The Structure of Tri(cyclohexyl)tin Chloride between 108 and 298 K:  A Compound in Which Molecular Dimensions Vary with Temperature

Abstract

Care is necessary when relating physical data obtained at one temperature on compounds showing significant intermolecular interactions to X-ray data obtained at other temperatures. This is revealed by the determination of the structure of tri(cyclohexyl)tin chloride at nine different temperatures between 108 and 298 K. In the crystal, the molecules pack in chains parallel to the c axis with the Sn and Cl atoms close to the plane, with y = 0.25. At low temperature, successive molecules in the chain are related by the glide plane in space group P2(1)/c, and there is significant intermolecular interaction. As the temperature is raised, the Cy(3)SnCl.Sn interactions weaken and the intramolecular Sn-Cl bonds strengthen. At about 248 K, there is an order-disorder transition to space group P2(1)/m with the c axis halved, and at room temperature the structure is best described as comprising discrete molecules, as previously reported. Thus, some of the molecular dimensions, in particular the Sn-Cl bond lengths, are not constant but are functions of temperature.

Luminescence as a probe of phase changes in transition metal complexes

“…Spectral differences between the phases are unclear as there are overlapping component bands. For tri(cyclohexyl) tin chloride the earlier data [6] showed relatively smooth variations with lattice parameters over the range 108 to 298 K for powder samples but an energy release in the DTA near 240 K [7]. Luminescence data are consistent with the lattice parameter measurements, with no evidence of signal discontinuities that might be associated with structural changes Luminescence sensitivity is influenced by long range interactions of 10 to 100 nm and for powder this constitutes a large fraction of the grains.…”

“…However, it has not been attempted previously with transition metal complexes. This extension of the luminescence method was considered since recent X-ray structural analy-ses of tri(cyclohexyl) tin chloride [6] record lattice parameter changes which are relatively continuous with temperature, whilst DTA of the compound indicated two energy release events near 240K [7]. Alternative probes of the changes might resolve if these difference.…”

The differences in solid state structures of C,N-chelated nbutyltin(IV) fluorides

“…[19]). On the other hand, isomer 3b retained unchanged in the range of 100-250 K. This is probably caused by a repulsion of p-electrons of Ph rings in 3c.…”

“…The NMR spectra were recorded as solutions in methanol-d 4, or CDCl 3 on a Bruker Avance 500 spectrometer (equipped with Z-gradient 5 mm probe) at 300, 250 or 220 K 1 H (500.13 MHz), 119 Sn{ 1 H} (186.50 MHz) and 19 F{ 1 H} (470.53 MHz). The solutions were obtained by dissolving of 5-40 mg of each compound in 0.5 ml of deuterated solvents.…”

Evaluation of PM3 calculations applied to organotin compounds: crystal structure of [Ph2SnCl2 (1,10‐phenanthroline‐5,6‐dione)]·2Me2CO

“…A conflicting conclusion regarding the solid-state structure was reached a few years later by Harris et al, 38 who reported solid state as well. More recently, Asadi et al 39 investigated the X-ray crystal structure of 20 over the temperature range 120-298 K and clearly revealed the importance of the intermolecular contacts. Of interest is that, as the temperature is reduced, the 'intramolecular' Sn-Cl bond lengths increased and the 'intermolecular' Sn-Cl [Sn-Cl ] distances decreased.…”