J O U R N A L O F C H E M I S T R Y Materials Hybrid open frameworks (MIL-n). Part 4† Synthesis and crystal structure of MIL-8, a series of lanthanide glutarates with an open framework, [Ln(H2O)]2[O2C(CH2)3CO2]3·4H2O F. Serpaggi and G. Fe� rey* Institut Lavoisier,UMR CNRS 173, Universite� de Versailles Saint-Quentin-en-Yvelines, 45, avenue des Etats-Unis, 78035 Versailles Cedex, France. E-mail: ferey@chimie.uvsq.fr Received 9th April 1998, Accepted 17th September 1998 The first series of rare-earth carboxylates with an open framework has been prepared hydrothermally (180 °C, 3 days) by the action of glutaric acid on the metal chlorides in the presence of base.The crystal structure of the neodymium compound [NdIII(H2O)]2[O2C(CH2)3CO2]3·4H2O has been determined by single-crystal X-ray diVraction.The composite material crystallizes in the monoclinic space group C2/c (no. 15) with a=8.1174(1) A° , b=15.1841(3) A° , c=19.8803(3) A° , b=93.762(1)° (final agreement factors R1=0.0279, wR2=0.0693). The organic– inorganic network is three-dimensional and consists of chains of edge-sharing rare-earth polyedra NdO8(H2O) along the [100] direction, linked together by the carbon chains along two directions.The connection involves the formation of channels parallel to the rare-earth chains in which weakly bonded water molecules are incorporated. The analogous compounds were obtained with Pr, Sm, Eu, Gd, Dy, Ho and Y. species react with inorganic compounds.4 While most of the Introduction papers cited in the literature concern non-functionalized mono- Since 1992, the ULM-n (n19) series of fluorinated micropo- phosphonates, with the aim of synthesizing layered comrous gallophosphates that our group discovered and charac- pounds,5 some attempts with diphosphonates6 and terized structurally led us to propose a hypothesis for the monophosphonates functionalized with –CO2H or –NH2 mechanism of their formation1 from solution during their groups7 led to a few three-dimensional compounds.The chelattemplated synthesis. Indeed, the structural studies showed that ing power of the diphosphonate group generally leads to a the inorganic skeleton of the porous solids was built up from pillaring between inorganic layers or chains. This property can a small number of well defined oligomers with a formal charge be utilised as a general method for obtaining composite solids of -2 (mainly gallophosphate tetramers Ga2P2 and hexamers in which the skeleton is built up simultaneously by organic Ga3P3).The hypothesis therefore claimed that the same oligo- and inorganic species. This approach can present three advanmers existed in the solution and that the charge density of the tages: (i) owing to the large number of commercial phosphonprotonated amine was the driving force of the synthesis.In ates and the possibility to prepare some of them by the the solution, we assumed that it controlled (i) the extent of Arbuzov reaction, a large modulation of the open framework the oligomeric condensation of monophosphate complexes of character of the corresponding materials may be expected, (ii) the gallium species up to the equalization of the charge it can allow non-templated syntheses of microporous samples, densities