Ba3(VN2)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 V sites. In the first V site, V(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing VN4 tetrahedra. In the second V site, V(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing VN4 tetrahedra. 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 V(1), and one V(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 V(1), and one V(2) atom.
Ba3(VN2)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 2.74 Å. There are a spread of Ba(1)-N(2) bond distances ranging from 2.77-2.90 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 3.11 Å. There are two shorter (2.95 Å) and two longer (2.99 Å) Ba(2)-N(1) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing VN4 tetrahedra. Both V(1)-N(1) bond lengths are 1.89 Å. Both V(1)-N(2) bond lengths are 1.88 Å. In the second V site, V(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing VN4 tetrahedra. Both V(2)-N(1) bond lengths are 1.93 Å. Both V(2)-N(2) bond lengths are 2.01 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 V(1), and one V(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 V(1), and one V(2) atom.