The synthesis and crystal structure of the title compound [systematic name: di-μ-acetato-tetrakis(μ₄-N,2-dioxidobenzene-1-carboximidato)hexamethanoltetramanganese(III)nickel(II) methanol disolvate monohydrate], [Mn₄Ni(C₇H₄NO₃)₄(C₂H₃O₂)₂(CH₄O)₆]·2CH₄O·H₂O or Ni(OAc)₂[12-MC_{Mn(III)N(shi)}-4](CH₃OH)₆·2CH₃OH·H₂O, where MC is metallacrown, ⁻OAc is acetate, and shi³⁻ is salicylhydroximate, are reported. The macrocyclic metallacrown is positioned on an inversion center located on the Ni^II ion that resides in the central MC cavity. The macrocycle consists of an Mn^III–N–O repeat unit that recurs four times to generate an overall square-shaped molecule. Both the Ni^II and Mn^III ions are six-coordinate with an octahedral geometry. In addition, the Mn^III ions possess an elongated Jahn–Teller distortion along the z-axis of the coordination environment. The interstitial water molecule is slightly offset from and disordered about an inversion center.