of the amine and the oligomer and (ii) the formation and (iii) this strategy can be extended to other chelating agents of a neutral ion pair which allows the infinite condensation and diVerent from phosphonates such as sulfonates and carbtherefore the formation of the solid. The structure of the latter, oxylates.Complexation of the lanthanide elements by carbwhich depends on the volume and the plasticity of the pair, is oxylates has already been studied and usually leads to the obtained using criteria of minimization of the lattice energy. formation of clusters, some of which have been structurally This hypothesis has just received a few weeks ago its first characterized.8 To our knowledge, only two-dimensional rareexperimental proof by Taulelle and coworkers2 by in situ earth oxalates have been mentioned previously,9 and no three- NMR experiments under hydrothermal conditions.dimensional lanthanide carboxylates with longer carbon chains Before this result, and considering that this hypothesis was have been reported.We report here the hydrothermal preptrue, we found for the first time some hitherto unknown aration and the crystal structure determination of the first magnetic microporous iron and vanadium phosphates,3 in three-dimensional lanthanide glutarates. which the total substitution of Ga by Fe or V induces new structural types. Supplementary work is currently in progress Experimental in this field with the use of other 3d transition metals.The extension of this idea to microporous rare earth phosphates Reagents unfortunately failed owing to the strong aYnity of phosphate LnCl3·xH2O (x=6 or 7) (Aldrich, 99.9%), glutaric acid and fluoride anions towards lanthanide elements which, what- (HO2C(CH2)3CO2H, Aldrich, 99%), and 1,3-diaminopropane ever the chemical conditions, leads to the formation of monaz- [H2N(CH2)3NH2, Aldrich, 99%] were used as received with ite type phosphates LnPO4 and fluorides LnF3.no further purification. In order to obtain lanthanide compounds with an open framework, it was then necessary to change our strategy and Preparation of lanthanide glutarates substitute phosphate anions by other chelating agents which prevent the formation of dense, insoluble inorganic species.Neodymium glutarate, [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O, This is the case for phosphonates and since the work of was hydrothermally synthesized in a 23 ml Teflon-lined Parr Alberti, Dines and Clearfield, it is well known that these bomb under autogeneous pressure (180 °C, 3 days). The starting reagents were neodymium(III) chloride hexahydrate (NdCl3·6H2O, Aldrich, 99.9%), glutaric acid [HO2C- †Part 3: preceding paper.J. Mater. Chem., 1998, 8, 2737–2741 2737Table 1 Crystal data and structure refinement for [Nd(H2O)]2- (CH2)3CO2H, Aldrich, 99%; pKa(1)=4.31 and pKa(2)= [O2C(CH2)3CO2]3·4H2O 5.4110], 1,3-diaminopropane [H2N(CH2)3NH2, Aldrich, 99%] and distilled water.The molar ratio was 1 NdCl3·6H2O51 Empirical formula C15H30Nd2O18 HO2C(CH2)3CO2H51.3 H2N(CH2)3NH25100 H2O. Neo- Formula weight 786.86 dymium chloride and glutaric acid were first dissolved sepa- Temperature/K 293(2) Wavelength/A° 0.71073 rately in 2 ml H2O. The amine was added to the glutaric