CSTA  Vol.9 No.2 , May 2020
Synthesis, Characterization and Thermal Analysis of an Organic-Inorganic Hybrid Salt Involving Trans-Diaquabis(oxalato-κ2O1,O2)chromate(III) Complex Anion with Piperidinium as Counter Cation
A new organic-inorganic hybrid salt pipéridinium trans-diaquabis(oxalato)- chromate(III) tetrahydrate, (C5H10NH2)[Cr(C2O4)2(H2O)2]·4H2O (1), has been synthesized in water and characterized by FTIR and UV-Vis spectroscopies, elemental and thermal analyses and by single-crystal X-ray diffraction. 1 crystallizes in the orthorhombic non-centrosymmetric space group Cmc21 with the unit cell parameters a = 7.4329(3), b = 9.9356(5), c = 23.6756(11) Å, α = β = γ = 90°, V = 1748.45(14) Å3 and Z = 4. The structure of 1 consists of [Cr(C2O4)2(H2O)2]- mononuclear anions, piperidinium cations and uncoordinated water molecules. The CrIII ion in the complex [Cr(C2O4)2(H2O)2]- is coordinated in a slightly distorted octahedral environment by four O atoms from two chelating oxalate dianions in the equatorial plane, and two O atoms from trans-coordinated water molecules occupying the apical positions. In the crystal, N-H···O and O-H···O hydrogen bond interactions connect the components into a 3-D framework. The IR spectrum of 1 is consistent with the presence of the various molecular building constituents, namely oxalato and aqua ligands, piperidinium cations and solvent water molecules. The UV-Vis spectrum shows two absorption bands around 564 and 416 nm which are compatible with an anionic chromium(III) complex in an octahedral environment. Thermal analysis shows a three-step decomposition of 1, leading to formation of a metal oxide residue.
Cite this paper: Ndong, P. , Signé, M. , Kenfack, P. , Mbiangué, Y. , Bebga, G. and Wenger, E. (2020) Synthesis, Characterization and Thermal Analysis of an Organic-Inorganic Hybrid Salt Involving Trans-Diaquabis(oxalato-κ2O1,O2)chromate(III) Complex Anion with Piperidinium as Counter Cation. Crystal Structure Theory and Applications, 9, 36-47. doi: 10.4236/csta.2020.92004.

[1]   Marinescu, G., Andruh, M., Lloret, F. and Julve, M. (2011) Bis(oxalato)chromium(III) Complexes: Versatile Tectons in Designing Heterometallic Coordination Compounds. Coordination Chemistry Reviews, 255, 161-185.

[2]   Ying, W., Ming, F., Yi, L., Jing, L., Wei, S., Jun, C. and Peng, C. (2010) A Porous 3d-4f Heterometallic Metal-Organic Framework for Hydrogen Storage. International Journal of Hydrogen Energy, 35, 8166-8170.

[3]   Song, F., Zhang, T., Wang, C. and Lin, W. (2012) Chiral Porous Metal-Organic Frameworks with dual Active Sites for Sequential Asymmetric Catalysis. Proceedings of the Royal Society A, 6, 1-18.

[4]   Sun, L., Li, G.Z., Xu, M.H., Li, X.J., Li, J.R. and Deng, H. (2012) Self-Assembly of 1D, 2D, and 3D Lanthanide-Metal Coordination Polymers Based on a 2-(Pyridin- 4-yl)-4,5-imidazoledicarboxylate Linker: Synthesis, Structures, and Luminescence. European Journal of Inorganic Chemistry, 2012, 1764-1772.

[5]   Yan, L., Liu, W., Li, C., Wang, Y., Ma, L. and Dong, Q. (2013) Hydrogen Bonded Supra-Molecular Framework in Inorganic-Organic Hybrid Compounds: Syntheses, Structures, and Photoluminescent Properties. Journal of Molecular Structure, 1035, 240-246.

[6]   Murase, R., Abrahams, B.F., D’Alessandro, D.M., Davies, C.G., Hudson, T.A., Jameson, G.N.L., Moubaraki, B., Murray, K.S., Robson, R. and Sutton, A.L. (2017) Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer. Inorganic Chemistry, 56, 9025-9035.

