Acta Crystallographica Section B

Structural Science

Volume 55, Part 6 (December 1999)

research papers

Acta Cryst. (1999). B55, 1014-1029 [ doi:10.1107/S0108768199006126 ]

Order-disorder phenomena determined by high-resolution powder diffraction: the structures of tetrakis(trimethylsilyl)methane C[Si(CH₃)₃]₄ and tetrakis(trimethylsilyl)silane Si[Si(CH₃)₃]₄

R. E. Dinnebier, W. A. Dollase, X. Helluy, J. Kümmerlen, A. Sebald, M. U. Schmidt, S. Pagola, P. W. Stephens and S. van Smaalen

Abstract: The compounds tetrakis(trimethylsilyl)methane C[Si(CH₃)₃]₄ (TC) and tetrakis(trimethylsilyl)silane Si[Si(CH₃)₃]₄ (TSi) have crystal structures with the molecules in a cubic closed-packed (c.c.p.) stacking. At room temperature both structures have space group $Fm{\bar 3}m$ (Z = 4) with a = 13.5218 (1) Å, V = 2472.3 (1) Å³ for TSi, and a = 12.8902 (2) Å, V = 2141.8 (1) Å³ for TC. X-ray scattering data can be described by a molecule with approximately sixfold orientational disorder, ruling out a structure with free rotating molecules. Upon cooling, TSi exhibits a first-order phase transition at T_c = 225 K, as is characterized by a jump of the lattice parameter of [Delta] a = 0.182 Å and by an exothermal maximum in differential scanning calorimetry (DSC) with [Delta] H = 11.7 kJ mol^-1 and [Delta] S = 50.0 J mol^-1 K^-1. The structure of the low-temperature phase is refined against X-ray powder data measured at 200 K. It has space group P2₁3 (Z = 4), a = 13.17158 (6) Å and V = 2285.15 (2) Å³. The molecules are found to be ordered as a result of steric interactions between neighboring molecules, as is shown by analyzing distances between atoms and by calculations of the lattice energy in dependence on the orientations of the molecules. TC has a phase transition at T_c1 = 268 K, with [Delta] a₁ = 0.065 Å, [Delta] H₁ = 3.63 kJ mol^-1 and [Delta] S₁ = 13.0 J mol^-1 K^-1. A second first-order phase transition occurs at T_c2 = 225 K, characterized by [Delta] a₂ = 0.073 Å, [Delta] H₂ = 6.9 kJ mol^-1 and [Delta] S₂ = 30.0 J mol^-1 K^-1. The phase transition at higher temperature has not been reported previously. New NMR experiments show a small anomaly in the temperature dependence of the peak positions in NMR to occur at T_c2. Rietveld refinements were performed for the low-temperature phase measured at T = 150 K [space group P2₁3, lattice parameter a = 12.609 (3) Å], and for the intermediate phase measured at T = 260 K [space group $Pa{\bar 3}$ , lattice parameter a = 12.7876 (1) Å]. The low-temperature phase of TC is formed isostructural to the low-temperature phase of TSi. In the intermediate phase the molecules exhibit a twofold orientational disorder.

Keywords: Domain size broadening; Molecular modelling; Order-disorder; Powder diffraction.