acid Crystal system Monoclinic solution which was then mixed with the neodymium chloride Space group C2/c (no. 15) solution.The initial pH was 6 (this pH value was reached by Unit cell dimensions the addition of the amine and was selected in order to a/A° 8.1174(1) deprotonate both acid groups of the diacid) and the resulting b/A° 15.1841(3) pH was 5–6. The replacement of 1,3-diaminopropane by c/A° 19.8803(3) b/degrees 93.762(1) diVerent bases (NaOH, NH3, ethylenediamine, tetramethylam- Volume/A° 3, Z 2445.07(7), 4 monium hydroxide) led to the same product.The crystalline Dc/g cm-3 2.138 product obtained was filtered oV, washed with distilled water Absorption coeYcient/mm-1 4.282 and dried at room temperature. Similar procedures were used F (000) 1536 to obtain the analogous compounds with Pr, Sm, Eu, Gd, Dy, Crystal size/mm 0.3×0.2×0.16 Ho and Y.h range for data collection/ 3.38–32.24 degrees Limiting indices -11h11, -15k22, X-Ray data collection -29l21 X-Ray powder diVraction (XRD) data were collected on a Reflections collected 9823 Independent reflections 4095 (Rint=0.0294) Siemens D5000 diVractometer with Cu-Ka radiation, in the Refinement method Full-matrix least-squares on F2 range 5<2h<60°, with step size 0.04° (2h) and acquisition Data/restraints/parameters 4095/0/160 with steps of 1 s (Fig. 1). Goodness-of-fit on F2 1.152 Final R indices [I>2s(I )] R1=0.0279, wR2=0.0681 Thermogravimetry R indices (all data) R1=0.0307, wR2=0.0693 Extinction coeYcient 0.0011(1) TG analysis was carried out on a TA Instrument type 2050 Largest diV. peak and 1.435 and -1.251 theralyzer under O2 gas flow with a heating rate of hole/e A° -3 5 °Cmin-1, from 30 to 900 °C.IR spectroscopy The final reliability factors converged to R1=0.0279 and wR2=0.0693. Final positional parameters and intramolecular FTIR spectra were obtained on a Nicolet Magna-IRTM 550 distances and angles are given in Tables 2 and 3. The cell spectrometer with the usual KBr pellet technique.parameters for the isotypic Pr, Nd, Sm, Eu, Gd, Dy, Ho and Y compounds are summarized in Table 4. Structure determination Full crystallographic details, excluding structure factors, A suitable single-crystal for X-ray analysis was mounted with have been deposited at the Cambridge Crystallographic Data Araldite on a glass fiber. The intensity data were collected on a Siemens SMART three-circle diVractometer equipped with Table 2 Atomic coordinates and equivalent isotropic displacement a CCD bidimensional detector.The crystal-to-detector disparameters (A° 2) for [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O tance was 45 mm allowing for data collection up to 65° (2h). Slightly more than one hemisphere of data were recorded. Atom x y z Ueq a Crystal data and details of the data collection for [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O are given in Table 1.An Nd 0.2456(1) 0.0377(1) 0.4881(1) 0.016(1) O1 0.5142(3) 0.0448(1) 0.4384(1) 0.024(1) empirical absorption correction was applied using the O2 0.2319(3) -0.0496(2) 0.5943(1) 0.034(1) SADABS program11 based on the method of Blessing.12 The O3 -0.0150(2) 0.0797(1) 0.5344(1) 0.024(1) cell was found to be monoclinic, space group C2/c (no. 15), O4 0.2661(2) -0.1158(1) 