Crystal and Molecular Structure of The Mixed-Metal Manganese(II) and Cobalt(II) Maleate Complex: [CoхMn1-x(OOCCH=CHCOO).(H2O)2]n

Abstract

For the first time, by the interaction of cobalt maleate tetrahydrate with Mn(II) acetate, a polymeric polynuclear mixed-metal maleate complex of manganese(II) and cobalt(II) was obtained: [CoхMn1-x(OOCCH=CHCOO).(H2O)2]n. The composition and structure of the resulting complexes were studied by IR spectroscopy, UV-Vis spectroscopy, EPR, and elemental and thermogravimetric analysis. The crystal structure of the complex was established by X-ray diffraction. The results of X-ray diffraction analysis showed that maleic acid dianions coordinate with Mn(II) and Co(II) ions in the bidentate bridging form, forming seven-membered chelate rings with manganese and cobalt ions. Each metal ion achieves octahedral symmetry with coordination from two oxygen atoms of two water molecules and two bridging oxygen atoms of the maleate ligands of neighboring complex molecules. The electronic absorption spectra show the absorption band at 965 nm, which should be attributed to the Mn(II) complex. The band at 516 nm refers to the cobalt complex. In the EPR spectrum, a wide single band with g = 2.031 is observed, indicating an electronic exchange interaction between Mn(II) and Co(II) ions. The presence of two metal ions in the complex was also confirmed by cyclic voltammetry. The voltammograms clearly show two reduction waves related to the two-electron reduction of Co2+ (Ec= -0.69 V) and Mn2+ (Ec= -0.985 V) ions.

Keywords

• Mn(II)
• Co(II) maleato complex
• crystal structure
• coordination polymer

References

1. 1. Thompson LK, Waldmann O, Xu Z. Polynuclear manganese grids and clusters—A magnetic perspective. Coord Chem Rev [Internet]. 2005 Dec 1;249(23):2677–90. Available from: .
2. 2. Kiskin MA, Eremenko IL. Chemical design of high spin polynuclear manganese(II) and iron(II) carboxylates. Russ Chem Rev [Internet]. 2006 Jul 31;75(7):559–75. Available from: .
3. 3. Ribas J, Escuer A, Monfort M, Vicente R, Cortés R, Lezama L, et al. Polynuclear NiII and MnII azido bridging complexes. Structural trends and magnetic behavior. Coord Chem Rev [Internet]. 1999 Oct 1;193–195:1027–68. Available from: .
4. 4. Rardin RL, Poganiuch P, Bino A, Goldberg DP, Tolman WB, Liu S, et al. Synthesis and characterization of novel trinuclear iron(II) and manganese(II) carboxylate complexes: structural trends in low valent iron and manganese carboxylates. J Am Chem Soc [Internet]. 1992 Jun 1;114(13):5240–9. Available from: .
5. 5. Durot S, Policar C, Pelosi G, Bisceglie F, Mallah T, Mahy J-P. Structural and Magnetic Properties of Carboxylato-Bridged Manganese(II) Complexes Involving Tetradentate Ligands:  Discrete Complex and 1D Polymers. Dependence of J on the Nature of the Carboxylato Bridge. Inorg Chem [Internet]. 2003 Dec 1;42(24):8072–80. Available from: .
6. 6. Christian P, Rajaraman G, Harrison A, Helliwell M, McDouall JJW, Raftery J, et al. Synthesis and studies of a trinuclear Mn(II) carboxylate complex. Dalt Trans [Internet]. 2004 Aug 9;2004(16):2550–5. Available from: .
7. 7. Ma C, Chen C, Liu Q, Chen F, Liao D, Li L, et al. Great Framework Variation of Polymers in the Manganese(II) Maleate/α,α′‐Diimine System: Syntheses, Structures, and Magneto‐Structural Correlation. Eur J Inorg Chem [Internet]. 2003 Aug 21;2003(15):2872–9. Available from: .
8. 8. Albela B, Corbella M, Ribas J, Castro I, Sletten J, Stoeckli-Evans H. Synthesis, Structural Characterization (X-ray and EXAFS), and Magnetic Properties of Polynuclear Manganese(II) Complexes with Chlorobenzoato Bridges. Inorg Chem [Internet]. 1998 Feb 23;37(4):788–98. Available from: .

