Kim, Jong-Young

Norquist, Alexander J.

O\u27Hare, Dermot

English

Haverford College: Haverford Scholarship

Haverford College Haverford Scholarship Faculty Publications Chemistry 2003 Incorporation of U(IV) into Metal-Organic Framework Solids, [UO2(C4H4O4)] H2O, [UO2F(C5H6O4)] 2H2O, and [(UO2)1.5(C8H4O4)2]2[(CH3)2NCOH2] H2O Jong-Young Kim Alexander J. Norquist Haverford College, anorquis@haverford.edu Dermot O'Hare Follow this and additional works at: https://scholarship.haverford.edu/chemistry_facpubs Repository Citation Kim, Jong-Young, Alexander J. Norquist, and Dermot O'Hare. "Incorporation of uranium (VI) into metal–organic framework solids,[UO2 (C4H4O4)]· H2O,[UO2F (C5H6O4)]· 2H2O, and [(UO2) 1.5 (C8H4O4) 2] 2 [(CH3) 2NCOH2]· H2O." Dalton Transactions 14 (2003): 2813-2814. This Journal Article is brought to you for free and open access by the Chemistry at Haverford Scholarship. It has been accepted for inclusion in Faculty Publications by an authorized administrator of Haverford Scholarship. For more information, please contact nmedeiro@haverford.edu. Incorporation of uranium(VI) into metal–organic framework solids,[UO2(C4H4O4)]H2O, [UO2F(C5H6O4)]2H2O, and[(UO2)1.5(C8H4O4)2]2[(CH3)2NCOH2]H2OJong-Young Kim, Alexander J. Norquist and Dermot O’Hare*Inorganic Chemistry Laboratory, South Parks RoadUniversity of Oxford, Oxford,UK OX1 3QR. E-mail: dermot.ohare@chem.ox.ac.ukReceived 12th June 2003, Accepted 18th June 2003First published as an Advance Article on the web 23rd June 2003Uranium–organic framework solids, in which uraniumbuilding units are connected by bidentate dicarboxylateanions such as succinate, glutarate, and isophthalate, weresynthesized; the glutarate and isophthalate compoundscontain cavities, in which occluded water and organictemplates reside.The preparation of microporous solids involving the co-ordination of metal centers to organic linker moieties with theaim of yielding open framework structures is the subject ofconsiderable effort. Dicarboxylate ligands have been exploitedrecently to form a variety of metal–organic frameworks toproduce zeolitic host–guest behavior. For example, Yaghi andco-workers have shown that the construction of metal–organicframeworks using dicarboxylate groups with variable sizes andshapes can provide an effective strategy to tailor the functional-ity and pore-size.1,2 Recently, Zheng and co-workers reportedthermally robust terephthalate and isophthalate polymerscontaining a Zn8SiO4 core.3,4 Despite the importance ofuranium-containing materials in catalysis,5 there are currentlyfew examples of uranium–organic framework solids.6 We haverecently synthesized a series of new organically templatedactinide materials such as uranium fluorides,7 phosphites,8aphosphates,8b molybdates,9 and thorium fluorides 10 by hydro-thermal reaction. In this work, we report the synthesis,structure, and characterization of new uranium–organicframework solids incorporating succinate (I), [UO2(C4H4O4)]H2O, glutarate (II), [UO2F(C5H6O4)]2H2O, and isophthalate(III), [(UO2)1.5(C8H4O4)2]2[CH3NCOH2]H2O.I and III are synthesized in a one-step process by the reactionof UO2(NO2)26H2O with succinic acid (1,4-butanedioic acid)or isophthalic acid (1,3-benzenedicarboxylic acid) in thepresence of DMF (N,N-dimethylformamide) and 40% HFunder hydrothermal conditions at 180 C. The materials areisolated in phase purity as octahedral- and rod-shaped yellowcrystals, respectively. II is synthesized as rod-shaped yellowcrystals by allowing the post heating solution to evaporateslowly for four weeks at room temperature.