The structure of a two-dimensional honeycomb optical lattice potential with small inversion asymmetry is characterized using coherent diffraction of 87 Rb atoms. We demonstrate that even a small potential asymmetry, with peak-to-peak amplitude of ≤ 2.3% of the overall lattice potential, can lead to pronounced inversion asymmetry in the momentum-space diffraction pattern. The observed asymmetry is explained quantitatively by considering both Kapitza-Dirac scattering in the RamanNath regime, and also either perturbative or full-numerical treatment of the band structure of a periodic potential with a weak inversion-symmetry-breaking term. Our results have relevance for both the experimental development of coherent atom optics and the proper interpretation of timeof-flight assays of atomic materials in optical lattices. DOI: 10.1103/PhysRevA.93.063613 In x-ray crystallography, the diffraction of light is analyzed to determine the exact crystalline structure of a material. Similarly, with the availability of ultracold sources of coherent matter waves of atoms, one can use atomic diffraction to characterize potentials experienced by the atoms. Of particular interest are the optical lattice potentials produced by periodic patterns of light intensity and polarization, formed by the intersection of several coherent plane waves of light or by direct imaging. Lattice potentials of various geometries and dimensionalities, some incorporating atomic-spin dependence and gauge fields, have been produced or proposed for the purpose of creating synthetic atomic materials by placing quantum-degenerate atoms within them [1][2][3]. Just as in condensed matter, the characteristics of such synthetic atomic materials derive from the nature of the optical crystal upon which they are based. Matter-wave crystallography therefore becomes a vital tool in the study of such synthetic quantum matter [4].A key first step in determining the structure of a lattice is the assignment of its point-group and space-group symmetries. The violation of a symmetry is identified in x-ray crystallography by a difference in the intensities of diffraction spots [5]. Following such work, here we detect the inversion asymmetry of an optical lattice by observing significant asymmetries in the diffraction of a coherent matter wave from the potential. For this, we produce a spin-polarized 87 Rb Bose-Einstein condensate at rest, and then impose for a variable pulse duration the two-dimensional honeycomb optical lattice potential produced by three light beams intersecting at equal angles [6]. The resulting Kapitza-Dirac diffraction is quantified by imaging the gas after it is allowed to expand freely. By tuning the pulse time and working with a deep optical lattice, we produce highly visible (over 50% contrast) * Electronic address: dmsk@berkeley.edu inversion asymmetry in the populations of the first-order diffraction peaks even while the inversion-asymmetric part of the potential is ≤ 2.3% of the overall lattice potential. This observation highlights the extre...