Crystals of 1, suitable for single crystal X-ray diffraction (scXRD) were grown by vapor diffusion of diethyl ether into a DCM solution of 1. The solid-state structure of 1 (Figure ) features two different cobalt centers of which one is bound in the PN binding pocket, and one is only bound to the phosphine of the second binding pocket. Both cobalt centers have a tetrahedral geometry. The structure of 1 features one bridging chloride atom and three terminal ones. Due to one of the cobalt atoms binding outside of the PNNP pocket, the Co-Co distance of 3.8838 (17)Å is larger than what is normally observed for PNNP complexes in which both metals are bound within the dinucleating binding pocket. The Co1-Cl1-Co2 angle of 113.07 (10)° is indicative of the chloride binding as an LX type ligand the cobalt centers. The Co-Cl1 bond distances (Table ) are also significantly longer than the Co-Cl bonds for the terminal chlorides, consistent with this LX-type binding description. The C1-C2 and C9-C10 bond lengths of 1.486(13) and 1.505 (11) Å are in line with C-C single bonds, which is indicative of a neutral PNNP backbone. The solid-state structure of 1 is consistent with the observed low symmetry in the paramagnetic 1 H NMR spectrum. This suggests that the solution state structure is similar to what is observed in the solid state.