The syntheses, crystal structures and magnetochemical characterization are reported for two new mixed-valent manganese complexes, [MnII2MnIII2(H2O)2(hmp)6(NO3)2][MnII(NO3)3hmpH]2 (1) and, [MnII2MnIII4O2(hmp)4(hmpH)2(EtC(Me)2COO)4Cl2](EtC(Me)2COO)2 (2) incorporating the anion of 2‑hydroxymethyl pyridine. Complexes were further characterized by elemental analysis, IR & UV–Visible spectroscopy, single-crystal X-ray diffraction and thermogravimetric analysis. Variable temperature, solid-state direct current (dc) magnetization studies were carried out on both the complexes 1 and 2 in the 5.0–310 K range, and they established the complexes to have ground state spin values of S = 9 for 1 and S = 4 for 2.