New Reactivity of 4‐Amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole: Synthesis and Structure of a Mononuclear Species, a Dinuclear Species, and a Novel Tetranuclear Nickel(II) Rectangle Box, and Magnetic Properties of the Dinuclear and Tetranuclear Complexes
- 31 July 2007
- journal article
- research article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 2007 (23) , 3710-3717
Abstract
Reactions of Ni(O2CMe)2·4H2O or NiCl2·6H2O, 4‐amino‐3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole (abpt) and NaN3 or KSCN in different molar ratios heated under reflux or hydrothermal conditions generate a mononuclear species with dimorphous phases, a dinuclear species incorporating an in situ deaminated [bpt‐H]– ligand and a tetranuclear rectangle box incorporating an unprecedented μ:η1:η2:η1 coordination mode of the deprotonated [abpt‐H]– ligand. Structural analysis reveals that a pair of [Ni2(μ1,1‐N3)(μ‐OAc)] motifs in [Ni4(abpt)2(abpt‐H)(N3)5(O2CMe)2]·5H2O (1) are bridged by two abpt and one [abpt‐H]– units into a rectangle box. [Ni2(bpt‐H)2(SCN)2(H2O)2]·2H2O (2) is a neutral centrosymmetric dinuclear NiII complex doubly bridged by abpt ligands. The complex [Ni(abpt)2(N3)2] (3) is a neutral centrosymmetric mononuclear NiII complex and crystallizes in polymorphous phases, showing an interesting example of temperature‐induced polymorphism. Variable‐temperature magnetic susceptibility measurements reveal that the ferromagnetic interaction via the (μ1,1‐N3)2(μ‐OAc) and (μ1,1‐N3)(μ1,1‐NHabpt–H)(μ‐OAc) bridges slightly dominates over the antiferromagnetic interaction via the abpt bridges, therefore indicative of an overall ferromagnetic coupling between NiII centers in 1, and a moderate antiferromagnetic interaction occurs in 2. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)Keywords
This publication has 32 references indexed in Scilit:
- Azide as a Bridging Ligand and Magnetic Coupler in Transition Metal ClustersEuropean Journal of Inorganic Chemistry, 2006
- Syntheses and crystal structures of two new cobalt(II) complexes derived from 3,5-bis(pyridin-2-yl)-4-amino-1,2,4-triazoleJournal of Chemical Crystallography, 2006
- Synthesis, structure and magnetic property of a new mixed-valence copper(I/II) complex derived from 3,5-bis(pyridin-2-yl)-1,2,4-triazoleJournal of Molecular Structure, 2006
- Synthesis, Crystal Structures, and Magnetic Properties of Three New Iron Complexes Derived from 3,5‐Bis(pyridin‐2‐yl)‐1,2,4‐triazoleZeitschrift für anorganische und allgemeine Chemie, 2006
- A Nonanuclear Iron(II) Single‐Molecule MagnetAngewandte Chemie International Edition, 2004
- Polymorphism and Pressure Driven Thermal Spin Crossover Phenomenon in [Fe(abpt) 2 (NCX) 2 ] (X = S, and Se): Synthesis, Structure and Magnetic PropertiesMonatshefte für Chemie - Chemical Monthly, 2003
- Light- and Thermal-Induced Spin Crossover in {Fe(abpt)2[N(CN)2]2}. Synthesis, Structure, Magnetic Properties, and High-Spin ↔ Low-Spin Relaxation StudiesInorganic Chemistry, 2001
- Polynuclear NiII and MnII azido bridging complexes. Structural trends and magnetic behaviorCoordination Chemistry Reviews, 1999
- Novel Hybrid Spin Systems of 7,7‘,8,8‘-Tetracyanoquinodimethane (TCNQ) Radical Anions and 4-Amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (abpt). Crystal Structure of [Fe(abpt)2(TCNQ)2] at 298 and 100 K, Mössbauer Spectroscopy, Magnetic Properties, and Infrared Spectroscopy of the Series [MII(abpt)2(TCNQ)2] (M = Mn, Fe, Co, Ni, Cu, Zn)Journal of the American Chemical Society, 1996
- Synthesis and co-ordination chemistry of a novel dinucleating chelating triazole ligand. The crystal structure of bis-µ-[4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole-N′, µ-N 1 ,µ-N 2 ,N″,]-bis[aquachloro-nickel( II )] dichloride tetrahydrateJ. Chem. Soc., Dalton Trans., 1984