Abstract
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Highlights
Monoclinic () tetrathiafulvalene [systematic name: 2-(1,3dithiol-2-ylidene)-1,3-dithiole], C6H4S4, undergoes a reversible second-order phase transition at ca 190 K through a displacive modulation with doubling of the a parameter
TTF appears in two polymorphic modi®cations, viz. the orange monoclinic form and the yellow triclinic form
The phase, which is more stable at elevated temperatures (Bozio et al, 1979; Venuti et al, 2001), was discovered by LaPlaca et al (1975), who reported its lattice parameters (Weidenborner et al, 1977)
Summary
Monoclinic () tetrathiafulvalene [systematic name: 2-(1,3dithiol-2-ylidene)-1,3-dithiole], C6H4S4, undergoes a reversible second-order phase transition at ca 190 K through a displacive modulation with doubling of the a parameter. The low-temperature phase () contains two crystallographically non-equivalent (but centrosymmetric) molecules of very similar geometry. The structure of the low-temperature phase was solved successfully in the space group P21/n, with two crystallographically non-equivalent molecules (A and B; Fig. 1b) lying at inversion centres at Using only the (low-temperature) data with h even, the structure of -TTF can be solved and re®ned as a 1:1 disordered structure having a lattice similar to that of the phase and P21/c symmetry. -TTF contains two symmetrically non-equivalent types of stacks, the differences between their geometries are negligible. Low-temperature studies of some cocrystals, where CT is ruled out by spectroscopic and conductivity evidence, have revealed a TTF molecular geometry very similar to the present results (see Table 1). For the preliminary publication on the phase traisition in TTF, see Batsanov et al (1998)
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