Synthesis, Crystal Structure and Electrochemical Property of New Rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)bis(azido)cobalt(III) Nitrate Methanol Solvate Complex

Abstract  

The new cobalt compound, Co(C₁₆H₃₅N₁₀]⁺(NO₃)⁻·CH₃OH (1), have been synthesized and characterized. It’s structure and electrochemical property were investigated using single-crystal X-ray diffraction and cyclic voltammetry in solutions of dimethyl sulfoxide (DMSO) and methanol (CH₃OH). The X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic space group P2₁/c with a = 9.8339 (10) ?, b = 16.4048 (17) ?, c = 15.3628 (16) ?, β = 104.96 (9)° and Z = 4. The complex 1 consists of one Co(C₁₆H₃₅N₁₀)]⁺ cation, one NO₃ ⁻ anions and one solvent CH₃OH molecule. The metal center of complex 1 is six-coordinated, with the four nitrogens of the macrocycle defining an equatorial plane and two axially ligated N₃]⁻ ions completing the cobalt coordination sphere. Moreover, hydrogen bonds of O–H⋯N, O–H⋯O and N–H⋯O and static force connect two components of the compound and maintain the crystal structure. Additionally, in situ spectro-electrochemical measurements support Co(III)/Co(II) reversible reduction processes with the observation of the corresponding spectral changes with the applied potentials E _app = −1.5 and 0.5 V. The results obtained by the method are in agreement with those by the CV methods.