Computational exploration of the copper(I)-catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives.

This computational study explores the copper (I) chloride catalyzed synthesis of (E)-1-(2,2-dichloro-1-phenylvinyl)-2-phenyldiazene (2Cl-VD) from readily available hydrazone derivative and carbon tetrachloride (CCl). 2Cl-VD has been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) and N,N,N,N-tetramethylethane-1,2-diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists.

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

In the title compound, CHNO, 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 (6) ring motif.

Crystal structure and Hirshfeld surface analysis of (3)-7-meth-oxy-3-(2-phenyl-hydrazinyl-idene)-1-benzo-furan-2(3)-one.

In the title compound, CHNO, pairs of mol-ecules are linked into dimers by N-H⋯O hydrogen bonds, forming an (12) ring motif, with the dimers stacked along the axis. These dimers are connected through π-π stacking inter-actions between the centroids of the benzene and furan rings of their 2,3-di-hydro-1-benzo-furan ring systems. Furthermore, there exists a C-H⋯π inter-action that consolidates the crystal packing.

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

In the title compound, CHFNO, 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.

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

In the title compound, CHClN, the planes of the benzene rings subtend a dihedral angle of 77.07 (10)°. In the crystal, mol-ecules are associated into inversion dimers short Cl⋯Cl contacts [3.

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

In the tile compound, CHClN, the dihedral angle between the benzene rings is 62.73 (9)°. In the crystal, there are no classical hydrogen bonds.

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

In the title compound, CHClFN, 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.

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

In the title compound, CHClNO, 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.