A novel organic-inorganic chromium(III) hybrid salt, triethylammonium trans-diaquabis(oxalato-κ2O1,O2)chromate(III), (C6H16N)[Cr(C2O4)2(H2O)2] (1), has been synthesized in aqueous solution and characterized by elemental and thermal analyses, FTIR and UV-Vis spectroscopies, and by single crystal X-ray structure determination. Compound 1 crystallizes in the orthorhombic system, Pbcn space group with the unit cell parameters a = 11.1776(10), b = 7.6105(10), c = 17.5654(2) Å, α = β = γ = 90°, V = 1494.24(3) Å3, Z = 4 and Z’ = 1/2. The structure of 1 consists of [Cr(C2O4)2(H2O)2]− mononuclear anions and triethylammonium [(C2H5)3NH]+ cations. In the anionic unit, the CrIII ion is six coordinated, in a distorted octahedral geometry, by four equatorial O atoms of two oxalate anions acting as chelating ligands and two O atoms from trans-coordinated water molecules occupying the apical positions with longer metal-oxygen distances. In the solid, O-H … O and N-H … O intra and inter molecular hydrogen bonding interactions connect the components into a 3D network. The triethylammonium cations are disordered among two possible orientations with occupancies rates around 50% for C4, N1, C1a, C1b, C4ii, N1ii, C1aii, C1bii (ii = −x + 1, y, −z + 1/2). The IR spectrum of 1 is consistent with the presence of the various molecular building constituents. 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 studies carried out in air between 25°C and 700°C confirm the anhydrous character of 1 and show that it is stable up to 210°C.
References
[1]
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.
https://doi.org/10.1021/acs.inorgchem.7b01038
[2]
Marinescu, G., Lescouëzec, R., Armentano, D., De Munno, G., Andruh, M., Uriel, S., Llusar, R., Lloret, F. and Julve, M. (2002) [Cr(bpym)(C2O4)2]− in Designing Heterometallic 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.
https://doi.org/10.1016/S0020-1693(02)00880-0
[3]
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.
https://doi.org/10.1016/j.ccr.2010.08.004
[4]
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.
https://doi.org/10.1016/j.ijhydene.2009.12.180
[5]
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. https://doi.org/10.1098/rspa.2012.0100
[6]
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. https://doi.org/10.1016/j.molstruc.2012.11.046
[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.
https://doi.org/10.1107/S2056989015013213
[8]
Makon ma Houga, N., Capet, F., Nenwa, J., Gouet, B. and Foulon M. (2015) Crystal Structure of Tris[4-(dimethylamino)-pyridinium] tris(oxalato-κ2O,O’)chromate(III) Tetrahydrate. Acta Crystallographica Section E, 71, 1408-1410.
https://doi.org/10.1107/S2056989015020113
[9]
Nguemdzi, C.F.N., Capet, F., Ngoune, J., Gouet, B., Foulon, M. and Nenwa, J. (2018) Two Tris(oxalato)ferrate(III) Hybrid Salts with Pyridinium Derivative Isomers as Counter Cations: Synthesis, Crystal Structures, Thermal Analyses, and Magnetic Properties. Journal of Coordination Chemistry, 71, 1484-1496.
https://doi.org/10.1080/00958972.2018.1463097
[10]
Dridi, R., Namouchi, S.C., Faouzi, M.Z. and Driss, A. (2013) 2-Amino-6-methy-lpyridiniumtrans-di-aquadioxalatochromate(III) Monohydrate. Acta Crystallographica Section E, 69, 489-490. https://doi.org/10.1107/S1600536813022058
[11]
Gouet, B., Signé, M., Nenwa, J., Mbarki, M. and Fokwa, B.P.T. (2013) Pyridinium Trans-diaquabis[oxalato(2-)-κ2O1,O2]chromate(III)urea Monosolvate. Acta Crystallographica Section E, 69, m567. https://doi.org/10.1107/S1600536813026135
[12]
Dridi, R., Dhieb, C., Cherni, S.N., Boudjada, N.C., Sadfi, Z.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. https://doi.org/10.1016/j.molstruc.2017.09.111
[13]
Dridi, R., Cherni, S. and Faouzi, Z.M. (2015) Synthesis, Crystal Structure and Characterization of a New Oxalate Chromium(III) Complex. Journal of Chemical Sciences, 128, 1427-1433. https://doi.org/10.1007/s12039-015-0920-0
[14]
Ndong, P.R., Signé, M., Kenfack, P.T., Mbiangué, Y.A., Gouet, B. 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. https://doi.org/10.4236/csta.2020.92004
[15]
Sheldrick, G.M. (2010) SADABS, Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen, Göttingen.
[16]
Sheldrick, G.M. (2015) SHELXT-Integrated Space-Group and Crystal-Structure Determination. Acta Crystallographica Section A, 71, 3-8.
https://doi.org/10.1107/S2053273314026370
Brandenburg, K. (1999) Diamond, Crystal Impact. GbR, Bonn.
