Ba3(WN2)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 three equivalent 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 W sites. In the first W site, W(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing WN4 tetrahedra. In the second W site, W(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing WN4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), one W(1), and one W(2) atom. In the second N site, N(2) is bonded to one Ba(2), three equivalent Ba(1), one W(1), and one W(2) atom to form a mixture of distorted corner, edge, and face-sharing NBa4W2 octahedra. The corner-sharing octahedral tilt angles range from 40-65°.
Ba3(WN2)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 three equivalent N(1) and three equivalent N(2) atoms. There are a spread of Ba(1)-N(1) bond distances ranging from 2.82-3.44 Å. There are a spread of Ba(1)-N(2) bond distances ranging from 2.78-3.00 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 3.14 Å. There are two shorter (3.01 Å) and two longer (3.09 Å) Ba(2)-N(1) bond lengths. There are two inequivalent W sites. In the first W site, W(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing WN4 tetrahedra. Both W(1)-N(1) bond lengths are 2.00 Å. Both W(1)-N(2) bond lengths are 1.97 Å. In the second W site, W(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing WN4 tetrahedra. Both W(2)-N(1) bond lengths are 2.01 Å. Both W(2)-N(2) bond lengths are 2.09 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), one W(1), and one W(2) atom. In the second N site, N(2) is bonded to one Ba(2), three equivalent Ba(1), one W(1), and one W(2) atom to form a mixture of distorted corner, edge, and face-sharing NBa4W2 octahedra. The corner-sharing octahedral tilt angles range from 40-65°.