CRYSTAL GROWTH & DESIGN
Lanthanide-Based Molecular Materials: Gel Medium Induced Polymorphism Carole Daiguebonne,† Andre´ Deluzet,† Magatte Camara,† Kamal Boubekeur,‡ Nathalie Audebrand,§ Yves Ge´rault,† Christophe Baux,† and Olivier Guillou*,†
2003 VOL. 3, NO. 6 1015-1020
GRCM, INSA-Rennes, 20 Avenue des buttes de Coe¨ smes, 35043 Rennes, France, Universite´ de Nantes, 2 rue de la houssinie` re, 44322 Nantes, France, LCSIM, UMR-6511, CNRS-Universite´ de Rennes 1, Rennes, France Received October 17, 2002
ABSTRACT: The reaction of Er3+ with polycarboxylate ligands in a gel medium frequently leads to coordination polymers that cannot be obtained via hydrothermal methods. A new Er3+ 1,2,4,5-benzenetetracarboxylate based coordination polymer, namely, Er4(C10H2O8)3(H2O)12‚12H2O, has been synthesized and its crystal structure is reported herein. It crystallizes in the space group P1 h (no. 2) with a ) 10.4005(2) Å, b ) 10.6486(2) Å, c ) 13.6321(3) Å, R ) 105.3070(7)°, β ) 93.8348(8)°, γ ) 108.9345(12)°, and Z ) 2. To investigate the influence of the gel medium on the observed polymorphism, the Ni2+/1,3,5-benzenetricarboxylate system was studied, and polymorphism was also observed in this case. The crystal structure of a new Ni2+-containing coordination compound, namely, the Ni3(C9H3O6)2h (H2O)14‚4H2O, has been synthesized and its crystal structure is also reported. It crystallizes in the space group P1 (no. 2) with a ) 6.6892(9) Å, b ) 10.7615(15) Å, c ) 12.3163(16) Å, R ) 98.907(16)°, β ) 102.171(16)°, γ ) 108.074(16)°, and Z ) 2. Its thermal behavior has also been studied and an hydration/dehydration cycle similar to the one already observed in the Er3+/1,3,5-benzenetricarboxylate is described. The availability for potential industrial applications of all the reported phases is discussed. Introduction The assembly of coordination polymers is a field of increasing interest.1-4 Work along this line is motivated by the concept that coordination polymers have potential technological applications such as optoelectronic devices and microporous materials for shape and size separations and catalysis.5-7 The advantage of these metal-organic open frameworks is to allow a wide choice in various parameters, including diverse electronic properties and coordination geometry of the metal ions as well as versatile functions and topologies of organic ligands. In this context, there has been current interest in using polycarboxylate as anionic linking groups to support stable polymeric coordination open frameworks with transition metal ions.8,9 The lanthanide ions, due to their very similar chemical and structural properties but very different physical properties from one to the other, could lead to materials exhibiting tunable properties via the choice of the rare earth ion. That is why rather numerous coordination polymers, resulting from the copolymerization of lanthanide ions and polycarboxylate anions, have been described.7,10-16 Most of them have been obtained via hydrothermal synthetic routes. However, reacting one lanthanide ion with one ligand via this synthetic approach usually leads to only one coordination polymer. On the other hand, our group has developed an alternative synthetic strategy involving gel media. Such an approach has recently allowed us to obtain three different coordination polymers, exhibiting different to* To whom correspondence should be addressed.
[email protected]. Tel: (+33) 02 23 23 84 38. † GRCM, INSA-Rennes. ‡ Universite ´ de Nantes. § CNRS-Universite ´ de Rennes 1.
E-mail:
pologies and dimensionality with the same ligand and lanthanide ion, by reacting Er3+ ions with 1,3,5-benzenetricarboxylate in agarose gel media.17,18 This result was of great interest for us because if this kind of polymorphism was confirmed for other systems it could allow one to tune the topology of a coordination polymer based on a given lanthanide ion-ligand system. Consequently, we have decided to investigate whether this polymorphism was induced by the use of the lanthanide ions or by the use of synthetic methods involving diffusion through the gel media. Thus, we have studied the Ni2+-btc3- system and the Er3+-btec4system, where btec4- stands for the 1,2,4,5-benzenetetracarboxylate ligand. Both systems have already been explored via hydrothermal synthetic methods, and in both cases only one compound was obtained, namely, Ni3btc2‚12H2O19 and Er4(btec)3‚16H2O.20 We report here the synthesis and crystal structure of Ni3(btc)2(H2O)14‚ 4H2O and of Er4(btec)3(H2O)12‚12H2O. The thermal study of the Ni2+-btc3- is also reported.
