Hybrid open frameworks (MIL-n). Part 5 Synthesis and crystal structure of MIL-9: a new three-dimensional ferrimagnetic cobalt(II) carboxylate with a two-dimensional array of edge-sharing Co octahedra with 12-membered rings

Abstract

Co₅(OH)₂(C₄H₄O₄)₄, a new cobalt(II) succinate with an open framework, was prepared hydrothermally (180°C, 72 h, autogenous pressure) from a 2:3:8:120 mixture of Co(II) chloride, succinic acid, potassium hydroxide and water. Its monoclinic structure was solved by single crystal X-ray diffraction [space group P2₁/c (no. 14) with a=9.5631(2) Å, b=9.4538(2) Å, c=12.5554(2) Å, β=96.968(1)°, V=1126.72(4) ų, Z=4] from 3077 unique reflections [I≥2σ(I)], R1=0.020 and wR2=0.054. The three-dimensional structure is built up from layers of edge sharing octahedra pillared by succinate ions. Within the layers, cobalt octahedra form 12-membered ring windows. Below 10 K, Co₅(OH)₂(C₄H₄O₄)₄, exhibits ferrimagnetic behavior.

References

1. R. C. Haushalter and L. A. Mundi, Chem. Mater., 1992, 4, 31.
2. S. Drumel, P. Janvier, M. Bujoli-Doeuff and B. Bujoli, Inorg. Chem., 1996, 35, 5786.
3. G. Ferey, C.R. Acad. Sci. Ser. C1, 1998, 1.
4. A. M. Chippindale and A. R. Cowley, Zeolites, 1997, 18, 176.
5. A. M. Chippindale, A. R. Cowley and R. I. Walton, J. Mater. Chem., 1996, 6, 611.
6. P. Feng, X. Bu and G. D. Stucky, Nature, 1997, 388, 735.
7. X. Bu, P. Feng and G. D. Stucky, Science, 1997, 278, 2080.
8. Q. M. Gao, A. M. Chippindale, A. R. Cowley and J. S. Chen, J. Phys. Chem. B, 1997, V101, 48, 9940.
9. P. Feng, X. Bu, S. H. Tolbert and G. D. Stucky, J. Am. Chem. Soc., 1997, 119, 2497.
10. P. Feng, X. Bu and G. D. Stucky, J. Solid State Chem., 1997, 131, 160 and 387.
11. D. L. Lohse and S. C. Sevov, Angew. Chem., Int. Ed. Engl., 1997, 36, 1619.
12. J. R. Debord, R. C. Haushalter and J. Zubieta, J. Solid State Chem., 1996, 125, 270.
13. F. Sanz, C. Parada, U. Amador and Mongema, J. Solid State Chem., 1996, 123, 129.
14. R. LaDuca, D. Rose, J. R. D. DeBord, R. C. Haushalter, C. J. O. Connor and J. Zubieta, J. Solid State Chem., 1996, 123, 408.
15. S. O. H. Gutschke, M. Molinier, A. K. Powell and P. T. Wood, Angew. Chem., Int. Ed. Engl., 1997, 36, 991.
16. F. Serpaggi and G. Férey, J. Mater. Chem., preceding paper.
17. G. M. Sheldrick, SADABS, a program for the Siemens Area Detector ABSorption correction, 1994.
18. G. M. Sheldrick, SHELXTL version 5.03, software package for the Crystal Structure Determination, 1994.
19. R. L. Carlin, Magnetochemistry, Springer-Verlag, Berlin, New York, 1986.
20. J. B. Goodenough, Magnetism and chemical bonds, Wiley-Interscience, New York, 1963.
21. M. Leblanc, T. Collin Fèvre and G. Férey, J. Magn. Magn. Mater., 1997, 167, 71.