O, comprises two similar mol-ecules, A and B, in which the dihedral angles between the two aromatic rings are 70.1 (3) and 73.2 (2)°, respectively. The crystal structure features short C-H⋯Cl and C-H⋯O contacts and C-H⋯π and van der Waals inter-actions. The title compound was refined as a two-component non-merohedral twin, BASF 0.1076 (5). The Hirshfeld surface analysis and two-dimensional fingerprint plots show that H⋯H (38.2% for mol-ecule A; 36.0% for mol-ecule B), Cl⋯H/H⋯Cl (24.6% for mol-ecule A; 26.7% for mol-ecule B) and C⋯H/H⋯C (20.0% for mol-ecule A; 20.2% for mol-ecule B) inter-actions are the most important contributors to the crystal packing.

Crystal structure and Hirshfeld surface analysis of 1,3-bis-{2,2-di-chloro-1-[(E)-phenyl-diazen-yl]ethen-yl}benzene.

In the mol-ecule of the title compound, C22H14Cl4N4, the central benzene ring makes dihedral angles of 77.03 (9) and 81.42 (9)° with the two approximately planar 2,2-di-chloro-1-[(E)-phenyl-diazen-yl]vinyl groups. In the crystal, mol-ecules are linked by C-H⋯π, C-Cl⋯π, Cl⋯Cl and Cl⋯H inter-actions, forming a three-dimensional network. The Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (30.4%), C⋯H/H⋯C (20.4%), Cl⋯H/H⋯Cl (19.4%), Cl⋯Cl (7.8%) and Cl⋯C/C⋯Cl (7.3%) inter-actions.

Crystal structure and Hirshfeld surface analysis of (2Z)-N,N-dimethyl-2-(penta-fluoro-phen-yl)-2-(2-phenyl-hydrazin-1-yl-idene)acetamide.

In the title compound, C16H12F5N3O, the dihedral angle between the aromatic rings is 31.84 (8)°. In the crystal, the mol-ecules are linked into dimers possessing crystallographic twofold symmetry by pairwise N-H⋯O hydrogen bonds and weak C-H⋯O hydrogen bonds and aromatic π-π stacking inter-actions link the dimers into a three-dimensional network. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from F⋯H/H⋯F (41.1%), H⋯H (21.8%), C⋯H/H⋯C (9.7%) C⋯C (7.1%) and O⋯H/H⋯O (7.1%) contacts. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9-18] in PLATON. The solvent contribution was not included in the reported mol-ecular weight and density.

Crystal structure and Hirshfeld surface analysis of (E)-1-(2,6-di-chloro-phen-yl)-2-(2-nitro-benzyl-idene)hydrazine.

In the title compound, C13H9Cl2N3O2, the 2,6-di-chloro-phenyl ring and the nitro-substituted benzene ring form a dihedral angle of 21.16 (14)°. In the crystal, face-to-face π-π stacking inter-actions occur along the a-axis direction between the centroids of the 2,6-di-chloro-phenyl ring and the nitro-substituted benzene ring. Furthermore, these mol-ecules show intra-molecular N-H⋯Cl and C-H⋯O contacts and are linked by inter-molecular N-H⋯O and C-H⋯Cl hydrogen bonds, forming pairs of hydrogen-bonded mol-ecular layers parallel to (20). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (23.0%), O⋯H/H⋯O (20.1%), Cl⋯H/H⋯Cl (19.0%), C⋯C (11.2%) and H⋯C/C⋯H (8.0%) inter-actions.

Crystal structure and Hirshfeld surface analysis of (E)-4-{2,2-di-chloro-1-[(3,5-di-methyl-phen-yl)diazen-yl]ethen-yl}-N,N-di-methyl-aniline.

In the title compound, C18H19Cl2N3, the planes of the benzene rings subtend a dihedral angle of 77.07 (10)°. In the crystal, mol-ecules are associated into inversion dimers via short Cl⋯Cl contacts [3.3763 (9) Å]. A Hirshfeld surface analysis indicates that the most important contact percentages for the different types of inter-actions are H⋯H (43.9%), Cl⋯H/H⋯Cl (22.9%), C⋯H/H⋯C (20.8%) and N⋯H/H⋯N (8.0%).