†‡The structure of I is composed of uranium pentagonalbipyramid (PBs) and succinate anions connected in a three-dimensional network.(Fig. 1) Each uranium center contains auranyl unit (OUO angle: 178.4(4); U(1)–O(1): 1.73(1) Å;U(1)–O(4): 1.750(9) Å) and is equatorially coordinated to fourFig. 1 View of I along [100] direction. Inorganic layers built up fromuranium pentagonal bipyramids (green polyhedra) are linked by theorganic group of succinate.oxides from succinate groups and one from a bound watermolecule. The uranium polyhedra form a layer in the ac plane,which is constructed by uranium PBs and dicarboxylate grouplinking each PBs (Fig. 1). The three dimensional architectureof I is completed by the bridging of the 2D-uranium layer bybidentate succinate units. The alkyl chains act as spacersbetween the layers.II exhibits a one-dimensional chain structure consisting ofuranium oxyfluoride dimers and cross-linking glutarate units.Each uranium is coordinated by six oxide and two fluorideligands in a hexagonal bipyramid arrangement, which shares anedge with each of the adjacent polyhedra to form dimers. Eachuranium center is bound axially to two oxides forming a uranylgroup (OUO angle: 179.6(5); U(1)–O(1): 1.779(8) Å). Thesix equatorial coordination sites around each uranium centreare occupied by four dicarboxylate and two fluoride ligands.The neutral [UO2F][C5O4H6] chain, which runs along [100]direction and the occluded water molecule in the cavity withinthe chain are shown in Fig. 2. Hydrogen bonding interactionsare observed between the waters and the oxides of uraniumdimer, (O(4)–H    O(3): 2.86 Å). As shown in Fig. 3, thelinkages between the anionic glutarates and the uraniumoxyfluoride dimers create a channel of width 3.4 × 2.0 Åalong [001] direction (shortest atom–atom contact distanceconsidering the van der Waals radii).The thermal behavior of II was studied using thermo-gravimetric analysis and X-ray powder diffraction. AroundFig. 2 Uranium glutarate chain of II running along [100] direction.Red and white spheres represent oxygen and carbon atoms, respectively.Fig. 3 Ball and stick representation of II along [001] directionshowing channels, in which occluded water molecules reside. Green,yellow, red, and white spheres correspond to uranium, fluorine, oxygen,and carbon atoms, respectively.DOI:10.1039/ b306733p2813T h i s  j o u r n a l  i s  ©  T h e  R o y a l  S o c i e t y  o f  C h e m i s t r y  2 0 0 3 D a l t o n  T r a n s . , 2 0 0 3 ,  2 8 1 3 – 2 8 1 4Downloaded by Haverford College on 22 March 2013Published on 23 June 2003 on http://pubs.rsc.org | doi:10.1039/B306733PView Article Online / Journal Homepage / Table of Contents for this issue100 C, a mass loss owing to the removal of the occluded wateris observed.(obs. 4.5, calcd. 4%) Beyond 200 C, furthermass losses corresponding to the decomposition of organiccomponent were observed (obs. 37.5, calcd. 35.8%). Porosityexperiment was unsuccessful owing to collapse of the structureupon removal of occluded water molecules.III has a one-dimensional chain structure consisting ofuranium hexagonal bipyramids (HPs) and anionic bridges of1,3-benzenedicarboxylate (BDC). The uranium HPs are com-posed of uranyl units and six equatorial oxide ligands from theBDC bridges or bound water. The uranium–BDC chain runningalong [100] direction is shown in Fig. 4(a). The connectivitycreates cavities within the chain, in which the protonated DMFmolecules reside. In