In comparison to other transition metals with d electronic configuration in an octahedral geometry, iron(II) complexes are well explored, where the spin state switching occurs between the low-spin (LS) (t 6 2g e 0 g, S = 0, 1 A1), and the high-spin (HS) (t 4 2g e 2 g, S = 2, 5 T2) states. In the past few decades, significant efforts have been given to switching the spin-state of iron(II) by modulation of numerous parameters, including ligand modification, counter anions, crystallizing solvents, matrix of the system, cooperativity, molecular dimensionality, etc. Apart from those tremendous efforts, iron(II) complexes exhibit two or more step SCO with symmetry breaking are less in number, while similar phenomena have also been reported with iron(III), cobalt(II), and manganese(III) complexes. Accordingly, exploring such interesting features in iron(II) through magneto-structural relationships remains challenging.