Structure and hydrogenation study of nickel substituted NdCo3NiB

► New quaternary intermetallic boride NdCo3NiB and its synthesised hydride. ► NdCo3NiB crystallizes with the centrosymmetric CeCo4B-type structure. ► No evidence for cobalt/nickel ordering was found in the structure. ► Hydrogenation of NdCo3NiB induces a symmetry decrease to non-centrosymmetric. ► Deuterium atoms occupy only types of interstices with no boron in their coordination sphere.