[19]
Singh, B.P. and Singh, B. (2000) Synthesis and Magnetic Properties of One-Dimensional Metal Oxalate Networks as Molecular-Based Magnets. Bulletin of Material Science, 23, 11-16. https://doi.org/10.1007/BF02708604
[20]
Kenfack, T.P., Hastürk, E., Fröhlich, 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. https://doi.org/10.1021/acs.cgd.9b00097
[21]
Bérézovsky, F., Hajem, A.A., Triki, S., Pala, J.S. and Molinie, P. (1999) Infinite Two-Dimensional Sheet-Like Array of a 2,2’-Bipyrimidine-bis-(oxalato)chromate(III) Complex: Synthesis, Crystal Structure and Magnetic Properties of
[K(H2O)Cr(C2O4)2(bpym)]. Inorganica Chimica Acta, 284, 8-13.
https://doi.org/10.1016/S0020-1693(98)00263-1
[22]
Lescouëzec, R., Marinescu, G., Vaissermann, J., Lloret, F., Faus, J., Andruh, M. and Julve, M. (2003) [Cr(AA)(C2O4)2]− and [Cu(bpca)]+ as Building Blocks in Designing New Oxalato-Bridged CrIII-CuII Compounds [AA = 2,2’-Bipyridine and 1,10-Phenanthroline; bpca = Bis(2-pyridylcarbonyl)amide anion]. Inorganica Chimica Acta, 350, 131-142. https://doi.org/10.1016/S0020-1693(02)01503-7
[23]
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.
https://doi.org/10.1016/0277-5387(95)00151-H
[24]
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. https://doi.org/10.1016/j.jaap.2014.03.015
[25]
Pointillart, F., Train, C., Boubekeur, K., Gruselle, M. and Verdaguer, M. (2006) Enantioselective Self-Assembly, Crystallographic Structure and Magnetic Properties of the Two Enantiomers of the Optically Active Canted Antiferromagnet
[Ru(bpy)3][Mn2(ox)3]. Tetrahedron: Asymmetry, 17, 1937-1943.
https://doi.org/10.1016/j.tetasy.2006.06.043
[26]
Gouet, B., 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 Kristallographie New Crystal Structures, 228, 175-176.
https://doi.org/10.1524/ncrs.2013.0069
[27]
Li, W., Jia, H.-P., Ju, Z.-F. and Zhang, J. (2008) A Rare Ferromagnetic μ1,1,2-Oxalato-Bridged Cu(II) Complex. Inorganic Chemistry Communications, 11, 591-594.
https://doi.org/10.1016/j.inoche.2008.02.016
[28]
Decurtins, S., Schmalle, H.W., Pellaux, R., Schneuwly, P. and Hauser, A. (1996) Chiral, Three-Dimensional Supramolecular Compounds: Homo- and Bimetallic Oxalate- and 1,2-Dithiooxalate-Bridged Networks. A Structural and Photophysical Study. Inorganic Chemistry, 35, 1451-1460. https://doi.org/10.1021/ic950791j
[29]
Coronado, E., Mascarós, J.R.G. and Gastaldo, C.M. (2006) Synthesis and Characterization of a Soluble Bimetallic Oxalate-Based Bidimensional Magnet:
[K(18-crown-6)]3[Mn3(H2O)4{Cr(ox)3}3]. Inorganic Chemistry, 45, 1882-1884.
https://doi.org/10.1021/ic0517570
[30]
Rajić, N., Stojakovic, D. and Gabrovšek, 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. https://doi.org/10.1023/A:1010152907304
[31]
Mercury CSD 3.9, Program for Crystal Structure Visualisation, Exploration and Data Analysis from the Cambridge Crystallographic Data Centre, 2001-2016.
http://www.ccdc.cam.ac.uk/mercury
[32]
Yu, X., Zhang, H., Cao, Y., Hu, Z., Chen, Y. and Wang, Z. (2006) Two Novel 3-D Bismuth Oxalates with Organic Amines Protruding in Channels. Journal of Solid State Chemistry, 179, 3095-3100. https://doi.org/10.1016/j.jssc.2006.06.004
[33]
Jana, N.C., Brandão, P. and Panja, A. (2016) Tuning the Geometry and Biomimetic Catalytic Activity of Manganese(III)-Tetrabromocatecholate Based Robust Platforms by Introducing Substitution at Pyridine. Journal of Inorganic Biochemistry, 159, 96-106. https://doi.org/10.1016/j.jinorgbio.2016.02.038
[34]
Bar, A.K., Kalita, P., Sutter, J.-P. and Chandrasekhar, V. (2018) Pentagonal-Bipyramid Ln(III) Complexes Exhibiting Single-Ion-Magnet Behavior: A Rational Synthetic Approach for a Rigid Equatorial Plane. Inorganic Chemistry, 57, 2398-2401.
https://doi.org/10.1021/acs.inorgchem.8b00059
[35]
Eboga, T.C., Gouet, B., Mbiangué, Y.A., Nfor, N.E., Djonwouo, 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.
https://doi.org/10.4236/ojic.2017.73005
[36]
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. https://doi.org/10.1021/ja808681m
[37]
Bélombé, M.M., Nenwa, J., Mbiangué, Y.A., Gouet, B., Majoumo, F., Hey-Hawkins, E. and Lönnecke, 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. https://doi.org/10.1016/j.ica.2007.03.003