• Views 1,549
• Citations 0
• ePub 29
• PDF 475
`International Journal of Inorganic ChemistryVolume 2013 (2013), Article ID 153023, 4 pageshttp://dx.doi.org/10.1155/2013/153023`
Research Article

## Synthesis and Crystal Structure of

Department of Chemistry, Sree Narayana College, Varkala, Kerala 695 145, India

Received 29 August 2012; Accepted 12 November 2012

Copyright © 2013 Thampidas V. S et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

#### Abstract

The title compound was synthesized by the reaction between a manganese(II) carboxylate and the tetradentate Schiff base ligand, 5-Br-salpnH2 [N,N′-bis(5-Br-salicylidene)-1,3-diaminopropane] produced in situ. The complex crystallizes in the P21/c space group with unit cell dimensions (10), (10), (3), , (10), and . The manganese(III) ion is in a distorted octahedral environment with longer axial bonds.

#### 1. Introduction

Recent advances in the coordination chemistry of manganese has been intimately connected to diverse fields such as, asymmetric catalysis [1, 2], molecular magnetism [35], and bioinorganic modeling [68]. With its accessible oxidation states of (II), (III), (IV), and (V), manganese plays several important roles in biological systems like the oxygen-evolving complex (OEC) of photosystem II [9, 10] and enzymes like superoxide dismutase, catalase, and arginase [11, 12]. Active sites of most of these systems contain manganese ligated mainly by N and O-donor atoms from the amino acid residues of the metalloproteins. Inorganic model complexes have made significant contributions to the progress in delineating the structural and functional aspects of the active sites of these systems [1316]. Ligands such as aliphatic, cyclic Schiff bases, polypyridyl systems, and carboxylic acids can stabilize manganese in its various oxidation states [17, 18]. Schiff base ligands with nitrogen and oxygen donor atoms may provide a chemical environment which can mimic the coordination spheres of manganese in biological systems better than any other ligand type. A whole host of manganese Schiff base complexes have been reported in this context during the last few decades [1927]. Among these, there is a sizeable number of complexes of the salpn [salpnH2 = -bis (salicylidene)-1, 3-diaminopropane] and substituted salpn ligands [1922]. We have been interested in the coordination chemistry of higher oxidation states of manganese for some time, and herein, we report the isolation of a new manganese(III) complex, [(5-Br-salpn)(DMF)2][B(C6H5)4].

#### 2. Experimental

##### 2.1. Materials and Physical Measurements

All chemicals were purchased from E-Merck and used without further purification. IR spectrum was recorded on a Nicolet 6700 spectrophotometer (KBr pellets, 4000–400 cm−1) while UV-Vis spectrum was taken on a Cary 100 Bio UV-Vis spectrophotometer. Elemental analyses were performed using a Perkin-Elmer 2400 CHNS analyzer.

##### 2.2. Synthesis of [MnIII(5-Br-salpn)(DMF)2][B(C6H5)4]

The starting material, [Mn2(Hsal)4(H2O)4], was prepared as reported earlier or alternatively by mixing hot aqueous solutions of sodium saliyclate and manganese(II)chloride (2 : 1 molar ratio), which gave pale pink crystals of the compound in yields greater than 80% in a day’s time [28]. To a solution of [Mn2(Hsal)4(H2O)4] (1.00 g, 2.19 mmol), 5-bromosalicylaldehyde (0.88 g, 4.38 mmol) and sodium tetraphenylborate (0.75 g, 2.19 mmol) in methanol/DMF mixture (20 mL, 1 : 1 v/v), 1,3-diaminopropane (0.16 g, 2.19 mmol) was added. The solution was stirred for a few minutes, filtered, and left to be evaporated in an open conical flask. Dark green crystals were deposited in 4-5 days. These were collected by filtration, washed with diethylether, and dried in air. Anal. calc. for C47H48BBr2MnN4O4: C, 58.84; H, 5.00; N, 5.84; Mn, 5.73. Found: C, 58.12.; H, 4.94; N, 5.29; Mn, 5.38%. IR (KBr pellet): /cm−1 = 3122 w, 3031 w, 1623 s, 1579 s, 1345 m, 1295 w, 1278 w, 1261 m, 1152 w, 999 w, 964 m, 798 s, 452 m. UV-Vis (methanol): λ/nm = 232 ( = 10136 mol−1 dm3 cm−1), 474 ( = 341 mol−1 dm3 cm−1).

