On allowing DABCOH2(HC2O4)2 to react with transition metal dihalides in ethanol, a new series of complexes of general formula M(oxalate)2 DABCOH22+. nDABCOH22+.2X- (n=1/2;1) have been obtained. When (n=1) a dimeric structure is suggested, the two monomeric species being hold together by biprotonated DABCO through N-H…O hydrogen bonds. In the case of the complex M(oxalate)2DABCOH22+ .1/2 DABCOH22+.2X- -M = Ni, Cu- the structure is an infinite chain. The environment around the metallic centers is octahedral or square pyramidal. The oxalate behaves as a monochelating and hydrogen bonds involved ligand or is only concerned by hydrogen bonds

ABDOULAYE  SAMB

LIBASSE  DIOP

MAMADOU  NDIAYE

Journal of Engineering Studies and Research

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Journal of Engineering Studies and Research – Volume 23 (2017) No. 3                                       26      NEW TRANSITION METAL OXALATO COMPLEXES WITH DABCOH22+ AS ADVERSE CATION: SYNTHESIS AND INFRARED STUDY  MAMADOU NDIAYE1, ABDOULAYE SAMB1, LIBASSE DIOP*2  1University Cheikh Anta Diop, Dakar, Senegal, Faculty of Sciences and Technics, Department of Chemistry, Laboratory of Natural Products (L.P.N)  2University Cheikh Anta Diop, Dakar, Senegal, Faculty of Sciences and Technics, Department of Chemistry, Laboratory of Mineral and Analytical Chemistry (LA.CHI.MI.A)   Abstract: On allowing DABCOH2(HC2O4)2 to react with transition metal dihalides in ethanol, a new series of complexes of general formula M(oxalate)2 DABCOH22+. nDABCOH22+.2X- (n=1/2;1) have been obtained. When (n=1) a dimeric structure is suggested, the two monomeric species  being hold together by biprotonated DABCO through N-H…O hydrogen bonds. In the case of the complex M(oxalate)2DABCOH22+ .1/2 DABCOH22+.2X- -M = Ni, Cu- the structure is an infinite chain. The environment around the metallic centers is octahedral or square pyramidal. The oxalate behaves as a monochelating and hydrogen bonds involved ligand or is only concerned by hydrogen bonds.   Keywords: fullerene, dimeric or infinite chain structures, hydrogen bonds, monochelating ligand, octahedral or square planar environments    1. INTRODUCTION  The acidic substituted ammonium salts, because of their solubility in organic solvents have been used by several groups to reach new complexes of metals, transitional or not [1-5]. In this dynamic focusing in oxalic acid salts, our group has yet reported several papers in this field [6-8]. Rao et al. [9] have reported the crystal structure of DABCOH2(HC2O4)2. We initiate here the study of the interactions between Rao et al. salt [9] and some transitional metal halides which has yielded ten new complexes containing the core DABCOH2(C2O4).MC2O4.nDABCOH2.2X- (X = Cl, Br) (n=1/2;1) whose infrared study have been carried out then structures suggested on the basis of infrared data.   2. MATERIALS AND METHODS  We have obtained Rao et al. salt [9] – DABCOH2(HC2O4)2 – (L) on mixing DABCO and oxalic acid in ethanol in ½ ratio after a slow solvent evaporation.  The studied adducts have been obtained on mixing – DABCOH2(HC2O4)2 – (L) with CoCl2.6H2O, CuBr2, NiCl2.6H2O and CuCl2.2H2O in various ratios in ethanol. All the mixtures give a clear solution; a powder is obtained after a slow solvent evaporation.  