Experimental Section Synthesis of the Microcrystalline Powder of Ni3(btc)2(H2O)14‚4H2O. 1,3,5-Benzenetricarboxylic acid and hydrated nickel(II) chloride were purchased from Acros Organics. They were used without further purification. Twenty milliliters of aqueous solutions containing 1 mmol of hydrated nickel(II) chloride and 1 mmol of the sodium salt
10.1021/cg020060b CCC: $25.00 © 2003 American Chemical Society Published on Web 06/06/2003
1016 Crystal Growth & Design, Vol. 3, No. 6, 2003 of 1,3,5-benzenetricarboxylic acid were mixed. An abundant precipitation occurred immediately. Then, the mixture was left under stirring for half an hour to allow the completion of the reaction. The crystalline powder was then filtered and slightly dried in air. Anal. Calc. for Ni3(btc)2(H2O)14‚4H2O (found): Ni 19.3% (19.3); C 23.6% (23.0); O 52.5% (53.0); H 4.6 (4.1). Yield is almost 100%. Synthesis of the Anhydrous Phase Ni3(btc)2. The polycrystalline powder obtained by direct precipitation, namely, Ni3(btc)2(H2O)14‚4H2O, was heated under nitrogen to 300 °C during 2 h. The resulting polycrystalline white powder was rather well crystallized and exhibited an original X-ray diffraction pattern. Infra-Red spectra clearly show the btc3ligand had not been destroyed during the thermal treatment and the elemental analysis results fit well with the chemical formula Ni3(btc)2. Anal. Calc. for Ni3(btc)2 (found): Ni 29.8% (29.8); C 36.6% (37.0); O 32.5% (32.0); H 1.0 (0.7). The yield is 100%. Despite great efforts, we have not succeeded, until now, in obtaining single crystals. Synthesis of the Single Crystals of Ni3(btc)2(H2O)14‚ 4H2O and Ni3(btc)2(H2O)12. Agarose was purchased from Prolabo and used without further purification. Dilute aqueous solutions of hydrated nickel(II) chloride and sodium salt of 1,3,5-benzenetricarboxylic acid were allowed to slowly diffuse, in an U-shaped tube, through agar-agar gel media at room temperature. After a few weeks of diffusion, single crystals of both phases were obtained depending on the strength of the gel medium. Anal. Calc. for Ni3(btc)2(H2O)14‚4H2O (found): Ni 19.3% (19.5); C 23.6% (23.5); O 52.5% (52.4); H 4.6% (4.4). Anal. Calc. for Ni3(btc)2(H2O)12 (found): Ni 21.9% (22.0); C 26.8% (27.2); O 47.6% (47.5); H 3.7% (3.3). Synthesis of the Single Crystal of Er4(btec)3(H2O)12‚ 12H2O. Agarose was purchased from Prolabo and used without further purification. Dilute aqueous solutions of hydrated erbium(III) chloride and the sodium salt of 1,2,4,5-benzenetetracarboxylic acid were allowed to slowly diffuse, in an U-shaped tube, across agaragar gel media at room temperature. After a few weeks of diffusion, single crystals were obtained. Anal. Calc. for Er4(btec)3(H2O)12‚12H2O (found): Er 36.1% (36.6); C 19.5% (19.5); O 41.5% (41.4); H 2.9% (2.4). Yield is almost 100%. Full details of the X-ray structure determination of Er4(btec)3(H2O)12‚12H2O (CCDC no. 194697) and of Ni3(btc)2(H2O)14‚4H2O (CCDC no. 151345) have been deposited with the Cambridge Crystallographic Data Center and can be obtained, on request, from the authors and the reference to this publication. X-ray Powder Experiments. X-ray powder patterns have been collected using a Rigaku DMAX II diffractometer 30 kV, 10 mA for Cu-KR (λ ) 1.5406 Å), with a scan speed of 0.1 deg min-1 and a step size of 0.002° in 2θ. The calculated patterns were produced using the Powdercell and WinPLOTR software programs.21-23 Thermal Analysis. DTA and TGA curves were respectively recorded using TDA Adamel Lhomargy 67 and TGA Linseis L81/064. Ni3(btc)2(H2O)14‚4H2O microcrystalline powder samples (100 mg) were heated under nitrogen flow in alumina (DTA) and quartz (TGA) crucibles up to 900 °C at a heating rate of 5 °C min-1. The performed TGA shows a first loss of mass between ambient temperature and 60 °C, corresponding to the departure of six water molecules. An X-ray powder diffraction analysis revealed that this powder is Ni3(btc)2(H2O)12. A second loss of water is then observed between 60 and 140 °C corresponding to the departure of the 12 remaining water molecules. The compound Ni3(btc)2 then obtained is then stable over a large range of temperatures (between 140 and 360 °C). At last, a decomposition occurs finally leading to a microcrystalline powder. An X-ray powder diffraction analysis revealed that this powder is actually NiO.