0.4401(1) 0.029(1) a=8.1174(1) A° , b=15.1841(3) A° , c=19.8803(3) A° , b= O5 0.1534(3) 0.0551(2) 0.3665(1) 0.029(1) 93.762(1)°. The structure was solved using direct methods of O6 0.1679(3) 0.1778(1) 0.4258(1) 0.026(1) the SHELXTL package.13 Nd and O atoms were first located Ow1 0.3882(3) 0.1483(2) 0.5619(1) 0.032(1) Ow2 0.607(1) -0.4081(4) 0.6992(3) 0.181(4) and C atoms were found from diVerence-Fourier maps.Ow3 0.875(1) -0.4304(7) 0.7825(6) 0.223(5) Hydrogen atoms were refined with geometrical constraints. C1 0.3798(3) -0.0742(2) 0.6015(1) 0.018(1) C2 0.4283(4) -0.1410(2) 0.6554(2) 0.022(1) C3 0.3594(5) -0.2332(2) 0.6356(2) 0.029(1) C4 -0.0518(4) 0.2256(2) 0.5782(2) 0.030(1) C5 -0.1157(3) 0.1359(2) 0.5568(2) 0.020(1) C6 0.1334(3) 0.1379(2) 0.3701(2) 0.020(1) C7 0.0746(4) 0.1903(2) 0.3080(2) 0.024(1) C8 0 0.1340(3) b 0.027(1) H2A 0.3856(4) -0.1228(2) 0.6977(2) 0.026 H2B 0.5476(4) -0.1438(2) 0.6618(2) 0.026 H3A 0.3705(5) -0.2716(2) 0.6746(2) 0.035 H3B 0.2427(5) -0.2281(2) 0.6221(2) 0.035 H4A -0.0620(4) 0.2647(2) 0.5396(2) 0.036 H4B 0.0647(4) 0.2206(2) 0.5920(2) 0.036 H7A 0.1672(4) 0.2231(2) 0.2923(2) 0.029 H7B -0.0074(4) 0.2326(2) 0.3206(2) 0.029 H8A 0.0851(4) 0.0964(3) 0.2335(2) 0.033 H8B -0.0851(4) 0.0964(3) 0.2665(2) 0.033 aUeq is defined as one third of the trace of the orthogonalized Uij tensor.) Fig. 1 X-Ray pattern for [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O. 2738 J. Mater. Chem., 1998, 8, 2737–2741Table 3 Bond lengths (A° ) and angles (degrees) for [Nd(H2O)]2[O2C- (CH2)3CO2]3·4H2Oa Nd–O3 2.445(2) C1–C2 1.508(4) Nd–O1 2.455(2) C2–C3 1.549(4) Nd–Ow1 2.467(2) C3–C4c 1.524(4) Nd–O5 2.498(2) C4c–C5c 1.509(4) Nd–O2 2.500(2) C5c–O3c 1.282(3) Nd–O6 2.521(2) C5c–O4d 1.264(3) Nd–O4 2.529(2) C6–O5 1.270(3) Nd–O3a 2.602(2) C6–O6 1.278(3) Nd–O1b 2.671(2) C6–C7 1.518(4) C1–O1b 1.288(3) C7–C8 1.528(4) C1–O2 1.257(3) O3–Nd–O1 162.32(7) Ow1–Nd–O1b 72.37(7) Fig. 2 Schematic of the open framework of [Nd(H2O)]2- O3–Nd–Ow1 89.02(8) O5–Nd–O1b 137.79(7) [O2C(CH2)3CO2]3·4H2O showing neodymium chains linked along O1–Nd–Ow1 79.32(8) O2–Nd–O1b 50.29(7) two directions by two types of carboxylates, in order to form tunnels O3–Nd–O5 97.17(8) O6–Nd–O1b 144.57(7) along the metal chains. O1–Nd–O5 79.78(8) O4–Nd–O1b 73.15(7) Ow1–Nd–O5 126.99(8) O3a–Nd–O1b 105.31(7) O3–Nd–O2 74.55(8) C1b–O1–Nd 155.6(2) O1–Nd–O2 116.96(7) C1b–O1–Ndb 90.3(2) Ow1–Nd–O2 84.53(9) Nd–O1–Ndb 113.25(8) O5–Nd–O2 147.80(9) C1–O2–Nd 99.2(2) O3–Nd–O6 76.70(7) C5–O3–Nd 153.1(2) O1–Nd–O6 87.98(7) C5a–O3a–Nd 92.7(2) Ow1–Nd–O6 79.04(8) Nd–O3–Nda 112.75(8) O5–Nd–O6 52.07(7) C5a–O4–Nd 96.6(2) O2–Nd–O6 146.97(8) C6–O5–Nd 94.7(2) O3–Nd–O4 117.55(7) C6–O6–Nd 93.5(2) O1–Nd–O4 78.83(7) O2–C1–O1b 119.9(3) Ow1–Nd–O4 144.28(7) O2–C1–C2 118.9(2) O5–Nd–O4 75.83(8) O1b–C1–C2 121.1(2) O2–Nd–O4 80.66(9) C1–C2–C3 110.7(3) O6–Nd–O4 127.80(8) C2–C3–C4c 112.4(3) O3–Nd–O3a 67.25(8) C3–C4c–C5c 114.3(3) O1–Nd–O3a 127.50(7) O4d–C5c–O3c 119.8(3) Ow1–Nd–O3a 150.79(8) O4d–C5c–C4c 121.3(2) O5–Nd–O3a 74.92(8) O3c–C5c–C4c 118.9(2) O2–Nd–O3a 73.20(8) O5–C6–O6 119.7(3) O6–Nd–O3a 109.84(7) O5–C6–C7 120.5(3) O4–Nd–O3a 50.81(6) O6–C6–C7 119.8(3) O3–Nd–O1b 122.37(7) C6–C7–C8 114.1(3) O1–Nd–O1b 66.75(8) C7–C8–C7e 111.9(4) aSymmetry