Two pressure-induced structural phase transitions in TiOCl

We studied the crystal structure of TiOCl up to pressures of $p$=25~GPa at room temperature by x-ray powder diffraction measurements. Two pressure-induced structural phase transitions are observed: At $p_{c1}$$\approx$15~GPa emerges an 2$a$$\times$2$b$$\times$$c$ superstructure with $b$-axis unique monoclinic symmetry (space group P2$_1$/$m$). At $p_{c2}$$\approx$22~GPa all lattice parameters of the monoclinic phase show a pronounced anomaly. A fraction of the sample persists in the ambient orthorhombic phase (space group $Pmmn$) over the whole pressure range.