9. 9. Zheng Y-Q, Kong Z-P. A New Maleato-Bridged Mn(II) Phen Complex: Structure and Magnetic Properties of Mn(phen)(C4H2O4). J Coord Chem [Internet]. 2002 Jan 1;55(11):1241–7. Available from: .
10. 10. Hua Q, Su Z, Zhao Y, Okamura T, Xu G-C, Sun W-Y, et al. Synthesis, structure and property of manganese(II) complexes with mixed tetradentate imidazole-containing ligand and benzenedicarboxylate. Inorganica Chim Acta [Internet]. 2010 Oct 25;363(13):3550–7. Available from: .
11. 11. Lazarou KN, Psycharis V, Perlepes SP, Raptopoulou CP. Complexes derived from the copper(II) perchlorate/maleamic acid/2,2′-bipyridine and copper(II) perchlorate/maleic acid/2,2′-bipyridine reaction systems: Synthetic, reactivity, structural and spectroscopic studies. Polyhedron [Internet]. 2009 Apr 23;28(6):1085–96. Available from: .
12. 12. Zhang L, Liu L, Huang C, Han X, Guo L, Xu H, et al. Polynuclear Ni(II)/Co(II)/Mn(II) Complexes Based on Terphenyl–Tetracarboxylic Acid Ligand: Crystal Structures and Research of Magnetic Properties. Cryst Growth Des [Internet]. 2015 Jul 1;15(7):3426–34. Available from: .
13. 13. Chen M, Chen M-Z, Zhou C-Q, Lin W-E, Chen J-X, Chen W-H, et al. Towards polynuclear metal complexes with enhanced bioactivities: Synthesis, crystal structures and DNA cleaving activities of CuII, NiII, ZnII, CoII and MnII complexes derived from 4-carboxy-1-(4-carboxybenzyl) pyridinium bromide. Inorganica Chim Acta [Internet]. 2013 Aug 24;405:461–9. Available from: .
14. 14. Huang D, Wang W, Zhang X, Chen C, Chen F, Liu Q, et al. Synthesis, Structural Characterizations and Magnetic Properties of a Series of Mono‐, Di‐ and Polynuclear Manganese Pyridinecarboxylate Compounds. Eur J Inorg Chem [Internet]. 2004 Apr 22;2004(7):1454–64. Available from: .
15. 15. Andruh M, Roesky HW, Noltemeyer M, Schmidt H-G. Synthesis and x-ray structure of the polynuclear complex bis(μ-trifluoroacetato,O,O′)(1,10-phenanthroline)manganese(II). Polyhedron [Internet]. 1993 Dec 1;12(23):2901–3. Available from: .
16. 16. Lis T. Structure of manganese(II) maleate trihydrate, [Mn(C4H2O4)].3H2O (I), and reinvestigation of the structure of manganese(II) hydrogen maleate tetrahydrate, [Mn(C4H3O4)2].4H2O (II). Acta Crystallogr Sect C Cryst Struct Commun [Internet]. 1983 Jan 15;39(1):39–41. Available from: .
17. 17. Ghoshal D, Mostafa G, Kumar Maji T, Zangrando E, Lu T-H, Ribas, J, et al. Synthesis, crystal structure and magnetic behavior of three polynuclear complexes: [Co(pyo)2(dca)2]n, [Co3(ac)4(bpe)3(dca)2]n and [{Co(male)(H2O)2}(H2O)]n [pyo, pyridine-N-oxide; dca, dicyanamide; ac, acetate; bpe, 1,2-bis-(4-pyridyl)ethane and male, maleate]. New J Chem [Internet]. 2004 Oct 1;28(10):1204–13. Available from: .
18. 18. Sergienko VS, Koksharova T V., Surazhskaya MD, Mandzii T V., Churakov A V. Synthesis, Crystal Structure, and Molecular Structure of Maleate Tris(Benzohydrazide) Cobalt(II) Tetrahydrate [Co(L1)3](Mal) 4H2O and Maleate Tris(Phenylacethydrazide) Nikel(II) Monohydrate [Ni(L2)3](Mal) H2O. Russ J Inorg Chem [Internet]. 2019 Nov 11;64(11):1396–404. Available from: .
19. 19. Yang J, Puchberger M, Qian R, Maurer C, Schubert U. Zinc(II) Complexes with Dangling Functional Organic Groups. Eur J Inorg Chem [Internet]. 2012 Sep 16;2012(27):4294–300. Available from: .
