Ba3(NbN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. In the second Ba site, Ba(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a distorted tetrahedral geometry to two equivalent N(1) and two equivalent N(2) atoms. In the second Nb site, Nb(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(2), one Nb(1), and one Nb(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ba(2), three equivalent Ba(1), one Nb(1), and one Nb(2) atom.
Ba3(NbN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. The Ba(1)-N(1) bond length is 2.86 Å. There are a spread of Ba(1)-N(2) bond distances ranging from 2.82-3.01 Å. In the second Ba site, Ba(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. Both Ba(2)-N(2) bond lengths are 3.16 Å. There are two shorter (3.03 Å) and two longer (3.15 Å) Ba(2)-N(1) bond lengths. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded in a distorted tetrahedral geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Nb(1)-N(1) bond lengths are 2.04 Å. Both Nb(1)-N(2) bond lengths are 2.02 Å. In the second Nb site, Nb(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Nb(2)-N(1) bond lengths are 2.06 Å. Both Nb(2)-N(2) bond lengths are 2.16 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 2-coordinate geometry to one Ba(1), two equivalent Ba(2), one Nb(1), and one Nb(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ba(2), three equivalent Ba(1), one Nb(1), and one Nb(2) atom.