Nb5N6 crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to six equivalent N(1) atoms to form a mixture of edge and corner-sharing NbN6 octahedra. In the second Nb site, Nb(2) is bonded to six equivalent N(1) atoms to form a mixture of distorted edge and corner-sharing NbN6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 3°. N(1) is bonded to two equivalent Nb(1) and three equivalent Nb(2) atoms to form a mixture of edge, corner, and face-sharing NNb5 square pyramids.
Nb5N6 crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to six equivalent N(1) atoms to form a mixture of edge and corner-sharing NbN6 octahedra. All Nb(1)-N(1) bond lengths are 2.15 Å. In the second Nb site, Nb(2) is bonded to six equivalent N(1) atoms to form a mixture of distorted edge and corner-sharing NbN6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 3°. There are four shorter (2.20 Å) and two longer (2.21 Å) Nb(2)-N(1) bond lengths. N(1) is bonded to two equivalent Nb(1) and three equivalent Nb(2) atoms to form a mixture of edge, corner, and face-sharing NNb5 square pyramids.