  Temperature-dependent x-ray diffraction of the low-dimensional spin 1/2
quantum magnet TiOCl shows that the phase transition at T_{c2} = 90 K
corresponds to a lowering of the lattice symmetry. Below T_{c1} = 66 K a
twofold superstructure develops, that indicates the formation of spin-singlet
pairs via direct exchange between neighboring Ti atoms, while the role of
superexchange is found to be negligible. TiOCl thus is identified as a
spin-Peierls system of pure 1D chains of atoms. The first-order character of
the transition at T_{c1} is explained by the competition between the
structurally deformed state below T_{c2} and the spin-Peierls state below
T_{c1}.
