One-Dimensional Coordination Polymers of 12-Metallacrown-4 Complexes: {Na2(L)2[12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4]} n , where L is Either O2CCH2CH3 or O2CCH2CH2CH3


The metallacrown one-dimensional coordination polymers {Na2(O2CCH2CH3)2[12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4](DMF)4(H2O)2}, 1, and {Na2(O2CCH2CH2CH3)2[12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4](DMF)4(H2O)2}, 2, where shi3− is salicylhydroximate and DMF is N,N-dimethylformamide, have been synthesized and characterized by single-crystal X-ray diffraction. Both compounds crystallize in the triclinic space group \(P\overline{1}\)with a = 8.0212(5) Å, b = 13.2214(8) Å, c = 13.3724(8) Å, α = 102.459(2)°, β = 97.185(2)°, γ = 93.545(2)°, V = 1368.11(14) Å3, and Z = 2 for 1 and with a = 8.0141(8) Å, b = 13.3871(13) Å, c = 13.5008(14) Å, α = 99.311(4)°, β = 96.308(4)°, γ = 92.249(3)°, V = 1418.3(2) Å3, and Z = 2 for 2. The one-dimensional chains are generated by neighboring metallacrown molecules being linked by a total of four propionate, 1, or butyrate, 2, anions (two per metallacrown face) through the ring MnIII ions. Under certain synthetic conditions, the discrete complex Na2(O2CCH2CH2CH3)2[12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4](DMF)6·DMF·HO2CCH2CH2CH3, 3, may be produced instead of the coordination polymer. Characterization of 3 by single-crystal X-ray diffraction yields the triclinic space group \(P\overline{1}\) with a = 10.703(2) Å, b = 12.036(2) Å, c = 14.810(3) Å, α = 77.915(3)°, β = 76.417(3)°, γ = 80.043(3)°, V = 1798.0(6) Å3, and Z = 1. The individual 12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4 frameworks of 1 and 2 are distorted to a greater extent with a higher degree of a ruffled structure when compared to 3. For 1 and 2, the benzene rings of the shi3− ligands are at a greater distance from the mean plane of the ring MnIII ions (MnP). When measured from the carbon para to the phenolate oxygen atom of the shi3− to the MnMP, the distances in 1 and 2 are greater than that in 3: 2.0760(22), 2.0025(59), and 1.2370(34) Å, respectively.

Graphical Abstract

This manuscript provides structural descriptions of two one-dimensional coordination polymers formed by manganese-based metallacrown molecules and bridging carboxylate anions. The four carboxylate anions, propionate or butyrate, link ring MnIII ions of adjacent [12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4] building blocks to produce a one-dimensional chain.

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This work was funded by the Shippensburg University Foundation Grant UGR2013/2014-1 to KAM and CMZ and by the Shippensburg University SURE Program to EJL and CMZ. The Smart Apex diffractometer was funded by National Science Foundation Grant 0087210, by Ohio Board of Regents Grant CAP-491, and by YSU. The D8 Quest X-ray diffractometer was funded by NSF Grant 1337296. The authors thank Dr. Arunpatcha Roldan for the collection of unit cell data. The authors declare that they have no conflict of interest.

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Correspondence to Curtis M. Zaleski.

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Mengle, K.A., Longenecker, E.J., Zeller, M. et al. One-Dimensional Coordination Polymers of 12-Metallacrown-4 Complexes: {Na2(L)2[12-\({\rm{M}}{{\rm{C}}_{{\rm{M}}{{\rm{n}}^{{\rm{III}}}}{\rm{(N)shi}}}}\)-4]} n , where L is Either O2CCH2CH3 or O2CCH2CH2CH3 . J Chem Crystallogr 45, 36–43 (2015).

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  • Metallacrown
  • Manganese
  • Coordination polymer
  • One-dimensional chain