20. 20. Cañada-Vilalta C, Streib WE, Huffman JC, O’Brien TA, Davidson ER, Christou G. Polynuclear Manganese Complexes with the Dicarboxylate Ligand m -Phenylenedipropionate:  A Hexanuclear Mixed-Valence (3MnIII, 3MnIV) Complex. Inorg Chem [Internet]. 2004 Jan 1;43(1):101–15. Available from: .
21. 21. Stamatatos TC, Christou G. Mixed valency in polynuclear MnII/MnIII, MnIII/MnIV and MnII/MnIII/MnIV clusters: a foundation for high-spin molecules and single-molecule magnets. Philos Trans R Soc A Math Phys Eng Sci [Internet]. 2008 Jan 13;366(1862):113–25. Available from: .
22. 22. Tangoulis V, Malamatari DA, Soulti K, Stergiou V, Raptopoulou CP, Terzis A, et al. Manganese(II/II/II) and Manganese(III/II/III) Trinuclear Compounds. Structure and Solid and Solution Behavior. Inorg Chem [Internet]. 1996 Jan 1;35(17):4974–83. Available from: .
23. 23. Suffren Y, O’Toole N, Hauser A, Jeanneau E, Brioude A, Desroches C. Discrete polynuclear manganese(II) complexes with thiacalixarene ligands: synthesis, structures and photophysical properties. Dalt Trans [Internet]. 2015 Apr 23;44(17):7991–8000. Available from: .
24. 24. Thompson LK, Matthews CJ, Zhao L, Xu Z, Miller DO, Wilson C, et al. Synthesis, Structure, and Magnetism of a Series of Self-Assembled Polynuclear Mn(II), Co(II), and Cu(II) Cluster Complexes. J Solid State Chem [Internet]. 2001 Jul 1;159(2):308–20. Available from: .
25. 25. Chen H-B, Zhang H, Yang J-M, Zhou Z-H. Transformation of maleato manganese(II): temperature effect and coordination modes. Polyhedron [Internet]. 2004 Mar 25;23(6):987–91. Available from: .
26. 26. Gómez V, Corbella M. Versatility in the Coordination Modes of n ‐Chlorobenzoato Ligands: Synthesis, Structure and Magnetic Properties of Three Types of Polynuclear MnII Compounds. Eur J Inorg Chem [Internet]. 2009 Oct 12;2009(29–30):4471–82. Available from: .
27. 27. Ming-Xing Li, Gao-Yang Xie, Song-Lin Jin, Yi-Dong Gu, Ming-Qin Chen, Jie Liu, et al. Synthesis and magnetic properties of novel maleato-bridged cyclic tetranuclear manganese(II) complexes: Crystal structure of [Mn4(μ-maleate)2(bipy)8](ClO4)4·(MeOH)2(H2O2)2. Polyhedron [Internet]. 1996 Feb 1;15(3):535–9. Available from: .
28. 28. Wang H, Qin J. Two Polynuclear Manganese(II) Complexes Based on Multidentate N-Heterocyclic Aromatic Ligand and V-Shaped Polycarboxylate Ligand: Synthesis, Crystal Structure Analysis and Magnetic Properties. Crystals [Internet]. 2022 Feb 17;12(2):278. Available from: .
29. 29. Cakic S, Nikolic G, Stamenkovic J, Konstantinovic S. Physico-chemical characterization of mixed-ligand complexes of Mn(III) based on the acetylacetonate and maleic acid and its hydroxylamine derivative. Acta Period Technol [Internet]. 2005;(36):91–8. Available from: .
30. 30. Karmakar A, Baruah JB. Metal carboxylate complexes of L-3-phenyl-2-(3-phenyl-ureido)-propionic acid. Inorg Chem Commun [Internet]. 2009 Feb 1;12(2):140–4. Available from: .
31. 31. Nockemann P, Thijs B, Hecke K Van, Meervelt L Van, Binnemans K. Polynuclear Metal Complexes Obtained from the Task-Specific Ionic Liquid Betainium Bistriflimide. Cryst Growth Des [Internet]. 2008 Apr 1;8(4):1353–63. Available from: .
32. 32. Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds, part B: applications in coordination, organometallic, and bioinorganic chemistry. John Wiley & Sons; 2009. 33. Sukhotin AM. Handbook of chemistry. Leningrad “Chemistry.” 1981.