Daiguebonne et al. Temperature Dependent X-ray Powder Diffraction. Temperature-dependent X-ray powder diffraction (TDXD) was carried out, in a nitrogen stream, by using a diffractometer equipped with an INEL (CPS120) curved position detector. The detector was used in a semi-focusing geometry by reflection (CuKR1 radiation) described elsewhere.24 The stationary sample was located at the center of the goniometer. An angle of 6° was selected between the incident beam and the surface of the sample. The specimen was located in a monitored hightemperature device (Rigaku). To ensure satisfactory counting statistics, a counting time of 3600 s per pattern was selected. The thermal dependent X-ray diffraction diagram together with the TDA curve recorded allow us to assume that the departure of the six first water molecules and the crystallographic transition phase are occurring simultaneously. The TDXD experiment also clearly shows that there is no additional stable phase in the Ni2+-btc3- system. X-ray Data Collection and Structure Determination of Ni3(btc)2(H2O)14‚4H2O and Ni3(btc)2(H2O)12. A transparent platelike single crystal of Ni3(btc)2(H2O)14‚4H2O and a transparent needlelike crystal of Ni3(btc)2(H2O)12 were sealed in glass capillaries and mounted on a STOE IPDS single φ axis diffractometer with a 2D area detector based on Imaging Plate Technology. For the two crystals, 130 images were recorded by using the rotation method (0 e φ e 260°) with ∆φ ) 2.0° increments, an exposure time of 3 min, and a crystalto-plate distance of 60 mm (EXPOSE25). The images were processed with the set of programs from STOE25 (DISPLAY, PROFILE, INDEX, CELL, INTEGRATE), and the data were corrected by an empirical absorption correction25 (ABSORB). The structures were solved by direct method and difference Fourier techniques and refined (on F2s) by full matrix least squares calculations using the software package SHELXS-97 and SHELXL-97.26 X-ray Data Collection and Structure Determination of Er4(btec)3(H2O)12‚12H2O. Single-crystal data collection has been performed at room temperature with a Nonius KappaCCD diffractometer (Centre de Diffractome´trie, Universite´ de Rennes, France), with Mo KR radiation (λ ) 0.71073 Å). A crystal-to-detector distance of 32.4 mm has been used, and the data collection strategy (determination and optimization of the detector and goniometer positions) has been performed with the help of the COLLECT program27 to measure Bragg reflections of the asymmetric triclinic basal unit cell until θ ) 27.5°. A total of 716 frames were recorded, using ∆ω ) 0.8° rotation scans to fill the asymmetric unit cell (exposition time ) 90 s/deg). Finally, 54 652 reflections have been indexed, Lorentz-polarization corrected, and then integrated in the monoclinic symmetry (C2 point group) by the DENZO program of the KappaCCD software package.28 Numerical absorption corrections have been performed using the Gaussian facilities29,30 included in the WinGX program suite.31 Structure determination has been performed with the SIR9732 solving program, revealing all the non-hydrogen atoms. The SHELXL program26,33,34 has been used to refine the structure. Description of the Structure of Er4(btec)3(H2O)12‚ 12H2O. A view of an extended asymmetric unit is reproduced in Figure 1. Selected experimental data are listed in Table 1. The crystal structure of Er4(btec)3(H2O)12‚12H2O can be depicted as a succession, along the b c-axis, of two-dimensional molecular motifs spreading parallel to the (a b,b B) plane. These layers are constituted of two planes of Er3+ ions very strongly connected by two crystallographically independent 1,2,4,5benzenetetracarboxylate ligands (hereafter noted A and B) per four Er3+ ions. The planes are connected to each other by another (btec)4- ligand (hereafter named C) forming a threedimensional network (see Figure 2). The A and B ligands coordinate six Er3+ ions. The aromatic parts of these two ligands stay very planar and have quite the same orientation (perpendicular to the (b B,c b) plane), but the carboxylato groups largely stray out of the plane (from 45° to 90° depending on the considered carboxylato group). The