##### 2.3. X-Ray Crystallography

Data were collected on a Bruker APEX II diffractometer, equipped with a CCD area detector (Cu-Kα radiation, graphite monochromator, λ = 1.54178 Å, at 100(2) K). The crystal structure was solved by direct methods and refined by full-matrix least-squares methods based on values against all reflections including anisotropic displacement parameters for all non-H atoms, using SHELXS97 and SHELXL97 [29]. All the nonhydrogen atoms were located from a Fourier map and refined anisotropically. Hydrogen site locations were inferred from neighbouring sites and were treated by a mixture of independent and constrained refinement. The molecular graphics were done with MERCURY 2.0 [30]. Crystal data and parameters for data collection are listed in Table 1.

Table 1: Crystal data and parameters for data collection for [MnIII(5-Br-salpn)(DMF)2][B(C6H5)4].

#### 3. Results

##### 3.1. Crystal Structure of [MnIII(5-Br-salpn)(DMF)2][B(C6H5)4]

The complex crystallizes in the monoclinic space group, /c. Molecular structure of [Mn(5-Br-salpn)(DMF)2]BPh4 is depicted in Figure 1. The cation, [Mn(5-Br-salpn)(DMF)2]+, is monomeric and octahedral. The 5-Br-salpn ligand, with its N2O2 donor set, holds the manganese(III) ion in an approximate square plane.

Figure 1: Molecular structure of [(5-Br-salpn)(DMF)2][B(C6H5)4]. Thermal ellipsoids are drawn at 50% probability level. Hydrogen atoms are omitted for clarity.

The Mn–Ophenol bonds [Mn–O2B = 1.8852(12) Å and Mn–O3B = 1.8955(12) Å] are slightly stronger than the Mn–Nimine bonds [Mn–N1 = 2.0259(14) Å and Mn–N4 = 2.0459(14) Å]. Oxygen atoms of the DMF solvent molecules coordinate with the manganese(III) ion and occupy the trans coordination positions of the complex. Jahn-Teller distortion causes an elongation of these axial bonds [Mn–O2 = 2.2119(12) Å, Mn–O1 = 2.2282(13) Å]. Selected bond angles and bond lengths of [Mn(5-Br-salpn)(DMF)2]+ are given in Table 2. The counter ions form helical chains about a screw axisand extend parallel to the (010) plane (Figures 2 and 3).

Table 2: Selected bond distances (Å) and bond angles (°) of [MnIII(5-Br-salpn)(DMF)2]+.
Figure 2: Crystal structure of [(5-Br-salpn)(DMF)2][B(C6H5)4] showing the close packing of the cationic Mn(III) complex and the counter ions.
Figure 3: Section of the crystal structure of [(5-Br-salpn)(DMF)2][B(C6H5)4] showing the helical array of [B(C6H5)4]- ions about a screw axis parallel to the (010) plane.

#### 4. Conclusions

The present work investigated a single-step reaction for the synthesis of a Schiff base complex of manganese(III) from a manganese(II) carboxylate. X-ray diffraction analysis of the complex has shown that the high spin manganese(III) ion is in octahedral environment and displays an elongation along the axial bonds on account of Jahn-Teller effect. Other structural features are similar to that of the reported structures of complexes with symmetrical N2O2 donor set ligands. See Supplementary Material available online at doi: 10.1155/2013/153023.

#### Acknowledgments

The authors are grateful to Prof. R. Lalancette, Rutgers University, Newark, NJ, USA, for X-ray diffraction analysis.

