Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O
Similar synthetic schemes yield two different metallacrown (MC) complexes: bis(μ-3-chlorobenzoato)hexakis(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)tetramanganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1,...
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| Format: | Article |
| Language: | English |
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International Union of Crystallography
2020-06-01
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| Series: | Acta Crystallographica Section E: Crystallographic Communications |
| Subjects: | |
| Online Access: | http://scripts.iucr.org/cgi-bin/paper?S2056989020006362 |
| _version_ | 1831691325021356032 |
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| author | Curtis M. Zaleski Matthias Zeller |
| author_facet | Curtis M. Zaleski Matthias Zeller |
| author_sort | Curtis M. Zaleski |
| collection | DOAJ |
| description | Similar synthetic schemes yield two different metallacrown (MC) complexes: bis(μ-3-chlorobenzoato)hexakis(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)tetramanganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1, and tetra-μ-aqua-tris(μ-3-chlorobenzoato)(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)pentamanganese(III)sodium(I) dimethylformamide tetrasolvate 0.72-hydrate, [Mn5Na(C7H4ClO2)3(C7H4NO3)4(C3H7NO)(H2O)4]·4C3H7NO·0.718H2O or MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O, 2, where shi3− is salicylhydroximate and DMF is N,N-dimethylformamide. Both complexes have the same framework consisting of four MnIII ions in the MC ring and four shi3− ligands, resulting in an overall square-shaped molecule. The MnIII ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 1 is nearly planar, and the MC binds two Na+ ions on opposite faces of the MC central cavity. The 3-chlorobenzoate anions also bind on opposite faces of the MC and form bridges between the central Na+ ions and the ring MnIII ions. For 1 the metallacrown molecule, except for the central Na+ ion, exhibits whole molecule disorder over two sets of sites. Both moieties are centrosymmetric and are related to each other by a pseudo-mirror operation with opposite sense of rotation around the Na...Na axis. The occupancy ratio of the main disorder of the metallacrown molecules and 3-chlorobenzoate anions refined to 0.9276 (9):0.0724 (9). The structure of 2 is slightly domed, and the MC binds both an MnII ion and an Na+ ion in the MC central cavity. The MnII ion is located on the convex side of the MC, while the Na+ ion binds to the concave side. Complex 2 represents the first instance of a [12-MCMn(III)N(shi)-4] molecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chlorobenzoate anions bind on the convex side of the MC and connect the MnII ion to three of the ring MnIII ions. |
| first_indexed | 2024-12-20T11:27:59Z |
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| issn | 2056-9890 |
| language | English |
| last_indexed | 2024-12-20T11:27:59Z |
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| publisher | International Union of Crystallography |
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| series | Acta Crystallographica Section E: Crystallographic Communications |
| spelling | doaj.art-f26b7397e8934032bf5aaab98fd734f32022-12-21T19:42:19ZengInternational Union of CrystallographyActa Crystallographica Section E: Crystallographic Communications2056-98902020-06-0176684885610.1107/S2056989020006362mw2160Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2OCurtis M. Zaleski0Matthias Zeller1Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, United StatesDepartment of Chemistry, Purdue University, West Lafayette, Indiana 479070, United StatesSimilar synthetic schemes yield two different metallacrown (MC) complexes: bis(μ-3-chlorobenzoato)hexakis(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)tetramanganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1, and tetra-μ-aqua-tris(μ-3-chlorobenzoato)(dimethylformamide)tetrakis(μ4-N,2-dioxidobenzene-1-carboximidato)pentamanganese(III)sodium(I) dimethylformamide tetrasolvate 0.72-hydrate, [Mn5Na(C7H4ClO2)3(C7H4NO3)4(C3H7NO)(H2O)4]·4C3H7NO·0.718H2O or MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O, 2, where shi3− is salicylhydroximate and DMF is N,N-dimethylformamide. Both complexes have the same framework consisting of four MnIII ions in the MC ring and four shi3− ligands, resulting in an overall square-shaped molecule. The MnIII ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 1 is nearly planar, and the MC binds two Na+ ions on opposite faces of the MC central cavity. The 3-chlorobenzoate anions also bind on opposite faces of the MC and form bridges between the central Na+ ions and the ring MnIII ions. For 1 the metallacrown molecule, except for the central Na+ ion, exhibits whole molecule disorder over two sets of sites. Both moieties are centrosymmetric and are related to each other by a pseudo-mirror operation with opposite sense of rotation around the Na...Na axis. The occupancy ratio of the main disorder of the metallacrown molecules and 3-chlorobenzoate anions refined to 0.9276 (9):0.0724 (9). The structure of 2 is slightly domed, and the MC binds both an MnII ion and an Na+ ion in the MC central cavity. The MnII ion is located on the convex side of the MC, while the Na+ ion binds to the concave side. Complex 2 represents the first instance of a [12-MCMn(III)N(shi)-4] molecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chlorobenzoate anions bind on the convex side of the MC and connect the MnII ion to three of the ring MnIII ions.http://scripts.iucr.org/cgi-bin/paper?S2056989020006362metallacrownmanganese complexsalicylhydroximatecrystal structure |
| spellingShingle | Curtis M. Zaleski Matthias Zeller Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O Acta Crystallographica Section E: Crystallographic Communications metallacrown manganese complex salicylhydroximate crystal structure |
| title | Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O |
| title_full | Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O |
| title_fullStr | Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O |
| title_full_unstemmed | Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O |
| title_short | Synthesis and crystal structure of two manganese-based 12-metallacrown-4 complexes: Na2(3-chlorobenzoate)2[12-MCMn(III)N(shi)-4](DMF)6 and MnNa(3-chlorobenzoate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O |
| title_sort | synthesis and crystal structure of two manganese based 12 metallacrown 4 complexes na2 3 chlorobenzoate 2 12 mcmn iii n shi 4 dmf 6 and mnna 3 chlorobenzoate 3 12 mcmn iii n shi 4 dmf h2o 4·4dmf·0 72h2o |
| topic | metallacrown manganese complex salicylhydroximate crystal structure |
| url | http://scripts.iucr.org/cgi-bin/paper?S2056989020006362 |
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