[7]   Djomo, E.D., Capet, F., Nenwa, J., Bélombé, M.M. and Foulon, M. (2015) Crystal Structure of 4-(dimethylamino)pyridinium cis-Diaquabis(oxalato-κ2O,O’) Ferrate(III) Hemihydrate. Acta Crystallographica Section E, 71, 934-936.

[8]   Bebga, G., Ndassa, I.M., Ndong, P.R., Misse, P.R.N. and Fokwa, B.P.T. (2013) Crystal Structure of Potassium trans-Diaquabis[oxalato-κ2O,O]chromate(III) Urea disolvate, K[Cr(C2O4)2(H2O)2]·2CO(NH2)2, C6H12CrKN4O12. Zeitschrift fur Kristallo- graphie—New Crystal Structures, 228, 175-176.

[9]   Nenwa, J., Bélombé, M.M., Ngoune, J. and Fokwa, B.P.T. (2010) 4-(Dimethylamino) Pyridinium trans-Diaquabis[oxalato(2-)-κ2O1,O2]chromate(III). Acta Crystallographica Section E, 66, m1410.

[10]   Marinescu, G., Lescouezec, R., Armentano, D., De Munno, G., Andruh, M., Uriel, S., Llusar, R., Lloret, F. and Julve, M. (2002) [Cr(bpym)(C2O4)2]- in Designing Hete- rometallic Complexes. Crystal Structures and Magnetic Properties of PPh4[Cr(bpym)(C2O4)2]·H2O and [Ag(bpym)][Cr(C2O4)2(H2O)2]·2H2O (bpym = 2,2’-bipyrimidine). Inorganica Chimica Acta, 336, 46-54.

[11]   Chérif, I., Abdelhak, J., Faouzi Zid, M. and Driss, A. (2012) 2-Amino-5-chloropyri- dinium cis-Diaquadioxalatochromate(III) Sesquihydrate. Acta Crystallographica Sec- tion E, 68, m824-m825.

[12]   Dridi, R., Cherni, S.N., Faouzi Zid, M. and Driss, A. (2013) 2-Amino-6-methyl pyridinium trans-Diaquadioxalatochromate(III) Monohydrate. Acta Crystallographica Section E, 69, m489-m490.

[13]   Dridi, R., Dhieb, C., Cherni, S.N., Boudjada, N.C., Sadfi Zouaoui, N. and Faouzi, Z.M. (2018) A New Supramolecular Chromium(III) Complex: Synthesis, Structural Determination, Optical Study, Magnetic and Antibacterial Activity. Journal of Molecular Structure, 1152, 294-302.

[14]   Chérif, I., Abdelhak, J., Faouzi, Z.M. and Driss, A. (2011) 4-Aminopyridinium Trans-Diaquadioxalatochromate(III) Monohydrate. Acta Crystallographica Section E, 67, m1648-m1649.

[15]   Kahlenberg, V., Wertl, W., Kremenovic, A., Schuster, P. and Schottenberger, H. (2008) Structural Investigations and Thermal Behavior of (NH4)[Cr(C2O4)2]·2H2O. Zeitschrift Für Anorganische Und Allgemeine Chemie, 634, 921-926.

[16]   Decurtins, S., Schmalle, H.W., Schneuwly, P. and Oswald, H.R. (1993) Photochemical Synthesis and Structure of a 3-Dimensional Anionic Polymeric Network of an Iron(II) Oxalato Complex with Tris(2,2’-bipyridine)iron(II) Cations. Inorganic Che- mistry, 32, 1888-1892.

[17]   Devi, K.P. and Venkatachalam, K. (2017) Growth, Spectroscopic, Mechanical, Thermal, Antimicrobial and DFT Studies of Piperidinium Hydrogen Oxalate. Journal of Materials Science: Materials in Electronics, 28, 8061-8073.

[18]   Jayashri, T.A., Krishnan, G. and Viji, K. (2017) Spectral, Thermal and Antimicrobial Studies of Gamma Irradiated Potassium Diaquabis(Oxalato)Cobaltate (II). Oriental Journal of Chemistry, 33, 371-377.

[19]   Mansoorabadi, P.E., Can, S.O., Reed, M.G.H. and Ragsdale, S.W. (2017). Properties of Intermediates in the Catalytic Cycle of Oxalate Oxidoreductase and Its Suicide Inactivation by Pyruvate. Biochemistry, 56, 2824-2835.

