The results of a high temperature single crystal X-ray diffraction study of synthetic titanite within the stability field of the A2/a (C2/c) paraphase (T > 500 K) are reported. The structure has been refined using a conventional model and one in which the Ca atom is disordered over two positions. A break in thermal expansion near T c = 825 K correlates with an effective volume contraction of the Ti octahedron. When refined with split Ca position a reorientation of the Ca displacement vector at T c is found, resulting in a more symmetrical structural arrangement of the disordered Ca cations with respect to the surrounding Ti cations. In the conventional model this reorientation is seen as a break in the thermal elongation of the shortest Ti-Ca distance. The observed temperature of the isosymmetrical structural instability is in agreement with previous observations based on Hard Mode IR and Raman spectroscopic measurements. A possible mechanism causing the observed structural changes and similarities to the thermal behaviour of the iso-structural malayaite, CaSnSiO5, are discussed.