Inorg. Chem. 2001, 40, 723-725
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Hydrothermal Synthesis and ab Initio Structural Resolution from X-ray Powder Diffraction of a New Open Framework Cu(II) Carboxyethylphosphonate: Na[Cu(O3P-(CH2)2-CO2)] Myriam Riou-Cavellec,* Morgane Sanselme, Nathalie Guillou, and Ge´ rard Fe´ rey Institut Lavoisier, UMR CNRS 8637, Universite´ de Versailles, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France ReceiVed July 11, 2000 Na[Cu(O3P-(CH2)2-CO2)], or MIL-39 (for Material of Institut Lavoisier), was synthesized hydrothermally at 443 K for 72 h under autogenous pressure. Its three-dimensional open structure was determined from X-ray powder diffraction. MIL-39 is monoclinic, it crystallizes in the space group P21/m, (No. 11) with the following cell parameters at 293 K: a ) 8.808(1) Å, b ) 6.4149(8) Å, c ) 5.3418(8) Å, β ) 105.75(1)°, Z ) 2. Its framework contains double rows built from isolated distorted CuO5 square pyramids linked by PO3C tetrahedral groups from (O3P-(CH2)2-CO2)3- organic moieties. At the other end of these latter moieties, the carboxylate group links two different Cu polyhedra of two neighboring chains. These connections define two types of channels along [010].
Table 1. Crystallographic Data for MIL-39
Introduction Recently, new, original open-framework materials have been synthesized hydrothermally using organic species such as diphosphonic1-6or di/tricarboxylic7-10 acids. The syntheses of hybrid organic-inorganic compounds using both functional carboxylic and phosphonic groups have also been reported in the literature.11-16 Layered compounds11,12 and also pillared/ three-dimensional13-16 open-framework compounds in which both different functional groups participate in the formation of the three-dimensional framework have been discovered. In this paper, we report the hydrothermal synthesis, the ab initio structural determination from X-ray powder diffraction of a new three-dimensional, open-framework copper carboxyethylphosphonate compound formulated as Na[Cu(O3P-(CH2)2CO2)], or MIL-39 (for Material of Institut Lavoisier). Structural * To whom correspondence should be addressed. E-mail: cavellec@ chimie.uvsq.fr. Fax: (33) (0) 1 39 25 43 58. (1) Le Bideau, J.; Payen, C.; Palvadeau, P.; Bujoli, B. Inorg. Chem. 1994, 33, 4885. (2) Thompson, M. E. Chem. Mater. 1994, 6, 1168. (3) Maeda, K.; Akimoto, J.; Kiyozumi, Y.; Mizukami, F. Angew. Chem., Int. Ed. Engl. 1995, 34 (11), 1199. (4) Bonavia, G.; Haushalter, R. C.; O’Connor, C. J.; Zubieta, J. Inorg. Chem. 1996, 35, 5603. (5) (a) Clearfield, A. Curr. Opin. Solid State Mater. Sci. 1996, 1, 268. (b) Chem. Mater. 1998, 10, 2801 and references therein. (6) Riou, D.; Roubeau, O.; Fe´rey, G. Microporous Mesoporous Mater. 1998, 23, 23. (7) Yaghi, O. M.; Davis, C. E.; Li, G.; Li, H. J. Am. Chem. Soc. 1997, 119, 2861. (8) Serpaggi, F.; Fe´rey, G. J. Mater. Chem. 1998, 8, 2737. (9) Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Guy Orpen, A.; Williams, I. D. Science 1999, 283, 1148. (10) Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Nature 1999, 402, 277. (11) Burwell, D. A.; Thompson, M. E. Chem. Mater. 1991, 3, 14 and references therein. (12) Bortun, A. I.; Bortun, L.; Clearfield, A.; Jaimez, E.; Villa-Garcia, M. A.; Garcia, J. R.; Rodriguez, J. J. Mater. Res. 1997, 12 (4), 1122. (13) Drumel, S.; Janvier, P.; Barboux, P.; Bujoli-Doeuff, M.; Bujoli, B. Inorg. Chem. 1995, 34, 148 and references therein. (14) Distler, A.; Sevov, S. C. Chem. Commun. 1998, 959. (15) Ayyapan, S.; Diaz de Delgado, G.; Cheetham, A. K.; Fe´rey, G.; Rao, C. N. R. J. Chem. Soc., Dalton Trans. 1999, 2905. (16) Riou-Cavellec, M.; Sanselme, M.; Fe´rey, G. J. Mater. Chem. 2000, 10, 745.
