Abstract
The structure of Rh4(CO)12 (1) has been redetermined at room temperature and at 173 K. Crystallographic data for 1 at 293 K are as follows: C12O12Rh4, space group P21/c, a=9.209(3), b=11.790(7), c=17.721(8) Å, β=90.46(3)°, V=1924.0(16) Å3, Z=4, 5570 reflections to θ=30.0°, and R=0.030. For 1 at 173 K the data are as follows: space group P21/c, a=9.127(3), b=11.672(6), c=17.492(13) Å, β=90.64(5)°, V=1863.3(18) Å3, Z=4, 3782 reflections to θ=26.3°, and R=0.033. There was no detectable phase change on cooling to 173 K. Crystals of 1 are twinned by pseudo-merohedry, but a satisfactory refinement was obtained by assuming a (100) twinning mirror plane. TLS analysis of the anisotropic displacement parameters at both temperatures has been undertaken. Investigation of the mean square displacement difference between the observed and the rigid body displacement parameters reveals there is a signficant internal motion of the carbonyl ligands relative to the metal skeleton. This motion is consistent with a normal mode or modes of C 3 symmetry.
Similar content being viewed by others
REFERENCES
(a) B. E. Mann (1997). J. Chem. Soc. Dalton Trans. 1457 and refs. therein. (b) B. F. G. Johnson (1997). J. Chem. Soc. Dalton Trans. 1473 and refs. therein. (c) D. Braga, C. E. Anson, A. Bott, B. F. G. Johnson, and E. Marseglia (1990). J. Chem. Soc. Dalton Trans. 3517.
(a) R. E. Benfield and B. F. G. Johnson (1978). J. Chem. Soc. Dalton Trans. 554; B. F. G. Johnson and Y. V. Roberts (1993). Polyhedron 12, 977.
(a) P. Corradini (1959). J. Chem. Phys. 31, 1676. (b) P. Corradini and A. Sirigu (1966). Ric. Sci. 36, 188. (c) C. H. Wei and L. F. Dahl (1966). J. Am. Chem. Soc. 88, 1821. (d) C. H. Wei (1969). Inorg. Chem. 8, 2384. (e) F. H. Carré, F. A. Cotton, and B. A. Frenz (1976). Inorg. Chem. 15, 380.
M. R. Churchill and J. P. Hutchinson (1978). Inorg. Chem. 17, 3528.
(a) M. A. Cohen, D. R. Kidd, and T. L. Brown (1975). J. Am. Chem. Soc. 97, 4408. (b) J. Evans, B. F. G. Johnson, J. Lewis, and T. W. Matheson (1975). J. Am. Chem. Soc. 97, 1245. (c) J. Evans, B. F. G. Johnson, J. Lewis, T. W. Matheson, and J. R. Norton (1978). J. Chem. Soc. Dalton Trans. 626. (d) S. Aime and L. Milone (1977). Prog. NMR Spectrosc. 11, 183. (e) S. Aime, L. Milone, D. Osella, and A. Poli (1978). Inorg. Chim. Acta 30, 45.
(a) B. E. Hanson and E. C. Lisic (1986). Inorg. Chem. 25, 716. (b) C. E. Anson, R. E. Benfield, A. W. Bott, B. F. G. Johnson, D. Braga, and E. A. Marseglia (1988). J. Chem. Soc. Chem. Commun. 889. (c) S. Aime, M. Botta, R. Gobetto, and B. E. Hanson (1989). Inorg. Chem. 28, 1196. (d) B. T. Heaton, J. Sabounchei, S. Kernaghan, H. Nakayama, T. Eguchi, S. Takeda, N. Nakamura, and H. Chihara (1990). Bull. Chem. Soc. Jpn. 63, 3019.
L. J. Farrugia, D. Braga, and F. Grepioni (1998). J. Organomet. Chem. 573, 60.
L. J. Farrugia and S. J. Coles, unpublished observations. The structural data for Ir4(CO)12 at the current state of refinement are C12O12Ir4, trigonal, space group P3, a = 26.4412(2), c = 8.9226(1) Å, V = 5402.37(1) Å3, Z = 12, 14,818 independent reflections to Ø = 27.5°, R = 0.14, λ = 0.6875, and T = 295 K. There are six independent molecules in the asymmetric unit, which show varying degrees of disorder. The unit cell is four times the volume of that previously reported (see Ref. 4), and several C and O positions are not directly determinable from the difference Fourier maps.
T. H. Walter, L. Reven, and E. Oldfield (1989). J. Phys. Chem. 93, 1320.
(a) C. H. Wei, G. R. Wilkes, and L. F. Dahl (1967). J. Am. Chem. Soc. 89, 4792. (b) C. H. Wei (1969). Inorg. Chem. 8, 2384.
(a) J. Evans, B. F. G. Johnson, J. Lewis, T. W. Matheson, and J. R. Norton (1978). J. Chem. Soc. Dalton Trans. 626. (b) F. A. Cotton, L. Kruczynski, B. L. Shapiro, and L. F. Johnson (1972). J. Am. Chem. Soc. 94, 6191.
