Acta Crystallographica Section B

Structural Science

Volume 58, Part 1 (February 2002)

research papers

Acta Cryst. (2002). B58, 52-61 [ doi:10.1107/S0108768101016688 ]

Structure of compounds E(SnMe₃)₄ (E = Si, Ge) as seen by high-resolution X-ray powder diffraction and solid-state NMR

R. E. Dinnebier, P. Bernatowicz, X. Helluy, A. Sebald, M. Wunschel, A. Fitch and S. van Smaalen

Abstract: The compounds tetrakis(trimethylstannyl)germane, Ge(SnMe₃)₄ (1), and tetrakis(trimethylstannyl)silane, Si(SnMe₃)₄ (2), have crystal structures with the quasispherical molecules in a closed-packed stacking. At room temperature both structures have the space group P $\bar 1$ (Z = 2) with a = 9.94457 (5), b = 14.52927 (8), c = 9.16021 (5) Å, [alpha] = 90.53390 (30), [beta] = 111.73080 (30), [bold gamma] = 90.0049 (4)°, and V = 1229.414 (12) Å³ for (1) and a = 9.92009 (7), b = 14.51029 (11), c = 9.13585 (7) Å, [alpha] = 90.4769 (4), [beta] = 111.6724 (4), = 89.9877 (6)°, and V = 1222.037 (16) Å³ for (2). The molecules are found to be ordered as a result of steric interactions between neighboring molecules, as shown by analyzing the distances between the atoms. Upon heating, both compounds undergo a first-order phase transition at temperatures T_c = 348 ± 5 K, as characterized by a relative jump of the lattice parameter of 16%. At 353 K, both structures have the space group P $\bar 1$ (Z = 4), with a = 14.2037 (2) Å, and V = 2865.52 (7) Å³ for (1) and a = 14.1346 (2) Å, and V = 2823.90 (7) Å³ for (2). Rietveld refinements were performed for the low-temperature phases measured at T = 295 K [R_wp = 0.0844 for (1), R_wp = 0.0940 for (2)] and for the high-temperature phases measured at T = 353 K [R_wp = 0.0891 for (1), R_wp = 0.0542 for (2)]. The combination of high-resolution X-ray powder diffraction measurements and variable-temperature magic-angle-spinning ¹³C, ²⁹Si and ¹¹⁹Sn NMR experiments demonstrates low crystallographic and molecular (C₁) symmetries for the low-temperature phases of (1) and (2) at temperatures T < 348 ± 5 K and high crystallographic symmetry due to rotational disorder for the high-temperature phases at temperatures T > 348 ± 5 K.

Keywords: High-resolution X-ray powder diffraction; MAS NMR; symmetry; simulated annealing; tetrakis(trimethylstannyl)germane; tetrakis(trimethylstannyl)silane.


	Rietveld powder data file (CIF format) (252.0 kbytes) Contains datablock sisnme

	Rietveld powder data file (CIF format) (221.9 kbytes) Contains datablock gesnme

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