The following compounds were obtained for specific ratios -(L)/metal halide-:                                             * Corresponding author, email: dlibasse@gmail.com  © 2017 Alma Mater Publishing House Journal of Engineering Studies and Research – Volume 23 (2017) No. 3                                       27 - L (4,2 10-4 mol) + CoCl2.6H2O (9.67 10-5 mol) in 2/1 ratio gives (A) as a yellow powder with a yield of 19.70 %; - L (4,2 10-4 mol) + CuBr2 (9.58 10-5 mol) in 2/1 ratio gives (B) as a yellow powder with a yield of     22.5 %; - L (4,2 10-4 mol) + NiCl2.6H2O (1.26 10-4 mol) in 2/1 ratio gives (C) as a yellow powder with a yield of  36.25 %; - L (4,2 10-4 mol) + CuCl2 (1.58 10-4 mol) in 2/1 ratio gives (D) as a yellow powder with a yield of     36.25 %; - L (4,2 10-4 mol) + CoCl2.6H2O (1.26 10-4 mol) in 2/1 ratio gives (E) as a beige powder with a yield of  24.17 %; - L (4,2 10-4 mol) + CuBr2 (5.06 10-4 mol) in 1/2 ratio gives (F) as a yellow powder with a yield of    12.05 %; - L (4,2 10-4 mol) + CuBr2 (1.26 10-4 mol) in 2/1 ratio gives (G) as a yellow powder with a yield of  14.29 %; - L (4,2 10-4 mol) + NiCl2.6H2O (3.83 10-4 mol) in 1/2 ratio gives (H) as a yellow powder with a yield of  11,57 %; - L (4,2 10-4 mol) + NiCl2.6H2O (4.63 10-5 mol) in 2/1 ratio gives (I) as a yellow powder with a yield of  50 %; - L (4,2 10-4 mol) + CuBr2 (1.93 10-4 mol) in 2/1 ratio gives (J) as a yellow powder with a yield of   12.38 %.  The analytical data reported below have allowed suggesting the following formulae for the ten new complexes (Table 1).  Table 1. Chemical composition of suggested compounds.  Compound   Suggested compounds Chemical composition [% mass] C H N Calc. Found Calc. Found Calc. Found (A) DABCOH2C2O4.CoC2O4.DABCOH2Cl2.2EtOH.3H2O 35.96 35.96 5.24  5. 32 10.49 10.41 (B) DABCOH2C2O4.CuC2O4.DABCOH2Br2.4EtOH.1/2DABCO 37.36  37.34 6.69  6.61 8.07  8.03 (C) DABCOH2C2O4.NiC2O4.DABCOH2Cl2.1/2DABCO.H2O 39.25   38.91 6.93 6.95 13.47   13.37 (D) [DABCOH2]C2O4.CuC2O4.2[DABCOH2Cl2].2H2O 34.76   35.02 6.07 6.06 11.06   11.14 (E) 3[DABCOH2]C2O4.CoC2O4.[DABCOH2Cl2] 44.10  44.26   7.35  7.59 14.70  14.23 (F) 2[DABCOH2]C2O4.CuC2O4.2[DABCOH2Br2] 44.10  43.78 7.35  7.49 14.7  14.61 (G) DABCOH2C2O4.CuC2O4.DABCOH2Cl2.DABCO.H2O 39.49  39.33 6.28  6.33 12.5  12.34 (H) DABCOH2C2O4.NiC2O4.DABCOH2Cl2.1/2H2O 37.59  37.43 6.26 6.33 9.74  9.68 (I) DABCOH2C2O4.Ni(C2O4).1/2[DABCOH2Cl2] 35.36  .35.49 4.98  4.95 9.52    9.44 (J) DABCOH2C2O4.CuC2O4.1/2[ DABCOH2Cl2].EtOH 34.12  34.22 5.12  5.16 7.96  8.06  Elemental analyses and IR spectra (performed on a Brucker FT-IR spectrometer) have been obtained from Rhodes University of Grahamstown-South Africa.   IR abbreviations: br (broad) vs (very strong); s (strong); m (medium). Chemical reagents are purchased from ALDRICH Company (Germany) and used as received.   