In the crystal structure of the polymeric title compound, (C2H8N)[Eu(C2O4)2(H2O)]·3H2O, the independent oxalate that lies on a general position chelates to two Eu atoms, as do the other two oxalates that lie on different centres of inversion, the bridging mode of the oxalates giving rise to a three-dimensional anionic network. The water-coordinated Eu atom exists in a tricapped trigonal–prismatic geometry. The cations and solvent water mol­ecules occupy the cavities of the network and are involved in hydrogen bonding with each other and with the network.published_or_final_versio

Ng, SW

Wong, WT

Yang, YY

Zai, SB

ACS Nano

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Title Poly[dimethylammonium aquadi-μ-oxalato-europate(III)trihydrate]Author(s) Yang, YY; Zai, SB; Wong, WT; Ng, SWCitation Acta Crystallographica Section E: Structure Reports Online,2005, v. 61 n. 10, m1912-m1914Issued Date 2005URL http://hdl.handle.net/10722/68944Rights The definitive version is available at www.blackwell-synergy.commetal-organic papersm1912 Yang et al.  (C2H8N)[Eu(C2O4)2(H2O)]3H2O doi:10.1107/S1600536805027467 Acta Cryst. (2005). E61, m1912–m1914Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368Poly[dimethylammonium aquadi-l-oxalato-europate(III) trihydrate]Yang-Yi Yang,a Shao-Bo Zai,aWing-Tak Wongb and Seik WengNgc*aSchool of Chemistry and Chemical Engineering,Sun Yat-Sen University, Guangzhou 510275,People’s Republic of China, bDepartment ofChemistry, University of Hong Kong, HongKong, and cDepartment of Chemistry, Universityof Malaya, 50603 Kuala Lumpur, MalaysiaCorrespondence e-mail: seikweng@um.edu.myKey indicatorsSingle-crystal X-ray studyT = 295 KMean (C–C) = 0.005 A˚R factor = 0.026wR factor = 0.062Data-to-parameter ratio = 14.7For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2005 International Union of CrystallographyPrinted in Great Britain – all rights reservedIn the crystal structure of the polymeric title compound,(C2H8N)[Eu(C2O4)2(H2O)]3H2O, the independent oxalatethat lies on a general position chelates to two Eu atoms, as dothe other two oxalates that lie on different centres ofinversion, the bridging mode of the oxalates giving rise to athree-dimensional anionic network. The water-coordinatedEu atom exists in a tricapped trigonal–prismatic geometry.The cations and solvent water molecules occupy the cavities ofthe network and are involved in hydrogen bonding with eachother and with the network.CommentSome rare earth/monovalent-cation oxalates contain water,and compounds formulated as [M][(C2O4)2Ln].nH2O havebeen studied in order to understand the nature of the watermolecules, as water is crucial to their applications. Such doubleoxalates have been structurally authenticated by both single-crystal and powder-diffraction methods; the ammonium deri-vative is a monohydrate, and the water molecule is involved incoordination to the Y atom in [NH4][(C2O4)2(H2O)Y](McDonald & Spink, 1967). The nine-coordinate metal atomdisplays capped trigonal–prismatic coordination. The caesiumanalogue also has the rare earth atom in such a geometry(Bataille et al., 2000), as does the trihydrated sodium salt(Bataille & Loue¨r, 1999). Another aquadioxalatoyttrate, apropyl-1,2-diammonium salt, has two solvent water moleculesthat interact with the cation (Vaidhyanathan et al., 2001).Double salts with other nine-coordinate water-coordinatedrare earths include the erbium (Steinfink & Brunton, 1970),lanthanum (Fourcade-Cavillou & Trombe, 2002), neodymium(Fourcade-Cavillou & Trombe, 2002; Kahwa et al., 1984),samarium, europium, gadolinium and terbium (Kahwa et al.,1984) complexes.The title dimethylammonium aquadioxalatoeuropate(III)exists as the trihydrate, (I) (Fig. 1). The Eu atom is surroundedReceived 30 August 2005Accepted 1 September 2005Online 7 September 2005by the eight atoms of four oxalates and the water molecule in acapped trigonal–prismatic environment (Fig. 2). The cationsand solvent water molecules interact with each other along thechannels of the polymeric anion (Fig. 3); extensive hydrogenbonds (Table 2) give rise to a tightly held network structurethat has no solvent-accessible cavities.ExperimentalA mixture of dieuropium trioxalate x-hydrate (0.012 g, 0.02 mmol),1,3,5-benzenetricarboxylic acid (0.011 g, 0.05 mmol) and water (4 ml)was heated to 333 K, and to this mixture was added di-n-propyl-ethylamine (0.04 g, 0.05 mmol). The solution was placed in a Teflon-lined Parr bomb, which was heated to 453 K for 48 h. It was cooled ata rate of 5 K h1 to 333 K to yield colourless crystals of (I). Asbenzenetricarboxylic acid was not incorporated in the product, thereaction is essentially one between dieuropium trioxalate anddipropylethylamine; the dimethylammonium cation in the productprobably results from the decomposition of dipropylethylamine.Crystal data(C2H8N)[Eu(C2O4)2(H2O)]3H2OMr = 446.16Monoclinic, P21=na = 9.674 (1) A˚b = 11.761 (1) A˚c = 12.315 (2) A˚ = 99.285 (2)V = 1382.8 (3) A˚3Z = 4Dx = 2.143 Mg m3Mo K radiationCell parameters from 885reflections = 2.4–27.2 = 4.60 mm1T = 295 (2) KBlock, colourless0.06  0.05  0.05 mmData collectionBruker SMART 1000 area-detectordiffractometer’ and ! scansAbsorption correction: multi-scan(SADABS; Sheldrick, 1996)Tmin = 0.702, Tmax = 0.8038455 measured reflections3113 independent reflections2578 reflections with I > 2(I)Rint = 0.026max = 27.5h = 12 ! 7k = 15 ! 14l = 15! 15RefinementRefinement on F 2R[F 2 > 2(F 2)] = 0.026wR(F 2) = 0.062S = 0.993113 reflections212 parametersH atoms treated by a mixture ofindependent and constrainedrefinementw = 1/[2(Fo2) + (0.0359P)2]where P = (Fo2 + 2Fc2)/3(/)max = 0.001max = 1.07 e A˚3min = 0.42 e A˚3Table 1Selected geometric parameters (A˚, ).Eu1—O1 2.412 (2)Eu1—O2i 2.430 (2)Eu1—O3 2.476 (2)Eu1—O4i 2.469 (2)Eu1—O5 2.430 (3)Eu1—O6ii 2.465 (3)Eu1—O7 2.471 (3)Eu1—O8iii 2.492 (3)Eu1—O1w 2.505 (3)O1—Eu1—O2i 136.0 (1)O1—Eu1—O3 66.4 (1)O1—Eu1—O4i 72.7 (1)O1—Eu1—O5 138.9 (1)O1—Eu1—O6ii 123.9 (1)O1—Eu1—O7 71.5 (1)O1—Eu1—O8iii 111.5 (1)O1—Eu1—O1w 71.2 (1)O2i—Eu1—O3 144.2 (1)O2i—Eu1—O4i 66.5 (1)O2i—Eu1—O5 84.7 (1)O2i—Eu1—O6ii 71.7 (1)O2i—Eu1—O7 134.1 (1)O2i—Eu1—O8iii 69.7 (1)O2i—Eu1—O1w 82.0 (1)O3—Eu1—O4i 137.5 (1)O3—Eu1—O5 82.7 (1)O3—Eu1—O6ii 72.5 (1)O3—Eu1—O7 73.5 (1)O3—Eu1—O8iii 136.0 (1)O3—Eu1—O1w 82.2 (1)O4i—Eu1—O5 138.7 (1)O4i—Eu1—O6ii 125.4 (1)O4i—Eu1—O7 104.7 (1)O4i—Eu1—O8iii 70.3 (1)O4i—Eu1—O1w 73.9 (1)O5—Eu1—O6ii 65.9 (1)O5—Eu1—O7 74.1 (1)O5—Eu1—O8iii 72.3 (1)O5—Eu1—O1w 132.7 (1)O6ii—Eu1—O7 129.7 (1)O6ii—Eu1—O8iii 124.5 (1)O6ii—Eu1—O1w 66.8 (1)O7—Eu1—O8iii 65.2 (1)O7—Eu1—O1w 141.2 (1)O8iii—Eu1—O1w 140.9 (1)Symmetry codes: (i) xþ 32; y 12;zþ 12; (ii) xþ 1;yþ 1;zþ 1; (iii)xþ 2;yþ 1;zþ 1.metal-organic papersActa Cryst. (2005). E61, m1912–m1914 Yang et al.  (C2H8N)[Eu(C2O4)2(H2O)]3H2O m1913Figure 1A view of a portion of the three-dimensional structure, showing thegeometry of the Eu atom in polymeric (I). Displacement ellipsoids aredrawn at the 50% probability level. [Symmetry codes: (i) 32 x, y 12,12 z; (ii) 1  x, 1  y, 1  z; (iii) 2  x, 1  y, 1  z.]Figure 2The trigonal–prismatic geometry of the Eu atom in (I). (Symmetry codesas in Fig. 1.)Table 2Hydrogen-bond geometry (A˚, ).D—H  A D—H H  A D  A D—H  AO1w—H1w1  O2w 0.85 (1) 1.92 (1) 2.759 (5) 169 (4)O1w—H1w2  O2wiv 0.85 (1) 2.05 (2) 2.862 (5) 162 (4)O2w—H2w2  O7i 0.85 (1) 2.30 (2) 3.071 (5) 151 (4)O2w—H2w2  O8i 0.85 (1) 2.37 (4) 3.011 (4) 133 (5)O3w—H3w1  O4v 0.85 (1) 2.02 (2) 2.838 (5) 162 (7)O3w—H3w2  O4w 0.84 (1) 2.00 (3) 2.770 (6) 151 (5)O4w—H4w1  O2iv 0.85 (1) 2.08 (2) 2.893 (4) 159 (5)O4w—H4w2  O3vi 0.85 (1) 2.12 (1) 2.962 (5) 173 (5)N1—H1n1  O3w 0.85 (1) 1.96 (1) 2.792 (6) 167 (4)N1—H1n2  O6ii 0.85 (1) 2.05 (2) 2.879 (5) 165 (5)Symmetry codes: (i) xþ 32; y 12;zþ 12; (ii) xþ 1;y þ 1;zþ 1; (iv)xþ 1;yþ 1;z; (v) x 12;yþ 32; z 12; (vi) xþ 12; y 12;zþ 12.The C-bound H atoms were placed in calculated positions, withC—H = 0.96 A˚ and Uiso(H) = 1.5Ueq(C), and were included in therefinement in the riding-model approximation. Water and ammoniumH atoms were located in difference Fourier maps, and were refinedwith distance restraints of O—H = N—H = 0.85 (1) A˚ and H  H =1.39 (1) A˚ and with Uiso(H) = 1.2Ueq(O,N). The short H1w2  H2w1distance of 2.08 A˚ is probably a consequence of some disorder inatomO2w, but the disorder could not be resolved. The largest peak inthe final difference Fourier map of 1.08 e A˚3 was about 1 A˚ fromEu1.Data collection: SMART (Bruker, 2000); cell refinement: SAINT(Bruker, 2000); data reduction: SAINT; program(s) used to solvestructure: SHELXS97 (Sheldrick, 1997); program(s) used to refinestructure: SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEPII (Johnson, 1976); software used to prepare material forpublication: SHELXL97.The authors thank the Guangdong Natural Science Foun-dation (grant No. 04300564), the Scientific Research Foun-dation for Returned Overseas Chinese Scholars of the StateEducation Ministry of China (grant No. 2004–527), theUniversity of Hong Kong and the University of Malaya forsupporting this study.ReferencesBataille, T., Auffre´dic, J.-P. & Loue¨r, D. (2000). J. Mater. Chem. 10, 1707–1711.Bataille, T. & Loue¨r, D. (1999). Acta Cryst. C55, 1760–1762.Bruker (2000). SAINT and SMART. Bruker AXS Inc., Madison, Winsonsin,USA.Fourcade-Cavillou, F. & Trombe, J.-C. (2002). Solid State Sci. 4, 1199–1208.Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge NationalLaboratory, Tennessee, USA.Kahwa, I. A., Fronczek, F. R. & Selbin, J. (1984). Inorg. Chim. Acta, 68, 181–186.McDonald, T. R. R. & Spink, J. M. (1967). Acta Cryst. 23, 944–949.Sheldrick, G. M. (1996). SADABS. University of Go¨ttingen, Germany.Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University ofGo¨ttingen, Germany.Steinfink, H. & Brunton, G. D. (1970). Inorg. Chem. 9, 2112–2115.Vaidhyanathan, R., Natarajan, S. & Rao, C. N. R. (2001). Chem. Mater. 13,185–191.metal-organic papersm1914 Yang et al.  (C2H8N)[Eu(C2O4)2(H2O)]3H2O Acta Cryst. (2005). E61, m1912–m1914Figure 3Aview of the polymeric [(C2O4)2(H2O)Eu] network in (I). H atoms havebeen omitted.

Poly[dimethylammonium aquadi-μ-oxalato-europate(III) trihydrate]

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Poly[dimethylammonium aquadi-μ-oxalato-europate(III) trihydrate]

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