A series of Fe(II) complexes with (ClO4)(-)(SeCN)(-), (ClO4)(-)(SCN)(-), (Fe2OCl6)(2-), and 2(BF4)(-) counter-anions for complexes 1-4, derived from dmbpy (4,4-dimethyl-2,2-bipyridine), were prepared. The single-crystal studies and the Hirshfeld surfaces analysis revealed that the (Fe2OCl6)(2-) anion results more distortional octahedral geometry of the cation than other anions. In particular, the (ClO4)(-)(SCN)(-) and (Fe2OCl6)(2-) anions lead to complexes 2 and 3 stabilized via C-H interactions and interactions, which were not found in the other two complexes. However, the double-chain structure of complex 4 was formed by C-HF and C-HC hydrogen bonds interactions. Due to the influence of different anions, magnetic susceptibility measurements showed that complex 1 was in high-spin (HS) state and complex 2 was in low-spin (LS) state.