3. RESULTS AND DISCUSSION  Let us consider the infrared data of complexes (A), (B), (C), (D), (E), (F), (G), (H), (I)  and (J) in cm-1: (A): νas(CO2) 1670(vs), νs(CO2) 1281(s), δ(CO2) 780(s), νas(H2O) 3350(br), (νOH +νNH) 2880(br); (B): νas(CO2) 1692.84(vs), νs(CO2) 1285.88(m), δ(CO2) 781.93(m), (νOH +νNH) 3521.18(br), 3035.8(br); (C): νas(CO2) 1691.93(vs), νs (CO2) 1323.10(m), δ(CO2) 772.04(m), νas(H2O) 3519.64(br), (νNH) 3479.36(br), 2986.21(br); (D): νas(CO2) 1618.74(vs), νs(CO2) 1311.09(m), δ(CO2) 794.77(m), νas(H2O) 3369.04(br), (νNH) 2977.94(br); (E): νas(CO2) 1618.40(s), νs(CO2) 1233.84(m), δ(CO2) 793.99(m), (νNH) 3367.16(br), 2921.71(br); (F): νas(CO2)1623(m), νs(CO2) 1372.56(s), δ(CO2) 797.87(s), (νNH) 3362.74(br), 2920.07(br); Journal of Engineering Studies and Research – Volume 23 (2017) No. 3                                       28 (G): νas(CO2) 1615.04(vs), νs(CO2) 1308.54(m), δ(CO2) 761.15(m), νas(H2O) 3415.32(br), (νNH) 3014.33(br); (H): νas(CO2) 1692.56(s), νs(CO2) 1325.08(m), δ(CO2) 805.15(m), νas(H2O) 3525.45(br), (νNH) 3448.93(br), 2850.17(br); (I): νas(CO2) 1678(vs), νs(CO2) 1297.8(s), δ(CO2) 782.5(vs), (νNH) 2975(br); (J):νas(CO2) 1693.07(vs), νs(CO2) 1322.88(m), δ(CO2) 783.14(m), (νOH+νNH) 3450.93(br), 3034.96(br). The adducts (A), (H), (B), (G) and (C) are only different by the lattice molecules involved, so we will chose the first compound as the parent molecule. The suggested structure is a dimer with a CoCl2 surrounded by two monochelating oxalates, the environment around the metallic centre being octahedral, the two cores being connected via N-H…..O hydrogen bonds by the biprotonated DABCO. The water and ethanol molecules are lattice (Figure 1).   Fig. 1. Proposed structure for (A).  NB These other complexes are only different through the number of lattice molecules (EtOH, DABCO, H2O) involved. The suggested structure for (B) is similar to the one of (A), the chlorido atoms being replaced by bromido ones, the ethanol and the DABCO molecules being lattice.  For the complex (D) we can maintain the dimeric nature of the above complexes but in this case the string connecting the two complexe –anions is DABCOH22+……Cl-……..DABCOH22+ rather than one DABCOH22+. The two chloride atoms involved in the strings are then connected by another DABCOH22+……Cl-……..DABCOH22+ string, the remaining chloride atom  being involved in electrostatic interactions with the main component of the structure. The hydrogen bonds between the biprotoned DABCO and the oxalates are bifurcated ones (Figure 2).  Fig. 2. Proposed structure for (D). Journal of Engineering Studies and Research – Volume 23 (2017) No. 3                                       29 (E) 3[DABCOH2]C2O4.CoC2O4.[DABCOH2Cl2]  This compound is (A) to which has been added two molecules of DABCOH2C2O4 the suggested structure is a monomer consisting of a [CoCl2(C2O4)]2- core as in (A) to which are connected in both sides [(DABCOH2)2C2O4]2+; the structure is reported in Figure 3.    Fig. 3. Proposed structure for (E).  (F) 2[DABCOH2]C2O4.CuC2O4.2[DABCOH2Cl2]  This complex of copper contains the core [CuCl2(C2O4)2]4- and a long DABCOH22+…Cl-…DABCOH22+…oxalate…DABCOH22+…Cl-…DABCOH22+ connecting through bifurcated N-H…O,O hydrogen bonds the two monochelating oxalates (Figure 4).   Fig. 4. Proposed structure for (F).   (I) DABCOH2C2O4.Ni(C2O4).1/2[DABCOH2Cl2],   (J) DABCOH2C2O4.CuC2O4.1/2[ DABCOH2Cl2].EtOH  The structure of the complex (I) is also dimeric, the core being [NiCl(C2O4)2]3- (the environment around the metallic centre is a square based pyramid), the biprotoned DABCO connecting through bifurcated N-H…O,O hydrogen bonds the oxalates of each core but also the chlorido atoms through N-H…Cl leading to an infinite chain structure reported in Figure 5. For (J) a lattice molecule of ethanol is added to the (I) structure.  