formula fw (g mol-1) cryst syst space group a (Å) b (Å) c (Å) β (deg) V (Å-3) Z figures of merit radiation (Å) 2θ range (deg) no. reflns no. atoms no. structural params RP RWP RB RF
Na[Cu(O3P-(CH2)2-CO2)] 237.51 monoclinic P21/m 8.808(1) 6.4149(8) 5.3418(8) 105.75(1) 290.48(5) 2 M20 ) 79; F30 ) 80 (0.0075, 50) 1.5418 8-108 785 10 21 0.034 0.045 0.059 0.058
comparison with the three-dimensional compound MIL-26,16 or Na[VIVO(O3P-(CH2)2-CO2)](H2O)2, will be presented. Experimental Section Synthesis. MIL-39 was synthesized hydrothermally from CuCl2, 2H2O (Prolabo), carboxyethylphosphonic acid (Aldrich, 94%), and water. The molar ratios in the initial mixture were 1:1:100 CuCl2‚2H2O/ H2O/H2O3P-(CH2)2-CO2H/H2O. The pH of the above solution was controlled and raised to ca. 6-7 using a NaOH solution (10 mol L-1) in order to deprotonate the acidic groups. Reactants were introduced in a Teflon lined vessel, then sealed in a Parr acid digestion bomb. The latter was heated at 170 °C for 72 h under autogenous pressure. At the end of the reaction, the pH of the solution was ca. 6, and the resulting product was filtered, washed with water, and dried at room temperature. It consisted of a well-crystallized blue powder. Analysis. Semiquantitative energy dispersive X-ray (EDX) analysis of the obtained powder (performed on a JEOL 5800 LV scanning microscope equipped with Oxford Linkisis analyzer) gave us the following ratio: 1:1:1 Cu/P/Na. Elemental analysis results indicated the following (wt %): Cu, 26.66 (calcd, 26.75); P, 12.56 (calcd, 13.04); C, 14.53 (calcd, 15.15); Na, 9.36 (calcd, 9.68). This confirmed the ratio 1:1:3:1 Cu/P/C/Na.
10.1021/ic000758j CCC: $20.00 © 2001 American Chemical Society Published on Web 01/11/2001
724 Inorganic Chemistry, Vol. 40, No. 4, 2001
Riou-Cavellec et al.
Table 2. X-ray Powder Diffraction Pattern of MIL-39 hkl
2θobsd (deg)
2θcalcd (deg)
dobsd (Å)
Iobsd
hkl
2θobsd (deg)
2θcalcd (deg)
dobsd (Å)
Iobsd
100 001 1h10 1h01 200 011 1h11 101 2h01 111 2h11 020 201 300 3h01 021 1h21 1h02 1h12 102 301 3h20 400 311
10.431 17.229 17.319 17.570 20.934 22.135 22.404 22.511 23.272 26.473 27.142 27.780 30.742 31.636 31.709 32.887 33.069 33.527 36.425 39.251 40.337 42.600
10.426 17.233 17.321 17.564 20.940 22.139 22.400 22.510 23.274 26.494 27.153 27.790 30.740 31.637 31.696 32.884 33.066 33.541 36.423 39.253 40.346 42.604 42.624 42.835
8.48 5.14 5.11 5.04 4.240 4.012 3.965 3.946 3.819 3.364 3.282 3.208 2.906 2.826 2.819 2.721 2.706 2.670 2.464 2.2933 2.2340 2.1204
100 21 14 19 15 14 2 2 26 1 2 34 4 19 9 5 18 2 5 5 17 4
3h12 130 1h22 410 022 2h22 031 202 131 212 2h31 122 321 3h22 401 411 231 5h11 500 302 3h03 222 1h32
42.978 43.612 44.086 45.002 45.203 45.712 45.937
42.972 43.616 44.098 45.011 45.163 45.719 45.925 45.952 46.063 48.208 48.768 48.775 49.698 49.821 50.818 52.918 53.131 54.028 54.041 54.329 54.521 54.555 54.972
2.1027 2.0735 2.0523 2.0127 2.0042 1.9831 1.9739
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