the cavity of width 4.2 × 4.0 Å (shortestatom–atom contact distance considering the van der Waalsradii), the DMF forms hydrogen bonding interactions with theoxides of the uranium HPs (O(13)–H    O(5): 2.79 Å; O(14)–H    O(11): 2.93 Å; N(1)–H    O(3): 2.94 Å). The uranium–BDC chains stack along the b axis as shown in Fig. 4(b).In summary, we have reported the syntheses and crystal struc-tures of a series of uranium–organic frameworks crosslinked bythree bidentate dicarboylate anions; succinate, glutarate, andisophthalate. These results give us encouragement that we maybe able to form stable porous actinide–organic frameworks.Notes and references† I and III were synthesized by combining UO2(NO3)26H2O (0.502 g),HF (0.120 g), H2O (5.00 g), and C4H6O4 (0.0945 g)/DMF (0.0146 g) orC8H6O4 (0.166 g)/DMF (0.584 g) at room temperature. The respectivemixtures were heated to 180 C for 24 h and cooled to room temper-ature at 3 C h1. Monophasic crystalline products were recovered forI and III in ∼46 and ∼65% yield based on uranium. For II, a mixtureof UO2(NO3)2H2O (0.502 g), HF (0.120 g), H2O (5.00 g), C5H8O4(0.396 g), and DMF (0.439 g) were heated to 180 C for 24 h and cooledslowly to room temperature. The resultant solution was kept standingfor four weeks and the crystalline product was filtrated and recoveredwith ∼15% yield.Elemental analyses: I: obsd. (calcd.): C 11.97 (11.89), H 1.49 (1.47),U 57.64 (58.90); II: obsd. (calcd.): C 13.83 (13.74), H 1.88 (1.85),U 53.46 (54.45); III: obsd. (calcd.): C 30.08 (27.65), H 2.35 (2.20),N 1.97 (1.70), U 40.97 (43.26).Fig. 4 (a) Uranium–BDC chain of III running along [100] direction.The protonated DMF cations in the cavity are disordered over twoorientations. (b) Packing of uranium–BDC chain of III. The DMFcations and hydrogen atoms are omitted for clarity. Green, red, whitecolours represent uranium, oxygen, carbon atoms, respectively.‡ Crystallographic data: Single crystals of dimension 0.04 × 0.04 × 0.08mm for I, 0.08 × 0.08 × 0.2 mm for II, and 0.08 × 0.08 × 0.2 mm for IIIwere used for structural determination. Data were collected using anEnraf Nonius FR 590 Kappa CCD diffractometer with graphite mono-chromated Mo Kα radiation (λ = 0.71073 Å). Crystals were mounted ona glass fibre using N-Paratone oil and cooled in situ using an OxfordCryostream 600 Series to 150 K for data collection. Frames werecollected, indexed and processed using Denzo SMN and the files scaledtogether using HKL GUI within Denzo SMN.11 The heavy atompositions were determined using SIR97 12 and SHELXL-97.13 All othernon-hydrogen atom were located from Fourier difference maps andrefined with anisotropic thermal parameters using full matrix leastsquares procedures on F02. Hydrogen atoms were placed in geo-metrically idealized positions. All calculations were performed usingCRYSTALS,14 CAMERON,15 or WINGX 16 software packages.For I: monoclinic, space group P21/n (No. 14), a = 7.5720(5) Å,b = 10.7786(8) Å, c = 9.5090(6) Å, β = 90.773 (5), V = 776.01(9) Å3,Z = 4, Dc = 3.442 g cm3, 3481 reflections collected of which 1768were independent and 1201 were observed [I > 3σ(I )]. Refinementconverged with R = 0.0389, wR = 0.0830.For II: orthorhombic, space group C2/m (No. 12), a = 11.3572(4) Å,b = 18.1700(8) Å, c = 7.1855(3) Å, β = 119.577 (2), V = 1289.58(9) Å3,Z = 4, Dc = 2.324 g cm3, 5396 reflections collected of which 1533were independent and 1382 were observed [I > 2σ(I )]. Refinementconverged with R = 0.0539, wR = 0.1277.For III: monoclinic, space group P21/n (No. 