transformations used to generate equivalent atoms: a -x, -y, -z+1; b-x+1, -y, -z+1; cx+1/2, y-1/2, z; d-x+1/2, -y-1/2, -z+1; e-x, y, -z+1/2.Centre (CCDC). See Information for Authors, J. Mater. Chem., 1998, Issue 1. Any request to the CCDC for this Fig. 3 Projection of the structure of [Nd(H2O)]2[O2C(CH2)3- material should quote the full literature citation and the CO2]3·4H2O along the [011] direction showing the linkage of the reference number 1145/120. chains of neodymium polyhedra by the carbon chains (in black) along the [101] direction (other carbon atoms, free water molecules and hydrogen atoms have been omitted for more clarity). Results Structure of [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O formation of small channels along the [100] direction (with free aperture 3.3 A° and parallel to the neodymium polyhedra The structure of [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O is threedimensional, consisting of chains of edge-sharing NdO8(H2O) chains), in which weakly bonded water molecules are incorporated.polyhedra, along the [100] direction, linked together by the carbon chains along the [010] and roughly [101] directions. As highlighted in Fig. 2, there are two types of carboxylates, in the ratio 152. The first type (carboxylate I, black in the The complex connection, schematized in Fig. 2, involves the Table 4 Cell parameters, unit cell volume, and calculated densities for [M(H2O)]2[O2C(CH2)3CO2]3·4H2O (M=Pr, Nd, Sm, Eu, Gd, Dy, Ho or Y) M a/A° b/A° c/A° b/degrees V/A° 3 Dc/g cm-3 Pr 8.1319(1) 15.1855(2) 19.8758(2) 93.732(0) 2449.2(1) 2.12 Nd 8.1174(1) 15.1841(3) 19.8803(3) 93.762(1) 2445.1(1) 2.14 Sm 8.0160(2) 15.0592(1) 19.7063(4) 93.940(1) 2373.2(1) 2.24 Eu 8.0161(3) 15.0740(5) 19.7237(6) 93.978(1) 2377.6(1) 2.24 Gd 7.9767(1) 15.0043(2) 19.6852(1) 94.326(1) 2349.3(1) 2.30 Dy 7.9516(1) 14.9801(2) 19.7034(3) 94.668(1) 2339.2(1) 2.34 Ho 7.9355(1) 14.9338(1) 19.6973(1) 94.808(1) 2327.6(1) 2.36 Y 7.9355(3) 14.9438(6) 19.6973(8) 94.808(1) 2327.6(3) 1.93 J.Mater. Chem., 1998, 8, 2737–2741 2739Fig. 6 Space filling representation of the structure of [Nd- (H2O)]2[O2C(CH2)3CO2]3·4H2O showing the open framework with small channels along the [100] direction.Fig. 4 Projection of the structure of [Nd(H2O)]2[O2C(CH2)3- coordinated O1b and O3a oxygen atoms, bonded to two CO2]3·4H2O along the [001] direction showing the linkage of the neodymium atoms and carbon; in the chelating –C6O5O6- chains of neodymium polyhedra by the carbon chains (in white) carboxylic group (carboxylate I ), the C6–O5 and C6–O6 along the [010] direction (other carbon atoms, free water molecules distances are equivalent [1.270(3) and 1.278(3) A° , respect- and hydrogen atoms have been omitted for more clarity).ively]. The chelating and bridging eVects of the carboxylic groups can also be evidenced by FTIR analysis. Indeed, the bands observed in the range 1600–1400 cm-1 (1536 cm-1, 1445 and 1411 cm-1) can be assigned to nCLO and nCKO vibrations for bridging and chelating carboxylic groups, as Deacon and Phillips showed for metal acetates and trifluoroacetates. 