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Figure 1. View of an extended asymmetric unit of Er4(btec)3(H2O)12‚12H2O along with the atomic numbering scheme. Table 1. Crystal Data and Final Structure Refinement of Er4(btec)3(H2O)12‚12H2O and Ni3(btc)2(H2O)14‚4H2O compound molecular formula formula weight crystal dimensions (mm) temperature crystal system space group a (Å) b (Å) c (Å) R (°) β (°) γ (°) Z Dcalc (gcm-3) F000 µ (mm-1) radiation hkl range θ range (°) data collected observed data (Fobs g 2σ(Fobs)) parameters refined goodness-of-fit on F2 final R indices (I > 2σ(I)) final shift/error residual density (e Å-3)
Er4(btec)3(H2O)12‚12H2O Er2C15H27O24 1851 0.24 × 0.145 × 0.065 298 K triclinic P1 h (no. 2) 10.4005(2) 10.6486(2) 13.6321(3) 105.3070(7) 93.8348(8) 108.9345(12) 2 2.264 890 6.235 Mo KR -14 e h e 13, -14 e k e 13, -18 e l e 19 1.57 e θ e 30.03 19707 6467 370 1.046 R1 ) 4.54% 0.000 2.498 (in the vicinity of Er)
12 carboxylato groups adopt various coordination modes as can be seen in Figure 1. The two independent Er3+ ions are both eight coordinated. The Er1 atom is coordinated by four oxygen atoms belonging to four different btec4- ligands as well as by four coordination water molecules leading to a slightly distorted square antiprism. The Er2 atom is eight-coordinated by six oxygen atoms belonging to four different (btec)4- ligands as well as by two coordination water molecules leading to a slightly distorded dodecahedron (Table 2). The shortest contacts between Er3+ ions are provided by bridging carboxylato groups. These infinite layers are connected to each other by uprights constituted by the third crystallographically independent ligand. In contrast to the two others, this pyromellitate ion coordinates only four Er3+ ions. The orientation of the phenyl core of this third ligand is almost parallel to the (b B,c b) plane.
Ni3(btc)2(H2O)14‚4H2O Ni1.5C9H21O15 914 0.2 × 0.15 × 0.1 298 K triclinic P1 h (no. 2) 6.6892(9) 10.7615(15) 12.3163(16) 98.907(16) 102.171(16) 108.074(16) 2 1.897 474 1.864 Mo KR -8 e h e 7, -13 e k e 13, 0 e l e 15 2.05 e θ e 26.09 2921 2479 233 2.784 R1 ) 9.91% 0.000 0.4 (in the vicinity of Ni)
The three-dimensional molecular network exhibits channels fulfilled with 12 crystallization water molecules. They are all involved in a complex hydrogen bonds network formed by the oxygen atoms from carboxylato groups and the coordination water molecules. The thermal ellipsoids of the crystallization water molecules are very anisotropic with an elongation axis parallel to the crystallographic B b axis. The high disorder observed and the high and strongly anisotropic coefficients of thermal agitation found suggest that these water molecules can easily be removed from the channels. Experimentally, we have actually observed that the crystals are destroyed in a few minutes if they are kept out of the mother solution. Description of the Structure of Ni3(btc)2(H2O)14‚4H2O. A view of an extended asymmetric unit along with the atomic numbering scheme is reproduced in Figure 3. Selected experimental data are listed in Table 1.