S. Martinengo, G. Giordano, and P. Chini (1990). Inorg. Synth. 28, 242.
A. C. T. North, D. C. Phillips, and F. S. Mathews (1968). Acta Crystallogr. A24, 351.
R. H. Blessing (1995). Acta Crystallogr. Sect. A A51, 33.
SHELXS-97 a program for crystal structure solution; G. M. Sheldrick (1997). University of Goöttingen, Göttingen, Germany.
SHELXL97 a program for crystal structure refinement; G. M. Sheldrick (1997). University of Góttingen, Góttingen, Germany.
R. Herbst-Irmer and G. M. Sheldrick (1998). Acta Cryst. B54, 443.
Tables 4.2.4.2, 4.2.6.8, and 6.1.1.4 from International Tables for Crystallography, Volume C Mathematical, Physical and Chemical Tables (Kluwer, Dordrecht, 1995).
(a) V. Schomacher and K. N. Trueblood (1968). Acta Crystallogr. B24, 63. (b) J. D. Dunitz and D. N. J. White (1973). Acta Crystallogr. A29, 93. (c) J. D. Dunitz, E. F. Maverick, and K. N. Trueblood (1988). Angew Chem. 100, 910.
W. Hummel, A. Raselli, and H.-B. Buürgi (1990). Acta Crystallogr. B46, 683.
W. Hummel, J. Hauser, and H.-B. Bürgi (1990). J. Mol. Graphics 8, 214.
L. J. Farrugia (1999). J. Appl. Cryst. 32, 837.
L. J. Farrugia (1997). J. Appl. Cryst. 30, 565.
H. Zabrosky, S. Peleg, and D. Avnir (1992). J. Am. Chem. Soc. 114, 7843.
H. Zabrosky, S. Peleg, and D. Avnir (1993). J. Am. Chem. Soc. 115, 8278.
T. Pilati and A. Forni (1998). J. Appl. Cryst. 31, 503.
M. R. Churchill, F. J. Hollander, and J. P. Hutchinson (1977). Inorg. Chem. 16, 2655.
D. Braga and F. Grepioni (1987). J. Organomet. Chem. 339, C9.
A. Martín and A. G. Orpen (1996). J. Am. Chem. Soc. 118, 1464.
R. Bender, P. Braunstein, A. Tiripicchio, and M. Tiripicchio Camellini (1985). Angew Chem. Int Ed. Engl. 24, 861.
F. L. Hirshfeld (1976). Acta Crystallogr. A32, 239.
D. Braga and B. T. Heaton (1987). J. Chem. Soc., Chem. Commun. 608.
B. F. G. Johnson and A. Rodgers, in D. F. Shriver, H. D. Kaesz, and R. D. Adams (eds.), Chemistry of Metal Cluster Complexes (VCH, New York, 1990), pp. 303-327.
(a) G. Bor, G. Sbrignadello, and K. Noak (1975). Helv. Chim. Acta 58, 815. (b) M. J. Sailor, M. J. Went, and D. F. Shriver (1988). Inorg. Chem. 27, 2666. (c) S. F. A. Kettle and P. L. Stanghellini (1987). Inorg. Chem. 26, 1626. (d) P. L. Stanghellini, R. Rossetti, G. D'Alfonso, and G. Longoni (1987). Inorg. Chem. 26, 2769. (e) G. A. Battison, G. Bor, U. K. Dietler, S. F. A. Kettle, R. Rossetti, G. Sbrignadello, and P. L. Stanghellini (1980). Inorg. Chem. 19, 1961.
G. Bor, F. H. Oldani and S. F. A. Kettle (1998). J. Clust. Sci. 9, 259.
F. A. Cotton (1966). Inorg. Chem. 5, 1083.
(a) B. F. G. Johnson, Y. V. Roberts, E. Parsini, and R. E. Benfield (1994). J. Organomet. Chem. 478, 21. (b) Y. V. Roberts, B. F. G. Johnson, and R. E. Benfield (1995). Inorg. Chim. Acta 229, 221.
(a) G. Suardi, A. Strawczynski, R. Ros, R. Roulet, F. Grepioni, and D. Braga (1990). Helv. Chim. Acta 73, 154. (b) A. Orlandi, U. Frey, G. Suardi, A. E. Merbach, and R. Roulet (1992). Inorg. Chem. 31, 1304.
J. W. Lauher (1986). J. Am. Chem. Soc. 108, 1521.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Farrugia, L.J. Structural Redetermination of Rh4(CO)12 at 293 and 173 K and Analysis of the Thermal Motion in Relation to the Dynamical Behavior. Journal of Cluster Science 11, 39–53 (2000). https://doi.org/10.1023/A:1009000428525
Issue Date:
DOI: https://doi.org/10.1023/A:1009000428525