Two nickel complexes supported by tridentate NS2 ligands,[Ni2 (κ‐N, S, S, S′‐NPh {CH2 (MeC6H2R′) S} 2) 2](1; R′= 3, 5‐(CF3) 2C6H3) and [Ni2 (κ‐N, S, S, S′‐NiBu {CH2C6H4S} 2) 2](2), were prepared as bioinspired models of the active site of [NiFe] hydrogenases. The solid‐state structure of 1 reveals that the [Ni2 (μ‐ArS) 2] core is bent, with the planes of the nickel centers at a hinge angle of 81.3 (5)°, whereas 2 shows a coplanar arrangement between both nickel (II) ions in the dimeric structure. Complex 1