(E)-1-(2,6-Di-chloro-phen-yl)-2-(3-nitro-benzyl-idene)hydrazine: crystal structure and Hirshfeld surface analysis.

The stabilized conformation of the title compound, C13H9Cl2N3O2, is similar to that of the isomeric compound (E)-1-(2,6-di-chloro-phen-yl)-2-(2-nitro-benzyl-idene)hydrazine. The 2,6-di-chloro-phenyl ring and the nitro-substituted benzene ring form a dihedral angle of 26.25 (16)°. In the crystal, face-to-face π-π stacking inter-actions along the a-axis direction occur between the centroids of the 2,6-di-chloro-phenyl ring and the nitro-substituted benzene ring. The mol-ecules are further linked by C-H⋯O contacts and N-H⋯O and C-H⋯Cl hydrogen bonds, forming pairs of hydrogen-bonded mol-ecular layers parallel to (100). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (22.1%), Cl⋯H/H⋯Cl (20.5%), O⋯H/H⋯O (19.7%), C⋯C (11.1%) and C⋯H/H⋯C (8.3%) inter-actions.

Crystal structure and Hirshfeld surface analysis of 4-{2,2-di-chloro-1-[(E)-(4-chloro-phen-yl)diazen-yl]ethen-yl}-N,N-di-methyl-aniline.

The title compound, C16H14Cl3N3, comprises three mol-ecules of similar shape in the asymmetric unit. The crystal cohesion is ensured by inter-molecular C-H⋯N and C-H⋯Cl hydrogen bonds in addition to C-Cl⋯π inter-actions. Hirshfeld surface analysis and two-dimensional fingerprint plots reveal that Cl⋯H/H⋯Cl (33.6%), H⋯H (27.9%) and C⋯H/H⋯C (17.6%) are the most important contributors towards the crystal packing.

Crystal structure and Hirshfeld surface analysis of 4-{2,2-di-chloro-1-[(E)-2-(4-methyl-phen-yl)diazen-1-yl]ethen-yl}-N,N-di-methyl-aniline.

In the tile compound, C17H17Cl2N3, the dihedral angle between the benzene rings is 62.73 (9)°. In the crystal, there are no classical hydrogen bonds. Mol-ecules are linked by a pair of C-Cl⋯π inter-actions, forming an inversion dimer. A short inter-molecular HL⋯HL contact [Cl⋯Cl = 3.2555 (9) Å] links the dimers, forming a ribbon along the c-axis direction. The Hirshfeld surface analysis and two-dimensional fingerprint plots reveal that the most important contributions for the crystal packing are from H⋯H (45.4%), Cl⋯H/H⋯Cl (21.0%) and C⋯H/H⋯C (19.0%) contacts.

Crystal structure and Hirshfeld surface analysis of 4-{2,2-di-chloro-1-[(E)-(4-fluoro-phen-yl)diazen-yl]ethen-yl}-N,N-di-methyl-aniline.

In the title compound, C16H14Cl2FN3, the dihedral angle between the two aromatic rings is 64.12 (14)°. The crystal structure is stabilized by a short Cl⋯H contact, C-Cl⋯π and van der Waals inter-actions. The Hirshfeld surface analysis and two-dimensional fingerprint plots show that H⋯H (33.3%), Cl⋯H/H⋯Cl (22.9%) and C⋯H/H⋯C (15.5%) inter-actions are the most important contributors towards the crystal packing.

Crystal structure and Hirshfeld surface analysis of (E)-4-{[2,2-di-chloro-1-(4-meth-oxy-phen-yl)ethen-yl]diazen-yl}benzo-nitrile.

In the title compound, C16H11Cl2N3O, the 4-meth-oxy-substituted benzene ring makes a dihedral angle of 41.86 (9)° with the benzene ring of the benzo-nitrile group. In the crystal, mol-ecules are linked into layers parallel to (020) by C-H⋯O contacts and face-to-face π-π stacking inter-actions [centroid-centroid distances = 3.9116 (14) and 3.9118 (14) Å] between symmetry-related aromatic rings along the a-axis direction. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from Cl⋯H/H⋯Cl (22.8%), H⋯H (21.4%), N⋯H/H⋯N (16.1%), C⋯H/H⋯C (14.7%) and C⋯C (9.1%) inter-actions.