Single crystals suitable for X-ray diffraction were grown by slow vapour diffusion of pentane into a saturated 1,4-dioxane solution of 3. The introduction of ZnCl 2 to the empty pocket next to the NHGe motif was confirmed in the solid-state structure of 3 (Figure ). The N1-Ge-N3 bond angle of 84.15 (17)° falls within the typical range for 5-membered NHGes. The Ge-Zn distance of 3.1110 (8) Å lies between the sum of their covalent and their van der Waals radii (2.42 and 4.68 Å respectively), albeit appreciably larger than reported Ge-Zn distances. The environment around the Zn centre is best described as tetrahedral with a distortion due to the proximity of Ge. For the Ge-side of the molecule, the bond metrics are consistent with C-N single bonds (C1-N3 = 1.378(6) Å, C2-N1 = 1.410(6) Å) and the presence of a C=C bond located outside of the naphthyridine ring system (C1-C2 = 1.361(7) Å). These features are in agreement with the two-electron reduction of that naphthyridine pocket. The alternating single and double C-C bonds in the respective ring of the naphthyridine motif confirm the two-electron reduction. This is in stark contrast to the other ring, where C-C bonds of more uniform length are observed (see ESI Table ). Additionally, the bond metrics consistent with a C=N double bond (C10-N4 = 1.283( ) Å) are too long to assign any meaningful bonding interaction between these two atom pairs. Figure : Displacement ellipsoid plot of 3 at 50% probability. Co-crystallised 1,4-dioxane molecules, hydrogen atoms and disordered components are omitted for clarity. The dipp substituents are depicted as wireframe for clarity.