[20]   Sheldrick, G.M. (2010) SADABS, Program for Empirical Absorption Correction of Area Detector Data. University of Gottingen, Gottingen.

[21]   Sheldrick, G.M. (2015) SHELXT-Integrated space-group and crystal-structure determination. Acta Crystallographica Section A, 71, 3-8.

[22]   Sheldrick, G.M. (2015) Crystal Structure Refinement with SHELXL. Acta Crystallographica Section C, 71, 3-8.

[23]   Brandenburg, K. (1999) Diamond, Crystal Impact GbR, Bonn.

[24]   Singh, B.P. and Singh, B. (2000) Synthesis and Magnetic Properties of One-Dimen- sional Metal Oxalate Networks as Molecular-Based Magnets. Bulletin of Material Sci- ence, 23, 11-16.

[25]   Kenfack, T.P., Hastürk, E., Frahlich, D., Wenger, E., Durand, P., Ngolui, L.J., Lecomte, C. and Janiak, C. (2019) Water Vapor Single-Gas Selectivity via Flexibility of Three Potential Materials for Autonomous Indoor Humidity Control. Crystal Growth and Design, 19, 2869-2880.

[26]   Onggo, D., Jahro, I.S., Martak, F. and Ismunandar (2008) Synthesis of Fe-Li-Cr Multinuclear Complexes as Molecular Magnet Materials. ITB Journal of Engineering Science, 40A, 62-70.

[27]   Chattopadhyay, S.K., Mak, T.C.W., Luo, B.S., Thompson, L.K., Rana, A. and Ghosh, S. (1995) Synthesis, Structural and Magnetic Studies of Imidazolium Bis(oxalato) Cuprate(II). Polyhedron, 14, 3661-3667.

[28]   Muraleedharan, K. and Kripa, S. (2014) Thermal Dehydration Kinetics of Potassium Bis(oxalato)cuprate(II) Dihydrate. Journal of Analytical and Applied Pyrolysis, 107, 298-305.

[29]   Nenwa, J., Gouet, B., Signé, M., Bélombé, M.M., Mbarki, M. and Fokwa, B.P.T. (2012) 2-Aminopyridinium trans-Diaquabis(oxalato-κ2 O,O)chromate(III). Acta Crys- tallographica Section E, 68, m1325-m1326.

[30]   Rajic, N., Stojakovic, D. and Gabrovsek, R. (2001) On the Thermal Decomposition of Trivalent Trioxalato Complexes of Al, Cr, Mn, Fe and Co. Journal of Thermal Analysis and Calorimetry, 63, 191-195.

[31]   Kenfack, T.P., Wenger, E., Ponou, S., Dahaoui, S., Lambi, J.N. and Lecomte, C. (2013) A New Heteroleptic Oxalate-Based Compound: Poly[[2-(aminomethyl)pyridine]di-μ6-oxalato-chromium(III)potassium(I)]. Acta Cry- stallographica Section C, 70, 12-15.

[32]   Mercury CSD 3.9, Program for Crystal Structure Visualisation, Exploration and Date Analysis from the Cambridge Crystallographic Data Center, 2001-2016.

[33]   Bélombé, M.M., Nenwa, J., Mbiangué, Y.A., Gouet, B., Majoumo, F., Hey-Hawkins, E. and Lonnecke, P. (2009) Water-Filled Pseudo-Nanotubes in Ag11.60H0.40[Cr(C2O4)3]4·15H2O: Synthesis, Characterization and X-Ray Structure. Inorganica Chimica Acta, 362, 1-4.

[34]   Teppei, Y., Masaaki, S. and Hiroshi, K. (2009) High Proton Conductivity of One- Dimensional Ferrous Oxalate Dihydrate. Journal of the American Chemical Society, 131, 3144-3145.

[35]   Eboga, T.C., Gouet, B. Mbiangué, Y.A., Nfor, N.E., Djonwoou, P.L., Bélombé, M.M. and Nenwa, J. (2017) Anionic Nanochannels Silver-Deficient Oxalatochromate(III) Complex with Hydronium as Counter Ion: Synthesis, Characterization and Crystal Structure. Open Journal of Inorganic Chemistry, 7, 75-87.