14 The whole arrangement leads to the formation of an open framework, as shown in Fig. 5 and 6. The channels are elliptical with free aperture dmin#3 A° (between two H atoms, RH=1.1 A° ) by dmax#5 A° (between two O atoms, RO= 1.5 A° ). Such dimensions do not allow any porosity.Two Nd–Nd distances, 4.20(1) and 4.28(1) A° occur in the chains. The neodymium atoms are nine-coordinated by one water molecule (Ow1) and eight oxygen atoms from five carboxylic groups, as shown in Fig. 7. Three carboxylate groups chelate the metal atom while two other carboxylate Fig. 5 Projection of the structure of [Nd(H2O)]2[O2C(CH2)3- CO2]3·4H2O along the [100] direction showing the channels and water molecules within them (for a better distinction between the carbon chains, both types of chains are represented in white and black, according to Fig. 3 and 4). figures), which connect the chains along the [101] direction, simply chelates one neodymium atom at each end, as shown in Fig. 3. The second type (carboxylate II, white in the figures) which ensures the linkage of the chains along the [010] direction chelates a metal atom but one of the chelating oxygen atoms is also shared with an adjacent metal atom, as shown in Fig. 4. Examination of the C–O distances shows two types of –CO2- carboxylate groups: both –C1O1bO2- and –C5aO3aO4-, which belong to carboxylate II, exhibit one Fig. 7 Representation of the coordination about the neodymium atom short [C1–O2 1.257(3), C5a–O4 1.264(3) A° ] and one longer in [Nd(H2O)]2[O2C(CH2)3CO2]3·4H2O including the numberings scheme used in the Tables.distance [C1–O1b 1.288(3), C5a–O3a 1.282(3) A° ], due to three- 2740 J. Mater. Chem., 1998, 8, 2737–2741P. Zappelli, Angew. Chem., Int. Ed. Engl., 1993, 32, 1357; groups share only one bridging oxygen atom.The angles G. Alberti, F. Marmottini, S. Murcia-Mascaro� s and R. Vivani, formed at the neodymium atom by the chelate rings are quite Angew. Chem., Int. Ed. Engl., 1994, 33, 1594; L. A. Vermeulen and small [O5–Nd–O6 52.1(1), O2–Nd–O1b 50.3(1), O4–Nd–O3a M. E. Thompson, Chem. Mater., 1994, 6, 77; V. Soghomonian, 50.8(1)°], leading to a highly distorted polyhedron around the Q.Chen, R. C. Haushalter and J. Zubieta, Angew. Chem., Int. Ed. neodymium. Moreover, each chelate ring has one short and Engl., 1995, 34, 223; V. Soghomonian, R. Diaz, R. C. Haushalter, C. J. O’Connor and J. Zubieta, Inorg. Chem., 1995, 34, 4460; one longer Nd–O bond [Nd–O2 2.50(1) and Nd–O1b H. Byrd, A. Clearfield, D. Poojary, K. P. Reis and M. E. 2.67(1) A° , Nd–O4, 2.53(1) and Nd–O3a 2.60(1) A° ].The pres- Thompson, Chem. Mater., 1996, 8, 2239; D. M. Poojary, ence of water molecules seen by the X-ray analysis and B. Zhang, P. Bellinghausen and A. Clearfield, Inorg. Chem., 1996, indicated by bond valence calculations15 is confirmed by TG 35, 4942; 5254; G. Bonavia, R. C. Haushalter, C. J. O’Connor and analysis, the curve indicating two successive weight losses of J.Zubieta, Inorg. Chem., 1996, 35, 5603; P. J. Zapf, D. J. Rose, 7.4 and 4.6 wt.% in the ranges 30–100 and 100–200 °C, which R. C. Haushalter and J. Zubieta, J. Solid State Chem., 1996, 125, 182; D. L. Lohse and S. C. Sevov, Angew. Chem., Int. Ed. Engl., can be attributed to the loss of free water molecules Ow2 and 1997, 36, 1619. Ow3 (9.2 wt.%) and coordinating water molecule Ow1 7 S.Drumel, P. Janvier, P. Barboux, M. Bujoli-DoeuV and (4.6 wt.