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How particular bonds form in quantum materials has been a long-standingpuzzle. Two key concepts dealing with charge degrees of freedom aredimerization (forming metal-metal bonds) and charge ordering (CO). Since the1930s, these two concepts have been frequently invoked to explain numerousexciting quantum materials, typically insulators. Here we report dimerizationand CO within the dimers coexisting in metallic NaRu$_2$O$_4$. By combininghigh-resolution x-ray diffraction studies and theoretical calculations, wedemonstrate that this unique phenomenon occurs through a new type of bonding,which we call Z-type ordering. The low-temperature superstructure has strongdimerization in legs of zigzag ladders, with short dimers in legs connected byshort zigzag bonds, forming Z-shape clusters: simultaneously, site-centeredcharge ordering also appears. Our results demonstrate the yet unknownflexibility of quantum materials with the intricate interplay among orbital,charge, and lattice degrees of freedom.

Coexisting Z-type charge and bond order in metallic NaRu$_2$O$_4$