#### References

1. E. N. Jacobsen, “Asymmetric catalytic epoxidation of unfunctionalised olefins,” in Catalytic Asymmetric Synthesis, I. Ojima, Ed., pp. 159–202, VCH, New York, NY, USA, 1993.
2. J. F. Larrow and E. N. Jacobsen, “Asymmetric processes catalyzed by Chiral (Salen) metal complexes,” Organometallic Chemistry, vol. 6, pp. 123–152, 2004.
3. G. Christou, “Single-molecule magnets: a molecular approach to nanoscale magnetic materials,” Polyhedron, vol. 24, no. 16-17, pp. 2065–2075, 2005.
4. A. J. Tasiopoulos, A. Vinslava, W. Wernsdorfer, K. A. Abboud, and G. Christou, “Giant single-molecule magnets: a $\left\{{\text{Mn}}_{\text{84}}\right\}$ torus and its supramolecular nanotubes,” Angewandte Chemie—International Edition, vol. 43, no. 16, pp. 2117–2121, 2004.
5. R. Sessoli, H.-L. Tsai, A. R. Schake et al., “High-Spin Molecules: [Mn12O12(O2CR)16(H2O)4],” Journal of the American Chemical Society, vol. 115, no. 5, pp. 1804–1816, 1993.
6. A. Gelasco, M. Baldwin, and V. L. Pecoraro, “A modelling approach for understanding the mechanism of manganese enzymes,” in Mechanistic Bioinorganic Chemistry, H. H. Thorp and V. L. Pecoraro, Eds., Advanced Chemistry Series, pp. 265–301, ACS Books, Washington, DC, USA, 1995.
7. V. L. Pecoraro and W. Y. Hsieh, “The use of model complexes to elucidate the structure and function of manganese redox enzymes,” Metal ions in Biological Systems, vol. 37, pp. 429–504, 2000.
8. G. Christou, “Manganese carboxylate chemistry and Its biological relevance,” Accounts of Chemical Research, vol. 22, no. 9, pp. 328–335, 1989.
9. V. K. Yachandra, K. Sauer, and M. P. Klein, “Manganese cluster in photosynthesis: where plants oxidize water to dioxygen,” Chemical Reviews, vol. 96, no. 7, pp. 2927–2950, 1996.
10. G. W. Brudvig, “Water oxidation chemistry of photosystem II,” Philosophical Transactions of the Royal Society B, vol. 363, no. 1494, pp. 1211–1218, 2008.
11. C. F. Yocum and V. L. Pecoraro, “Recent advances in the understanding of the biological chemistry of manganese,” Current Opinion in Chemical Biology, vol. 3, no. 2, pp. 182–187, 1999.
12. D. W. Yoder, J. Hwang, and J. E. Penner-Hahn, “Manganese catalases,” in Manganese and Its Role in Biological Processes, A. Sigel and H. Sigel, Eds., vol. 37, pp. 527–557, Marcel Dekker, Basel, Switzerland, 2000.
13. A. J. Wu, J. E. Penner-Hahn, and V. L. Pecoraro, “Structural, spectroscopic, and reactivity models for the manganese catalases,” Chemical Reviews, vol. 104, no. 2, pp. 903–938, 2004.
14. J. S. Kanady, E. Y. Tsui, M. W. Day, and T. Agapie, “A synthetic model of the Mn3Ca subsite of the oxygen-evolving complex in photosystem II,” Science, vol. 333, no. 6043, pp. 733–736, 2011.
15. A. Mishra, W. Wernsdorfer, K. A. Abboud, and G. Christou, “The first high oxidation state manganese-calcium cluster: relevance to the water oxidizing complex of photosynthesis,” Chemical Communications, no. 1, pp. 54–56, 2005.
16. T. G. Carrell, A. M. Tyryshkin, and G. C. Dismukes, “An evaluation of structural models for the photosynthetic water-oxidizing complex derived from spectroscopic and X-ray diffraction signatures,” Journal of Biological Inorganic Chemistry, vol. 7, no. 1-2, pp. 2–22, 2002.
