Synthesis and crystal structure of a pentacopper(II) 12-metallacrown-4: cis-diaquatetrakis(dimethylformamide-κO)manganese(II) tetrakis(μ3-N,2-dioxidobenzene-1-carboximidate)pentacopper(II) dimethylformamide monosolvate

The title compound, [Mn(C3H7NO)(4)(H2O)(2)][Cu-5(C7H4NO3)(4)]center dot C3H7NO or cis[Mn(H2O)(2)(DMF)(4)]{Cu[12-MCCu(II)N(shi)-4]}center dot 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 degrees 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 CuII ions in the MC ring and a CuII ion captured in the central cavity. Each CuII ion is four-coordinate with a square-planar geometry. The anionic {Cu[12-MCCu(II)N(shi)-4]}(2-) is charged-balanced by the presence of a cis[Mn(H2O)(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.