Disordered CuN6 Jahn-Teller Centers in Hexakis(l-methyltetrazole)copper(II) Tetrafluoroborate: A Temperature-Dependent X-ray Diffraction and EPR Study

Inorganic Chemistry

Volumn 35, Issue 5, 1996, Pages 1214-1222

  Wijnands, Paul E M ^a,c   Wood, John S ^b   Reedijk, Jan ^a   Maaskant, Wim J A ^a  

^a LEIDEN UNIVERSITY   (Netherlands)

^b UNIVERSITY OF MASSACHUSETTS   (United States)

^c DUPONT COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000598766     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic950315t     Document Type: Article

References (29)

1. Franke, P. L.; Groeneveld, W. L. Transition Met. Chem. 1981, 6, 54. Franke, P. L. Ph.D. Thesis, Leiden University, 1982.
2. Franke, P. L.; Groeneveld, W. L. Transition Met. Chem. 1981, 6, 54. Franke, P. L. Ph.D. Thesis, Leiden University, 1982.
3. Poganiuch, P.; Decurtins, S.; Gutlich, P. J. Am. Chem. Soc. 1990, 112, 3270.
4. Wijnands, P. E. M.; Maaskant, W. J. A.; Reedijk, J. Chem. Phys. Lett. 1986, 130, 536.
5. Murphy, A.; Hathaway, B. J.; King, T. J. J. Chem. Soc., Dalton Trans 1979, 1646.
6. Bertini, I.; Dapporto, P.; Gatteschi, D.; Scozzafava, A. J. Chem. Soc., Dalton Trans. 1979, 1409.
7. Dubler, E.; Linovsky, L, Klaui, W. Transition Met. Chem. 1979, 4, 191.
8. Couldwell, C.; Prout, K.; Robey. D.; Taylor, R.; Rossoti, F. J. C. Acta Crystallogr. 1978, B34, 1491.
9. Glass, R. S.; Steffen, L K.; Swanson, D. D.; Wilson, G. S., de Gelder, R.; de Graaff, R. A. G.; Reedijk. J. Inorg. Chim. Acta 1993, 207, 241.
10. Wijnands, P. E. M. Ph.D. Thesis. University of Leiden. 1989. Copies of the thesis are available upon request from P.E.M.W Address see ref 1c.
11. Reinen, D.; Friebel C. Struct. Bonding 1979, 37, 1.
12. Programs written by R. A. G. de Graaff and E. Rutten-Keulemans, Leiden University.
13. International Tables for X-Ray Crystallography: Kynocb Press: Birmingham. England, 1974; Vol. IV.
14. Cromer, D. T.; Liberman, D. J. Chem. Phys. 1970, 53, 1891.
15. Stewart, R. F., Davidson. R. F.; Simpson. W. T. J. Chem. Phys. 1965, 42, 3175.
16. Busmg, W. R.; Martin, K. O.; Levy, H. A. ORFLS. Report ORNLTM-305; Oak Ridge National Laboratory: Oak Ridge, TN, 1962.
17. Daul, C., Schlapfer, C. W.; Mohos, B.; Ammeter, J.; Gamp, E. Comput. Phys. Commun. 1981, 21, 385.
18. The description of the dynamic behavior of the A and B sites as pulsating follows the nomenclature introduced by Bersuker to describe the strong coupling situation where the system is in one of three configurations, performs vibrations around that configuration, and then rapidly switches to one of the other configurations (Bersuker, I. B. The Jahn -Teller Effect and Vibronic Interactions in Modern Chemistry; Plenum Press: New York, 1984). We suggest that the description, dynamic Jahn-Teller effect, be reserved for the case of a weak E ⊗ ε coupling, where there is little or no warping of the potential surface and which behaves very differently both theoretically and experimentally from the strong coupling case. See: Ham, F. S. In Electron Paramagnetic Resonance: Geschwind. S., Ed., Plenum Press: New York, 1972.
19. The description of the dynamic behavior of the A and B sites as pulsating follows the nomenclature introduced by Bersuker to describe the strong coupling situation where the system is in one of three configurations, performs vibrations around that configuration, and then rapidly switches to one of the other configurations (Bersuker, I. B. The Jahn -Teller Effect and Vibronic Interactions in Modern Chemistry; Plenum Press: New York, 1984). We suggest that the description, dynamic Jahn-Teller effect, be reserved for the case of a weak E ⊗ ε coupling, where there is little or no warping of the potential surface and which behaves very differently both theoretically and experimentally from the strong coupling case. See: Ham, F. S. In Electron Paramagnetic Resonance: Geschwind. S., Ed., Plenum Press: New York, 1972.
20. In an attempt to obtain information on the geometry of this center at a lower temperature, a single-crystal neutron study at 20 K was undertaken. However, on cooling of the large crystals needed for such a study, the mosaic spread of the orientation reflections increased to unacceptable levels, and the project was abandoned.
21. While in the present analysis the X-ray results for the zinc structures were used, it does appear that calculations using the data for copper complexes alone also give reasonable values for the Jahn-Teller radii and population distribution.
22. Ammeter, J. H , Burgi. H. B.; Gamp. E., Meyer-Sandrin, V.; Jensen, W. P. Inorg Chem. 1979, 18, 733.
23. 6 entities in the 117 K structure, and the Jahn-Teller radii were found to be 0.32 and 0.34 Å.
24. Keijzers, C. P.; McMullan, R. K.; Wood, J. S.; Van Kalkeren, G.; Snnivasan, R.; deBoer, E. Inorg. Chem. 1982, 21, 4275.
25. Crama, W. J.; Maaskant, W. J. A, Physica 1983, 121 B, 219.
26. Schomaker, V., Trueblood, K. N. Acta Crystallogr. 1968, B24, 63.
27. Mehran, F.; Stevens, K. W. H Phys. Rev. 1983, B27, 2899.
28. 22+, and these crystals exhibit different EPR and structural behavior very different from those of crystals grown from other solvents.
29. Nye, J. F. Physical Properties of Crystals. Their Representation by Tensors and Matrices, Clarendon Press: Oxford, England, 1960.