Full pattern Le-Bail refinement using x-ray powder diffraction profiles of Sr1-xCaxTiO3 for x=0.02, 0.04 in the temperature range 12 to 300 K reveals anomalies in the unit cell parameters at 170, 225 K due to an antiferrodistortive (cubic to tetragon
al I4/mcm) phase transition and at ~32, ~34 K due to a transition to a polar phase (tetragonal I4/mcm to orthorhombic Ic2m), respectively. The lower transition temperatures obtained by us are in excellent agreement with those reported on the basis of the dielectric studies by Bednorz and Muller, [10] who attributed these to ferroelectric transition. Rietveld analysis of the diffraction profiles of the polar phase reveals off-centre displacements of both Sr2+/Ca2+ and Ti4+ ions in the X-Y plane along <110> pseudocubic directions, in agreement with the experimentally reported direction of easy polarization by Bednorz and Muller, but the resulting dipole moments are shown to be ferrielectrically coupled in the neighbouring (001) planes along the [001] direction leading to anomalously low values of the spontaneous polarization at 12K.
