Synthesis and crystal structure of a penta­copper(II) 12-metallacrown-4: cis-di­aqua­tetra­kis­(di­methyl­formamide-κO)manganese(II) tetra­kis­(μ(3)-N,2-dioxido­benzene-1-carboximidate)penta­copper(II) di­methyl­formamide monosolvate

The title compound, [Mn(C(3)H(7)NO)(4)(H(2)O)(2)][Cu(5)(C(7)H(4)NO(3))(4)]·C(3)H(7)NO or cis-[Mn(H(2)O)(2)(DMF)(4)]{Cu[12-MC(Cu(II)N(shi))-4]}·DMF, where MC is metallacrown, shi(3−) is salicyl­hydroximate, and DMF is N,N-di­methyl­formamide, crystallizes in the monoclinic space group P2(1)/n. Two crystallographically independent metallacrown anions are present in the structure, and both anions exhibit minor main mol­ecule disorder by an approximate (non-crystallographic) 180° rotation with occupancy ratios of 0.9010 (9) to 0.0990 (9) for one anion and 0.9497 (8) to 0.0503 (8) for the other. Each penta­copper(II) metallacrown contains four Cu(II) ions in the MC ring and a Cu(II) ion captured in the central cavity. Each Cu(II) ion is four-coordinate with a square-planar geometry. The anionic {Cu[12-MC(Cu(II)N(shi))-4]}(2−) is charged-balanced by the presence of a cis-[Mn(H(2)O)(2)(DMF)(4)](2+) cation located in the lattice. In addition, the octa­hedral Mn(II) counter-cation is hydrogen bonded to both MC anions via the coordinated water mol­ecules of the Mn(II) ion. The water mol­ecules form hydrogen bonds with the phenolate and carbonyl oxygen atoms of the shi(3−) ligands of the MCs.