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Iron ludwigite exhibits a superstructure between 283 and 144 K. Anomalies in its transport properties are due to a structural transition related to a charge-ordering phenomenon in the low-dimensional structure. This ordering produces a commensurate transversal charge density wave in the system. To understand these structural characteristics, an X-ray single-crystal diffraction study has been performed at 300 and 15 K. No changes were found in the crystalline structure, except for contraction of the cell volume. The bond-valence sum for each cation shows that at room temperature each Fe4-Fe2-Fe4 triad is composed of three Fe3+ ions with one extra electron per triad, and at 15 K in each Fe4a-Fe2-Fe4b triad the extra electron is accommodated in the Fe4a-Fe2 pair of each triad.