The dij coefficients of the second-order susceptibility tensor for second harmonic generation were detemined for a calamitic ferroelectric liquid crystal (FLC) specifically designed for applications in non-linear optics. The measurements were performed at different temperatures in the SmC* phase. In accordance with the design methodology of these materials, the coefficient along the polar axis d22 is the greatest, and depicts an expected behaviour in the whole range of the ferroelectric phase. On the other hand, the temperature dependence of d21, d23, and d25, is anomalous to some extent, including a sign inversion of d23 at a certain temperature. These results, which contrast with those reported recently for non-calamitic FLCs, were qualitatively interpreted in the light of different conformations which, by virtue of plausible distortions of the molecular core, could coexist in the sample.