1018 Crystal Growth & Design, Vol. 3, No. 6, 2003
Daiguebonne et al.
Figure 2. Left: Different coordination modes of the (btec)4- ligand. Right: Projection view along the B b axis. The “C” (btec)4ligands are linking together the molecular bi-dimensional layers. Table 2. Er-O Distances and O-Er-O Angles in the Polyhedron of the Two Er Ions in Compound 1 Er 1
distance (Å)
Er 2
distance (Å)
O1 O4 O5 O6 O3A O1B O2B O2C
2.366(4) 2.372(5) 2.356(5) 2.361(4) 2.417(4) 2.249(4) 2.325(4) 2.357(4)
O2 O3 O1A O2A O3B O4B O1C O3C
2.417(4) 2.343(4) 2.228(4) 2.291(4) 2.469(4) 2.445(4) 2.320(4) 2.305(4)
atoms O1B O1B O2B O1B O2B O5 O1B O2B O5 O2C O1B O2B O5 O2C O6 O1B O2B O5 O2C O6 O1 O1B O2B O5 O2C O6 O1 O4
O2B O5 O5 O2C O2C O2C O6 O6 O6 O6 O1 O1 O1 O1 O1 O4 O4 O4 O4 O4 O4 O3A O3A O3A O3A O3A O3A O3A
angle (°) 104.54(15) 84.82(18) 145.19(17) 147.30(15) 79.76(14) 110.38(16) 85.93(17) 142.66(16) 70.22(18) 73.31(16) 73.12(15) 74.59(14) 139.41(17) 77.07(14) 74.52(17) 144.19(16) 81.24(19) 72.8(2) 68.28(15) 111.1(2) 140.63(16) 73.12(14) 75.92(14) 75.00(16) 137.77(13) 140.71(15) 127.06(14) 74.25(15)
atoms O1A O1A O2A O1A O2A O3C O1A O2A O3C O1C O1A O2A O3C O1C O3 O1A O2A O3C O1C O3 O2 O1A O2A O3C O1C O3 O2 O4B O1A O2A O3C O1C O3 O2 O4B O3B
O2A O3C O3C O1C O1C O1C O3 O3 O3 O3 O2 O2 O2 O2 O2 O4B O4B O4B O4B O4B O4B O3B O3B O3B O3B O3B O3B O3B C4B C4B C4B C4B C4B C4B C4B C4B
angle (°) 100.86(15) 91.52(14) 137.45(14) 80.89(14) 149.73(14) 72.13(14) 154.69(17) 73.79(15) 77.83(15) 116.44(15) 71.94(14) 71.34(14) 74.33(14) 135.73(14) 83.04(16) 126.95(14) 78.90(14) 124.45(14) 76.29(14) 77.05(16) 147.82(13) 74.39(13) 79.46(13) 142.95(13) 71.88(13) 127.03(15) 129.50(14) 53.17(13) 100.86(14) 76.24(15) 141.21(15) 73.79(15) 101.73(16) 144.46(15) 26.70(14) 26.56(13)
The crystal structure of Ni3(btc)2(H2O)14‚4H2O can be described as the juxtaposition of trinuclear molecular motifs. The
central Ni2+ ion is six coordinated by two oxygen atoms (belonging to the two (btc)3- ligands) as well as by four coordination water molecules so forming a slightly distorted octahedron. The two other Ni2+ ions are six coordinated by one oxygen atom belonging to a (btc)3- ligand as well as by five coordination water molecules, forming slightly distorted octahedra. Both (btc)3- ligands are linked to two Ni2+ ions in a unidentate fashion. So, four of the six oxygen atoms remain nonbounded. The trinuclear entities stack in such a way that all (btc)3groups lie in the (b B,c b) plane. All trinuclear entities are aligned along the b a axis forming a thick plane. Terminal Ni2+ ions are involved in a strong hydrogen-bond network spreading in the (a b,b B) plane. Crystallization water molecules are localized in the interplane space and are involved in the hydrogen bonds network. Description of the Structure Ni3(btc)2‚12H2O. This structure has already been reported19 and can be described as a condensation of the previous one (Figure 4). During the thermal treatment of Ni3(btc)2(H2O)14‚4H2O, six water molecules are first lost by the compound: four out of the six come from crystallization water molecules and the remaining two are coordinated water molecules. As suggested in Figure 4, the departure of these two coordinated water molecules could be concerted with the coordination decoordination process of oxygen atoms belonging to two carboxylato groups. As far as our explanation is correct, each outer Ni2+ ion of the trimer would lose one coordination water molecule. Simultaneously, they would rearrange in such a way that molecular zigzag chains would be obtained. So, one