Synthesis, Structure, and Magnetic Properties of a New Bis(maleonitriledithiolate)nickelate(III) Anion Salt Containing 1-(2′-Chlorobenzyl)-2-aminopyridinium

Abstract

A new salt, [2ClBz2NH₂Py][Ni(mnt)₂](1), ([2ClBz2NH₂Py]⁺ = 1-(2´-chlorobenzyl)-2-aminopyridinium, mnt²⁻ = maleonitril-edithiolate), was prepared and characterized structurally by means of CHN elemental analyses, IR, MS spectra and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group C2/c with lattice contents a = 24.947(2) Å, b = 12.658(1) Å, c = 15.045(2) Å, β = 97.41(1)°, V = 4711.0(8) ų, and Z = 8. The Ni(III) ions of 1 form a 1D spiral zigzag non-uniform magnetic chain within a [Ni(mnt)₂]⁻ column with the Ni···Ni distances of 3.971 and 4.386 Å, whereas two neighboring [2ClBz2NH₂Py]⁺ cations from a dimer by the short Cl···Cl interaction with a distance of 3.585 Å. The cations and anions are linked by N···π, S···π interactions and C-H···N, C-H···S hydrogen bonds. Magnetic susceptibility measurements in the temperature range 2–300 K show that the salt shows characteristic of spin-gap with Δ/k_b = 789.1 K.

Keywords:

• bis(maleonitriledithiolate)nickel(III)
• crystal structure
• magnetic properties
• substituted 2-aminopyridinium

Supplemental Material

Crystallographic data of 1 have been deposited at the Cambridge Crystallographic Data Center as supplementary publication No. CCDC-744653. Copies of the data may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: [phone]; [email protected] or www: http://www.ccdc.cam.ac.uk).

Additional information

Funding

This work has been partially supported by the Science and Technology Project (No. 2012B010200041) from Guangdong Science and Technology Department, the key Academic Program of the 3rd phase “211 Project” of South China Agricultural University (No. 2009B010100001), and the Undergraduates’ Innovative Experimental Program in University from Department of Education of Guangdong province (No. 1056412062).