A new example of intramolecular C—H...Ni anagostic interactions: synthesis, crystal structure and Hirshfeld analysis of cis-bis[4-methyl-2-(1,2,3,4-tetrahydronaphthalen-1-ylidene)hydrazinecarbothioamidato-κ² N ¹,S]nickel(II) dimethylformamide monosolvate

Abstract

The homoleptic nickel–thio­semicarbazonate complex shows structural features including an unusual cis-coordination and trans-anagostic Ni—H intra­molecular inter­actions. In the crystal, complex and DMF solvate mol­ecules build up a one-dimensional hydrogen-bonded polymer along [010].

Electron belt-to-σ-hole switch of noncovalently bound iodine(i) atoms in dithiocarbamate metal complexes

“…In (2)(3)(4)•FIB, the I⋯M (M = Ni, Pd, Pt) bond paths pass through the depleted ELF region on the I atoms (σh), and this observation confirms the electrophilic nature of iodine atoms when they interact with the metal centers. ELF projections in all clusters allow the identification of the ELF areas, corresponding to the d 9 -or d 8 -level, around the metal centers.…”

“…Fig. 9 shows a similar analysis of the C-I⋯M II interaction in four other (1)(2)(3)(4)•FIB isolated clusters. The binding energies (see Table S7 †) in this series of metal complexes show that platinum(II) is the best XB acceptor in line with the MEP results.…”

“…Square-planar metal complexes bearing unhindered and easily accessible metal centers can form several types of metal-involving noncovalent interactions (Fig. 1) including hydrogen bonding (A), 1 H-anagostic [2][3][4] (A) and agostic interactions, 5 metallophilic contacts (B), 6 semicoordination (C), 7 and metal-π interactions (E). [8][9][10] As far as metal⋯halogen contacts are concerned, noncovalent interactions with halides could be considered as the M δ+ ⋯X δ− semicoordination 7 (C) owing to the electrophilic nature of most metals in their compounds.…”

Exchanged Metal‐Hydrogen Anagostic Bonds and Resonance of Dithiocarbamate and Thioureide Mesomers**

“…[10] Anagostic bonds are frequent in square-planar d 8 metal complexes, usually formed by dithiocarbamate ligands. [11][12][13][14][15][16][17][18] Owing to their easy synthetic routes, versatile complexation and attractive properties, dithiocarbamates are intensively studied and developed. The dithiocarbamate ligand, which is obtained in an exothermic reaction of CS 2 and an amine in the presence of a base, is a highly attainable mono-anionic chelating agent that is capable of forming stable complexes with all transition-group, lanthanide, actinide and with the majority of main-group elements.…”

“…However, the bond character strongly depends on the metal cation and its electron configuration [10] . Anagostic bonds are frequent in square‐planar d 8 metal complexes, usually formed by dithiocarbamate ligands [11–18] …”