A new example of intra-molecular C-H⋯Ni anagostic inter-actions: synthesis, crystal structure and Hirshfeld analysis of cis-bis-4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amidato-κ2N1,Snickel(II) di-methyl-formamide monosolvate

• Published in: Acta crystallographica. Section E, Crystallographic communications Vol. 73; no. Pt 6; p. 859
• Main Authors: de Oliveira, Adriano Bof, Beck, Johannes, Mellone, Sônia Elizabeth Brown S, Daniels, Jörg
• Format: Journal Article
• Language: English
• Published: 01.06.2017
• ISSN: 2056-9890; 2056-9890
• DOI: 10.1107/S2056989017007198

The reaction of NiII acetate tetra-hydrate with 4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amide in a 2:1 molar ratio and recrystallization from di-methyl-formamide yielded the title compound, [Ni(C12H14N3S)2]·C3H7NO. The ligands act as monoanionic κ2N1,S-donors, forming five-membered metallarings. The NiII ion is fourfold coordinated in a distorted square-planar cis-configuration, which is rather uncommon for mono-thio-semicarbazone complexes. Intra-molecular H⋯Ni trans-inter-actions are observed [H⋯Ni distances are 2.50 and 2.57 Å] and thus anagostic inter-actions can be suggested. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are H⋯H (66.6%), H⋯S (12.3%) and H⋯C (10.9%) inter-actions. In the crystal, the complex mol-ecules are linked by di-methyl-formamide solvent mol-ecules through N-H⋯O inter-actions into one-dimensional hydrogen-bonded polymers along [010].The reaction of NiII acetate tetra-hydrate with 4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amide in a 2:1 molar ratio and recrystallization from di-methyl-formamide yielded the title compound, [Ni(C12H14N3S)2]·C3H7NO. The ligands act as monoanionic κ2N1,S-donors, forming five-membered metallarings. The NiII ion is fourfold coordinated in a distorted square-planar cis-configuration, which is rather uncommon for mono-thio-semicarbazone complexes. Intra-molecular H⋯Ni trans-inter-actions are observed [H⋯Ni distances are 2.50 and 2.57 Å] and thus anagostic inter-actions can be suggested. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are H⋯H (66.6%), H⋯S (12.3%) and H⋯C (10.9%) inter-actions. In the crystal, the complex mol-ecules are linked by di-methyl-formamide solvent mol-ecules through N-H⋯O inter-actions into one-dimensional hydrogen-bonded polymers along [010].