Journal of Engineering Studies and Research – Volume 23 (2017) No. 3                                       30  Fig. 5. Proposed structure for (I).   4. CONCLUSIONS  The studied complexes have dimeric -or infinite chain- structures, the environments being octahedral or square based pyramidal, the oxalate behaving as a monochelating and bifurcated hydrogen bonds involved ligand or only bifurcated hydrogen bonds concerned. Biprotonated DABCO alone or biprotonated DABCO, chlorido atoms and oxalate anion strings are involved in all the structures connecting oxalates or chloride and bromido atoms.     ACKNOWLEDGEMENTS  We deeply thank Professor Tebello Nyokong from Rhodes University, Grahamstown, South Africa, for her equipment support.  REFERENCES  [1] Umeyama, D., Lin, Y., Karunadasa, H.I., Red-to-Black Piezochromism in a Compressible Pb–I–SCN Layered Perovskite, Chemistry of Materials, vol. 28, no. 10, 2016, p. 3241–3244. [2] Arakcheeva, A., Chernyshov, D., Spina, M., Forro, L., Horvath, E., CH3NH3PbI3: precise structural consequences of water absorption at ambient conditions, Acta Crystallographica, vol. B72, 2016, 716-722. [3] Cao, G.-J., Lin, J., Fang, W-H., Zheng, S-T., Yang, G-Y., Open-framework aluminoborates co-templated by two types of primary amines, Dalton Transaction, vol. 40, 2011, p. 2940-2946. [4] Zhao, X-H., Huang, X-C., Zhang, S-L., Shao, D., Wei, H-Y., Wang, X-Y., Cation-dependent magnetic ordering and room temperature bistability in azido-bridged perovskite-type compounds, Journal of the American Chemical Society, vol. 135, no. 43, 2013,p. 16006 - 16009. [5] Gurzhiy, V.V., Tyshchenko, D.V., Krivovichev, S.V., Tananaev, I.G., Symmetry reduction in uranyl compounds with [(UO2)2(TO4)3]2-(T= Se, S, Mo) layers crystal structures of the new guanidinium uranyl selenate and methylammonium uranyl sulfate, Zeitschrift für Kristallographie, vol. 229, 2014, p. 368-377. Journal of Engineering Studies and Research – Volume 23 (2017) No. 3                                       31 [6] Sarr, M., Diasse-Sarr, A., Diallo, W., Plasseraud, L.,Cattey, H., Bis(cyclo-hexyl-ammonium) tetra-chlorido-(oxalato)stannate(IV), Acta Cryst. Sect. E, vol. 69, 2013, p. 473-474. [7] Sow, Y., Diop, L., Molloy, K.C., Kociok-Kohn, G., Ardisson, J.D., Crystal and molecular structure of bis(di-n-propylammonium) dioxalatodiphenylstannate, [n-Pr2NH2]2 [(C2O4)2SnPh2], Main Group Metal Chemistry, vol. 36, no. 5-6, 2013, p. 221-224. [8] Diop, M.B., Diop, L., Plasseraud, L., Maris, T., Crystal structure of bis-(2-methyl-1H-imidazol-3-ium) di-hydroxidobis(oxalato-κ2O1,O2)stannate(IV) monohydrate, Acta Crystallographica, vol. E72, 2016, p. 355–357. [9] Vaidhhyanathan, R., Natarajan, S., Rao, C.N.R., Hydrogen bonded structures in organic amines oxalates, Journal of Molecular structure, vol. 608, 2002, p. 123-133.  

NEW TRANSITION METAL OXALATO COMPLEXES WITH DABCOH22+ AS ADVERSE CATION: SYNTHESIS AND INFRARED STUDY

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NEW TRANSITION METAL OXALATO COMPLEXES WITH DABCOH22+ AS ADVERSE CATION: SYNTHESIS AND INFRARED STUDY

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