%), respectively. The final residue at 900 °C is the B. Bujoli, Inorg. Chem., 1995, 34, 148; S. Drumel, P. Janvier, D. neodymium oxide Nd2O3. The compound is able to reversibly Deniaud and B. Bujoli, J. Chem. Soc., Chem. Commun., 1995, adsorb and desorb free water molecules in the temperature 1051. range 25–100 °C; the study of this behaviour will be reported 8 J.W. Bats, R. Kalus and H. Fuess, Acta Crystallogr., Sect. B, 1979, 35, 1225; M. C. Favas, D. L. Kepert, B. W. Skelton and elsewhere.16 A. H. White, J. Chem. Soc., Dalton Trans., 1980, 54; M. S. Khiyalov, I. R. Amiraslanov, F. N. Musaev and Kh. S. Mamedov, Koord. Khim., 1982, 8, 548; H. Gries and H. Miklautz, Physiol. Acknowledgements Chem.Phys. Med. NMR, 1984, 16, 105; M. S. Konings, W. C. Dow, D. B. Love, K. N. Raymond, S. C. Quay and S. M. We are grateful to Dr. T. Loiseau for the X-ray data collection Rocklage, Inorg. Chem., 1990, 29, 1448; M. A. J. Moss and and Rhodia for financial support. C. J. Jones, J. Chem. Soc., Dalton Trans., 1990, 581; D. Zhi-Bang, J. Zhing-Sheng, W. Ge-Cheng and N.Jia-Zan, J. Struct. Chem., 1990, 9, 64; L. Ehnebom and B. F. Pedersen, Acta Chem. Scand., References 1992, 46, 126; S. J. Franklin and K. N. Raymond, Inorg. Chem., 1994, 33, 5794; C. Daiguebonne, Y. Gerault, O. Guillou, 1 G.Fe� rey, J. Fluorine Chem., 1995, 72, 187 and references therein; A. Lecerf, K. Boubekeur, P. Batail, M. Khan and O. Khan, C. R. Acad. Sci. Se�r. C, 1998, 2, 1 and references therein.International Conference on f Elements 3, Paris, France, 1997. 2 M. Haouas, C. In-Ge�rardin, F. Taulelle, C. Estournes, T. Loiseau 9 S. Romero, A. Mosset and J. C. Trombe, Eur. J. Solid State Inorg. and G. Fe� rey, J. Phys. Chem., 1998, 95, 320. Chem., 1997, 34, 209 and references therein. 3 D. Riou and G. Fe� rey, J. Solid State Chem., 1994, 111, 422; 10 Handbook of Chemistry and Physics, Boca Raton, FL, 77th edn., D.Riou, F. Taulelle and G. Fe� rey, Inorg. Chem., 1996, 35, 6392; 1996. M. Cavellec, D. Riou, C. Ninclaus, J.-M. Grene`che and G. Fe� rey, 11 G. M. Sheldrick, SADABS, a program for the Siemens Area Zeolites, 1996, 17, 250; M. Cavellec, D. Riou, J.-M. Grene`che and Detector ABSorption correction, 1994. G. Fe� rey, J. Magn. Magn. Mater., 1996, 163, 173; M. Cavellec, 12 R. Blessing, Acta Crystallogr., Sect. A, 1995, 51, 33. J.-M. Grene`che, D. Riou and G. Fe� rey, Microporous Mater., 1997, 13 G. M. Sheldrick, SHELXTL version 5.03, software package for 8, 103; M. Cavellec, J.-M. Grene`che and G. Fe� rey, Microporous the Crystal Structure Determination, 1994. Mater., 1998, 20, 45; M. Cavellec, C. Egger, J. Linares, 14 G. B. Deacon and R. J. Phillips, Coord. Chem. Rev., 1980, 33, 227. M. Nogues, F. Varret and G. Fe� rey, J. Solid State Chem., 1997, 15 N. E. Brese and M. O’KeeVe, Acta Crystallogr., Sect. B, 1991, 134, 349. 47, 192. 4 A. Clearfield, Curr. Opin. Solid State Mater. Sci., 1996, 1, 268 and 16 F. Serpaggi, T. Luxbacher, A. K. Cheetham and G. Fe� rey, J. Solid references therein. State Chem., submitted. 5 M. E. Thompson, Chem. Mater., 1994, 6, 1168 and references therein. 6 G. Alberti, U. Costantino, F. Marmottini, R. Vivani and Paper 8/02713G J. Mater. Chem., 199