Abstract:The structure determination of an HfSi 4 precipitate has been carried out by a combination of two precession electron diffraction techniques: high precession angle, 2.28, single pattern collection at eight different zone axes and low precession angle, 0.58, serial collection of patterns obtained by increasing tilts of 18. A threedimensional reconstruction of the associated reciprocal space shows an orthorhombic unit cell with parameters a ϭ11.4 Å, b ϭ11.8 Å, c ϭ14.6 Å, and an extinction condition of~hkl ! h ϩ k odd. The merged intensities from the high angle precession patterns have been symmetry tested for possible space groups~SG! fulfilling this condition and a best symmetrization residual found at 18% for SG 65 Cmmm. Use of the SIR2011 direct methods program allowed solving the structure with a structure residual of 18%. The precipitate objects of this study were reproducibly found in a newly implemented alloy, designed according to molecular orbital theory.