of them leaving a trimeric molecular fragment would be linked to a free carboxylato group belonging to an adjacent trimeric molecular fragment in a bidentate fashion. Meanwhile, the opposite Ni(II) ion would bind to the carboxylato group just left out, thus forming a molecular zigzag chain. Lastly, these polymeric chains condense once more leading probably to an anhydrous three-dimensional molecular network.19 Once the anhydrous Ni3(btc)2 compound has been obtained, we have checked its rehydration. So, if the anhydrous compound is left for several hours in a wet atmosphere, it rehydrates, leading successively to Ni3(btc)2‚12H2O and finally to Ni3(btc)2(H2O)14‚4H2O. Unfortunately, our synthetic approach does not allow us to obtain a single crystal of the anhydrous phases. The reversible cycle has been studied by TDXD and thermal analysis. Both studies clearly show that there is no additional phase in this cycle.
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Figure 3. View of an extended asymmetric unit of Ni3(btc)2‚18H2O along with the atomic numbering scheme.
Figure 4. Suggested condensation scheme for the thermally induced phase transition from Ni3(btc)2(H2O)14‚4H2O to Ni3(btc)2‚ 12H2O. The dotted lines symbolize bonds that are created or deleted during the phase transition.
Results and Discussion Using diffusion through gel synthetic methods, we have obtained new materials in both systems. First, these results confirm that these synthetic methods allow one to obtain new phases that cannot be obtained by classical hydrothermal synthetic routes. Second, they suggest that the polymorphism previously seen in the Er3+/btc3- system17,18 is actually induced by the gel medium used and is not specific to the metallic ion involved. Indeed, the Ni2+ ion is a rather soft metal ion that establishes rather covalent bonds with ligands, while the Er3+ ion is a very hard metal ion that establishes almost purely ionic bonds with ligands. In both cases, despite the very different chemical behaviors of the metal ions, we observed polymorphism. This synthetic approach allows us to obtain several compounds by reacting a given metal ion with a given ligand. This is of great interest insofar it is possible to tune the topology of a coordination polymer based on a given Ln3+/ligand system. This opportunity could be of great interest in the design of coordination polymers exhibiting potential
technological applications such as optoelectronic devices. For instance, for optical properties in which the separation of the erbium centers is a prerequisite to prepare efficient fluorescent materials for amplification fibers, the use of this synthetic strategy could be helpful. However, as far as technological applications are concerned, the availability of the material is crucial. This is obviously a problem because the technological use of coordination polymers implies that they can be obtained easily with great yields. This goal cannot be reached with synthetic methods such as diffusion through gel media. Fortunately, thanks to the use of diffusion methods through gel media it seems to be possible to crystallographically characterize most of the polymorphic phases of such systems. This knowledge of the dehydration process then makes possible the synthesis in reasonably good yields of the desired phase by simply controlling the dehydration of the phase obtained by direct precipitation. This observation could be of great interest in the design of new technologically interesting lanthanide-based coordination polymers.
