Synthesis, thermal stability and structural characterisation of iron(II) phthalocyanine complex with 4-cyanopyridine

Abstract

A new complex of bis-axially coordinated iron(II) phthalocyanine by 4-cyanopyridine (4-CNpy) has been obtained in crystalline form as an adduct with two 4-CNpy molecules. The [FePc(4-CNpy) 2] · 2(4-CNpy) crystallises in the monoclinic system, space group P2 1/ c with two molecules in the unit cell. The iron(II) coordinates four isoindole nitrogen atoms of the almost planar phthalocyaninato(2−) macroring and axially two nitrogen atoms of 4-CNpy molecules. The coordination polyhedron around the Fe(II) atom approximates to a tetragonal by-pyramid. Four equatorial Fe–N bonds are shorter (1.936(2) Å) than two axial Fe–N bonds (2.027(2) Å). The centrosymmetric FePc(4-CNpy) 2 molecules form alternating sheets parallel to the bc crystallographic plane and solvated 4-CNpy molecules that are anti-parallel oriented by their polar cyano groups are located between the sheets of FePc(4-CNpy) 2 molecules. Ligation of the intermediate-spin iron(II) phthalocyanine by 4-CNpy molecules leads to the low spin Fe(II) complex. The importance of the d(π) → π ∗(Pc) back donation is manifested in the difference between the values of C–N isoindole and C–N azamethine bond lengths of the Pc macrocycle. The thermal analysis of the crystals of [FePc(4-CN) 2] · 2(4-CNpy) shows two steps responsible for a loss of solvated (∼170 °C) and coordinated (∼235 °C) 4-CNpy molecules.