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分子内C-H⋯Ni弱相互作用的一个新例子:双-[4-甲基-2-(1,2,3,4-四氢萘-1-亚基)肼基硫代甲酰胺基-κ,]镍(II)二甲基甲酰胺单溶剂合物的合成、晶体结构及 Hirshfeld 分析

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

作者信息

de Oliveira Adriano Bof, Beck Johannes, Mellone Sônia Elizabeth Brown S, Daniels Jörg

机构信息

Departamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, 49100-000 São Cristóvão-SE, Brazil.

Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn, Germany.

出版信息

Acta Crystallogr E Crystallogr Commun. 2017 May 19;73(Pt 6):859-863. doi: 10.1107/S2056989017007198. eCollection 2017 Jun 1.

Abstract

The reaction of Ni 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(CHNS)]·CHNO. The ligands act as monoanionic κ,-donors, forming five-membered metallarings. The Ni ion is fourfold coordinated in a distorted square-planar -configuration, which is rather uncommon for mono-thio-semicarbazone complexes. Intra-molecular H⋯Ni -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].

摘要

四水合醋酸镍与4-甲基-2-(1,2,3,4-四氢萘-1-亚基)肼基硫代甲酰胺以2:1的摩尔比反应,并从二甲基甲酰胺中重结晶,得到标题化合物[Ni(CHNS)]·CHNO。配体作为单阴离子κ-供体,形成五元金属环。镍离子以扭曲的平面正方形构型进行四重配位,这在单硫代半卡巴腙配合物中相当少见。观察到分子内H⋯Ni相互作用[H⋯Ni距离为2.50和2.57 Å],因此可以认为存在螯合相互作用。 Hirshfeld表面分析表明,晶体堆积的主要贡献来自H⋯H(66.6%)、H⋯S(12.3%)和H⋯C(10.9%)相互作用。在晶体中,配合物分子通过N-H⋯O相互作用与二甲基甲酰胺溶剂分子相连,沿着[010]形成一维氢键聚合物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8ffb/5458310/6de273fe29f2/e-73-00859-fig1.jpg

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