14), a = 9.9344(2) Å,b = 15.6519(3) Å, c = 14.7961(3) Å, β = 104.4136 (7), V = 2228.26(8) Å3,Z = 8, Dc = 2.400 g cm3, 9840 reflections collected of which 5039were independent and 3491 were observed [I > 3σ(I )]. Refinementconverged with R = 0.0234, wR = 0.0532.CCDC reference numbers 210317–210319. See http://www.rsc.org/suppdata/dt/b3/b306733p/ for crystallographic data in CIF or otherelectronic format.1 H. Li, M. Eddaoudi, M. O’Keeffe and O. M. Yaghi, Nature, 1999,276, 402.2 M. Eddaoudi, J. Kim, N. Rossi, D. Vodak, J. Wachter, M. O’Keeffeand O. M. Yaghi, Nature, 2002, 295, 469.3 S. Y. Yang, L. S. Long, R. B. Huang and L. S. Zheng, Chem. Com-mun., 2002, 472.4 S. Y. Yang, L. S. Long, Y. B. Jiang, R. B. Huang and L. S. Zheng,Chem. Mater., 2002, 14, 3229.5 G. J. Hutchins, C. S. Heneghan, I. D. Hudson and S. H. Taylor,Nature, 1996, 384, 341.6 (a) A. Immirzi, G. Bombieri, S. Degetto and G. Marangoni, Acta.Crystallogr., Sect. B, 1975, 31, 1023; (b) G. Bombieri, E. Forsellini,G. Tomat, L. Magon and R. Graziani, Acta. Crystallogr., Sect. B,1974, 30, 2659; (c) G. Bombieri, F. Benetollo, R. M. Rojas, M. L.De Paz and A. Del Pra, Inorg. Chim. Acta, 1982, 61, 149; (d )Y. Zhang, D. Collison, F. R. Livens, A. K. Powell, S. Wocadlo andH. Eccles, Polyhedron, 2000, 19, 1757; (e) Y. Zhang, R. Livens,D. Collison, M. Helliwell, F. Heatley, A. K. Powell, S. Wocadlo andH. Eccles, Polyhedron, 2002, 21, 69–96.7 (a) R. J. Francis, P. S. Halasyamani and D. O’Hare, Angew. Chem.Int. Ed., 1998, 37, 2214; (b) S. M. Walker, P. S. Halasyamani,A. Simon and D. O’Hare, J. Am. Chem. Soc., 1999, 121, 10513; (c)R. J. Francis, P. S. Halasyamani, J. S. Bee and D. O’Hare, J. Am.Chem. Soc., 1999, 121, 1609; (d ) P. S. Halasyamani, S. M. Walkerand D. O’Hare, J. Am. Chem. Soc., 1999, 121, 7415.8 (a) M. Doran, S. M. Walker and D. O’Hare, Chem. Commun.,2001, 1988; (b) R. J. Francis, M. J. Drewitt, P. S. Halasyamani,C. Ranganathachar, D. O’Hare, W. Clegg and S. J. Teat, Chem.Commun., 1998, 279.9 P. S. Halasyamani, R. J. Francis, S. M. Walker and D. O’Hare, Inorg.Chem., 1999, 38, 271.10 J. Y. Kim, A. J. Norquist and D. O’Hare, Chem. Commun., 2002, 2198.11 Z. Otwinowski, Data Collection and Processing : DaresburyLaboratory, Warrington, 1993.12 G. Cascarano, C. Giacovazzo and A. Guagliardi, J. Appl. Crystal-logr., 1993, 26, 343.13 G. M. Sheldrick, SHELXL-97, Program for refinement of crystalstructures, University of Göttingen, Germany, 1997.14 D. J. Watkin, C. K. Prout, J. R. Carruthers, P. W. Betteridge andR. I. Cooper, CRYSTALS Issue 11, Chemical CrystallographyLaboratroy, Oxford, UK, 2001.15 D. J. Watkin, C. K. Prout and L. J. Pearce, CAMERON, ChemicalCrystallography Laboratroy, Oxford, UK, 1996.16 L. J. Farrugia, in WINGX—An integrated system of publicallyavailable windows programs for the solution, refinement, andanalysis of single-crystal X-ray diffraction data, ed. L. J. Farrugia,University of Glasgow, Glasgow, UK, 1998.2814 D a l t o n  T r a n s . , 2 0 0 3 ,  2 8 1 3 – 2 8 1 4Downloaded by Haverford College on 22 March 2013Published on 23 June 2003 on http://pubs.rsc.org | doi:10.1039/B306733PView Article Online

Incorporation of uranium(vi) into metal–organic framework solids, [UO2(C4H4O4)]·H2O, [UO2F(C5H6O4)]·2H2O, and [(UO2)1.5(C8H4O4)2]2[(CH3)2NCOH2]·H2O

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Incorporation of U(IV) into Metal-Organic Framework Solids, [UO2(C4H4O4)] H2O, [UO2F(C5H6O4)] 2H2O, and [(UO2)1.5(C8H4O4)2]2[(CH3)2NCOH2] H2O

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