1020 Crystal Growth & Design, Vol. 3, No. 6, 2003
Acknowledgment. The authors thank the “Region Bretagne” for financial support. The Center of Crystallography of the “Universite´ de Rennes” is acknowledged for recording crystallographic data. References (1) Kepper, C. J.; Rosseinsky, M. Chem. Commun. 1999, 375376. (2) Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science 1999, 283, 1148-1150. (3) Tong, M.-L.; Wu, Y.-M.; Ru, J.; Chen, X. M.; Chang, H.-C.; Kitagawa, S. Inorg. Chem. 2002, 41, 4846-4848. (4) Zaman, M. B.; Smith, M. D.; Ciurtin, D. M.; Loyal, H.-C. Inorg. Chem. 2002, 41, 4895-4903. (5) Chen, B.; Eddaoudi, M.; Hyde, S. T.; O’Keeffe, M.; Yaghi, O. M. Science 2001, 291, 1021-1023. (6) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469-472. (7) Reneike, T. M.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Angew. Chem., Int. Ed. Engl. 1999, 38, 2590-2594. (8) Marioni, P.-A.; Marty, W.; Stoeckli-Evans, H.; Whitaker, C. Inorg. Chim. Acta 1994, 219, 161-168. (9) Eddaoudi, M.; Kim, J.; Wachter, J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2001, 123, 4368-4369. (10) Reneike, T. M.; Eddaoudi, M.; Fehr, M.; Kelley, D.; Yaghi, O. M. J. Am. Chem. Soc. 1999, 121, 1651-1657. (11) Serpaggi, F.; Luxbacher, T.; Cheetham, A. K.; Ferey, G. J. Sol. State Chem. 1999, 145, 580-586. (12) Vaidhyanathan, R.; Natarajan, S.; Rao, C. N. R. Inorg. Chem. 2002, 41, 4496-4501. (13) Pan, L.; Woodlock, E. B.; Wang, X. Inorg. Chem. 2000, 39, 4174-4178. (14) Daiguebonne, C.; Guillou, O.; Ge´rault, Y.; Lecerf, A.; Boubekeur, K. Inorg. Chim. Acta 1999, 284, 139-145. (15) Daiguebonne, C.; Ge´rault, Y.; Guillou, O.; Lecerf, A.; Boubekeur, K.; Kahn, O.; Kahn, M. J. Alloys Compd. 1998, 275-277, 50-53. (16) Daiguebonne, C.; Guillou, O.; Boubekeur, K. J. Alloys Compd. 2001, 324-324, 199-203.
Daiguebonne et al. (17) Daiguebonne, C.; Guillou, O.; Boubekeur, K. Inorg. Chim. Acta 2000, 304, 161-169. (18) Daiguebonne, C.; Guillou, O.; Boubekeur, K. “Structural Diversity in Lanthanide Complex Chemistry: The Ln3+TMA3--H2O System” In Recent Research Developments in Inorganic Chemistry; Pandalai, S. G. Ed.; Transworld Research Network, Kerala, India, 2000; pp 165-183. (19) Yaghi, O. M.; Li, H.; Groy, T. L. J. Am. Chem. Soc. 1996, 118, 9096-9101. (20) Cao, R.; Sun, D.; Liang, Y.; Hong, T. K. M.; Shi, Q. Inorg. Chem. 2002, 41, 2087-2094. (21) Roisnel, T.; Rodriguez-Carjaval, J. Materials Science Forum 2002, Proceedings of the European Diffraction Conference (EPDIC7), in press. (22) Kraus W.; Nolze G. J. Appl. Cryst. 1996, 29, 301-303. (23) Rodriguez-Carjaval, J.; Roisnel, T. Newletter 1998, 20 (MayAugust). (24) Ple´vert, J.; Auffre´dic, J. P.; Loue¨r, D.; Loue¨r, M. J. Mater. Sci. 1989, 24, 1913-1918. (25) STOE IPDS software manual V2.75, STOE & Cie, Darmstadd, 1996. (26) Sheldrick, G. M.; Schneider, T. R. Macromol. Cryst. B 1997, 319-343. (27) COLLECT: KappaCCD software, Nonius Bv ed., The Netherlands, Delft 1998. (28) Otwinowski, Z.; Minor, W. Methods in Enzymology; Carter, C. W., Sweet, R. M., Eds.; Academic Press: New York, 1997; pp 307-326. (29) Busing, W. R.; Levy, H. A. Acta Crystallogr. 1957, 10 180182. (30) Coppens, P.; Leiserowitz, L.; Rabinovitch, D. Acta Crystallogr. 1965, 18, 1035-1038. (31) Farrigia, L. J. J. Appl. Cryst. 1999, 32, 837-838. (32) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R. J. Appl. Cryst. 1999, 32, 115-119. (33) Sheldrick, G. M. Acta Crystallogr. A 1990, 46, 467-473. (34) Sheldrick, G. M. Acta Cryst. D 1993, 49, 18-23.
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