A Novel N(3),N(4)‐Bridging Coordination Mode of 1‐R‐Tetrazole‐5‐thiolates – Synthesis, X‐ray Diffraction, Magnetic Properties and Quantum‐Chemical Study of a Macrocyclic Dinickel Complex Coligated by 1‐Methyltetrazole‐5‐thiolate

The dinuclear nickel(II) complex [Ni2L(μ‐ClO4)]ClO4, where L2– represents a 24‐membered macrocyclic bis(triamine–thiophenolate) ligand, reacts with 1‐methyltetrazole‐5‐thiol and triethylamine to give the complex [Ni2L(μ‐SCN4Me)]ClO4, which was subjected to metathesis with NaBPh4 yielding [Ni2L(μ‐SCN4Me)]BPh4. This new complex was characterized by elemental analysis, UV/Vis/NIR and IR spectroscopy. The structure of [Ni2L(μ‐SCN4Me)]BPh4 was determined by X‐ray crystallography, showing the 1‐methyltetrazole‐5‐thiolate ligand in an N(3),N(4)‐bridging mode generating a bis(octahedral) N3Ni(μ‐S)2(μ‐SCN4Me)NiN3 core. Quantum chemical calculations of the molecular electrostatic potential, natural population analysis and total energies of possible structures of [Ni2L(μ‐SCN4Me)]+ are in agreement with the structural data obtained. Temperature‐dependent magnetic susceptibility measurements revealed that the NiII ions in the dinuclear complex are weakly ferromagnetically coupled showing a coupling constant J of 19.5 cm–1 (H = –2JS1S2).