Hybrid open frameworks (MIL-n). Part 6 Hydrothermal synthesis and X-ray powder ab initio structure determination of MIL-11, a series of lanthanide organodiphosphonates with three-dimensional networks, Ln^IIIH[O₃P(CH₂)_nPO₃] (n=1-3)

Abstract

A series of lanthanide and yttrium propylenediphosphonates has been prepared hydrothermally (210°C, 4 days) by action of propylenediphosphonic acid on the metal chlorides. The crystal structure of the gadolinium compound Gd^IIIH[O₃P(CH₂)₃PO₃] has been determined ab initio from X-ray powder diffraction data and refined by the Rietveld method. The compound crystallizes in the monoclinic space group C2/m (no. 12) with a=8.2141(3) Å, b=18.9644(8) Å, c=5.2622(2) Å, β=111.999(2) ° and Z=4. The final agreement factors are R_p=0.113, R_wp=0.142, Bragg R=0.050, R_F=0.034 and χ²=1.91. In the three-dimensional structure, the gadolinium atoms are eight-coordinated. The framework consists of inorganic Gd-P-O sheets joined by organic groups with an interlayer spacing of 9.58 Å. The entire series of the lanthanide elements and yttrium give isotypic structures. Attempts with ethylenediphosphonic acid and gadolinium led to the analogous compound Gd^IIIH[O₃P(CH₂)₂PO₃] which crystallizes in the monoclinic space group P2₁/c (no. 14) with cell parameters a=5.2918(9), b=15.975(3), c=8.338(1) Å, β=111.491(6), Z=4 (final agreement factors R_p=0.078, R_wp=0.105, Bragg R=0.034, R_F=0.026 and χ²=1.50), and with an interlamellar distance of d=7.99 Å. Moreover, the action of methylenediphosphonic acid on La, Ce, Pr and Nd chloride led to a similar structure with a shorter interlamellar distance, d=7.03 Å for Pr^IIIH[O₃P(CH₂)PO₃] (space group C2/m, with a=8.3271(4), b=14.0645(7), c=5.3489(3) Å, β=111.433(2)°, Z=4, and final agreement factors R_p=0.092, R_wp=0.121, Bragg R=0.059, R_F=0.035 and χ²=1.98).

References

1. G. Férey, J. Fluorine Chem., 1995, 72, 187; C. R. Acad. Sci. Sér. C, 1998, 2, and references therein.
2. D. Riou and G. Férey, J. Solid State Chem., 1994, 111, 422; D. Riou, F. Taulelle and G. Férey, Inorg. Chem., 1996, 35, 6392; M. Cavellec, D. Riou, C. Ninclaus, J.-M. Grenèche and G. Férey, Zeolites, 1996, 17, 250; M. Cavellec, D. Riou, J.-M. Grenèche and G. Férey, J. Magn. Magn. Mater., 1996, 163, 173; M. Cavellec, J.-M. Grenèche, D. Riou and G. Férey, Microporous Mater., 1997, 8, 103; M. Cavellec, J.-M. Grenèche and G. Férey, Microporous Mater., 1998, 20, 45; M. Cavellec, C. Egger, J. Linares, M. Nogues, F. Varret and G. Férey, J. Solid State Chem., 1997, 134, 349.
3. A. Clearfield, Curr. Opin. Solid State Mater. Sci., 1996, 1, 268 andreferences therein.
4. M. E. Thompson, Chem. Mater., 1994, 6, 1168 and references therein.
5. (a) G. Alberti, U. Costantino, F. Marmottini, R. Vivani and P. Zappelli, Angew. Chem., Int. Ed. Engl., 1993, 32, 1357; (b) G. Alberti, F. Marmottini, S. Murcia-Mascarós and R. Vivani, Angew. Chem., Int. Ed. Engl., 1994, 33, 1594; (c) L. A. Vermeulen and M. E. Thompson, Chem. Mater., 1994, 6, 77; (d) V. Soghomonian, Q. Chen, R. C. Haushalter and J. Zubieta, Angew. Chem., Int. Ed. Engl., 1995, 34, 223; (e) V. Soghomonian, R. Diaz, R. C. Haushalter, C. J. O'Connor and J. Zubieta, Inorg. Chem., 1995, 34, 4460; (f) H. Byrd, A. Clearfield, D. Poojary, K. P. Reis and M. E. Thompson, Chem. Mater., 1996, 8, 2239; (g) D. M. Poojary, B. Zhang, P. Bellinghausen and A. Clearfield, Inorg. Chem., 1996, 35, 4942; (h) D. M. Poojary, B. Zhang, P. Bellinghausen and A. Clearfield, Inorg. Chem., 1996, 35, 5254; (i) G. Bonavia, R. C. Haushalter, C. J. O'Connor and J. Zubieta, Inorg. Chem., 1996, 35, 5603; (j) P. J. Zapf, D. J. Rose, R. C. Haushalter and J. Zubieta, J. Solid State Chem., 1996, 125, 182; (k) D. L. Lohse and S. C. Sevov, Angew. Chem., Int. Ed. Engl., 1997, 36, 1619.
6. A. Boultif and D. Loüer, J. Appl. Crystallogr., 1991, 24, 987.
7. Siemens AG, DIFFRACT^plus, Karlsruhe, Germany, 1996.
8. J. Rodriguez-Carjaval, in Collected Abstracts of Powder Diffraction Meeting, Toulouse, France, 1990, p. 127.
9. G. M. Sheldrick, Siemens Analytical X-ray Instruments, 1994.
10. R.-C. Wang, Y. Zhang, H. Hu, R. R. Frausto and A. Clearfield, Chem. Mater., 1992, 4, 864.
11. R. D. Shannon, Acta Crystallogr., Sect. A, 1974, 32, 751.
12. G. Cao, V. M. Lynch, J. S. Swinnea and T. E. Mallouk, Inorg. Chem., 1990, 29, 2112.