17. D. C. Weatherburn, S. Mandal, S. Mukhopadhyay, S. Bhaduri, and L. F. Lindoy, “Manganese,” Comprehensive Coordination Chemistry II, vol. 5, pp. 1–125, 2003.
18. J. C. Vites and M. M. Lynam, “Manganese 1995,” Coordination Chemistry Reviews, vol. 169, no. 1, pp. 153–186, 1998.
19. E. J. Larson and V. L. Pecoraro, “Catalytic disproportionation of hydrogen peroxide by [MnIV(μ2-O)(SALPN)]2,” Journal of the American Chemical Society, vol. 113, no. 20, pp. 7809–7810, 1991.
20. J. W. Gohdes and W. H. Armstrong, “Synthesis, structure, and properties of [Mn(salpn)(EtOH)2](ClO4) and its aerobic oxidation product [Mn(salpn)O]2,” Inorganic Chemistry, vol. 31, no. 3, pp. 368–373, 1992.
21. K. Rajender Reddy, M. V. Rajasekharan, and J.-P. Tuchagues, “Synthesis, structure, and magnetic properties of Mn(salpn)N3, a helical polymer, and Fe(salpn)N3, a Ferromagnetically Coupled Dimer (salpnH2 = N,N′-bis(salicylidene)-1,3-diaminopropane),” Inorganic Chemistry, vol. 37, no. 23, pp. 5978–5982, 1998.
22. M. Maneiro, M. R. Bermejo, A. Sousa et al., “Synthesis and structural characterisation of new manganese(II) and (III) complexes. Study of their photolytic and catalase activity and X-ray crystal structure of [Mn(3-OMe, 5-Br-salpn) (EtOH) (H2O)]ClO4,” Polyhedron, vol. 19, no. 1, pp. 47–54, 2000.
23. M. R. Bermejo, M. I. Fernández, A. M. González-Noya et al., “Novel peroxidase mimics: μ-Aqua manganese-Schiff base dimers,” Journal of Inorganic Biochemistry, vol. 100, no. 9, pp. 1470–1478, 2006.
24. M. R. Bermejo, M. I. Fernández, E. Gómez-Fórneas et al., “Self-assembly of dimeric MnIII-Schiff-base complexes tuned by perchlorate anions,” European Journal of Inorganic Chemistry, no. 24, pp. 3789–3797, 2007.
25. S. Mandal, A. K. Rout, M. Fleck, G. Pilet, J. Ribas, and D. Bandyopadhyay, “Synthesis, crystal structure and magnetic characterization of a series of four phenoxo-bridged binuclear manganese(III) Schiff base complexes,” Inorganica Chimica Acta, vol. 363, no. 10, pp. 2250–2258, 2010.
26. M. Á. Vázquez-Fernández, M. R. Bermejo, M. I. Fernández-García, G. González-Riopedre, M. J. Rodríguez-Doutón, and M. Maneiro, “Influence of the geometry around the manganese ion on the peroxidase and catalase activities of Mn(III)Schiff base complexes,” Journal of Inorganic Biochemistry, vol. 105, no. 12, pp. 1538–1547, 2011.
27. V. Peruzzo, S. Tamburini, and P. A. Vigato, “Manganese complexes with planar or tridimensional acyclic or cyclic Schiff base ligands,” Inorganica Chimica Acta, vol. 387, pp. 151–162, 2012.
28. M. Devereux, M. McCann, M. T. Casey et al., “Binuclear and polymeric manganese(II) salicylate complexes: synthesis, crystal structure and catalytic activity of [Mn2(Hsal)4(H2O)4] and [{Mn2(sal)2(Hsal)(H2O)-(H3O)(py)4·2py}n] (H2sal = salicylic acid, py = pyridine),” Journal of the Chemical Society, Dalton Transactions, no. 5, pp. 771–776, 1995.
29. G. M. Sheldrick, SHELXS-97. Program for Crystal Structure Analysis, University of Göttingen, Göttingen, Germany, 1997.
30. C. F. Macrae, P. R. Edgington, P. McCabe et al., “Mercury: visualization and analysis of crystal structures,” Journal of Applied Crystallography, vol. 39, no. 3, pp. 453–457, 2006.