Ba2VN3 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent N(1), two equivalent N(2), and three equivalent N(3) atoms to form distorted BaN7 pentagonal bipyramids that share corners with four equivalent Ba(1)N7 pentagonal bipyramids,  a cornercorner with one V(1)N4 tetrahedra, edges with three equivalent Ba(1)N7 pentagonal bipyramids, and edges with four equivalent V(1)N4 tetrahedra. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to two equivalent N(3) and three equivalent N(2) atoms. V(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form VN4 tetrahedra that share  a cornercorner with one Ba(1)N7 pentagonal bipyramid, corners with two equivalent V(1)N4 tetrahedra, and edges with four equivalent Ba(1)N7 pentagonal bipyramids. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Ba(1) and two equivalent V(1) atoms. In the second N site, N(2) is bonded to two equivalent Ba(1), three equivalent Ba(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing NBa5V octahedra. The corner-sharing octahedral tilt angles are 18°. In the third N site, N(3) is bonded in a distorted single-bond geometry to two equivalent Ba(2), three equivalent Ba(1), and one V(1) atom.
Ba2VN3 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent N(1), two equivalent N(2), and three equivalent N(3) atoms to form distorted BaN7 pentagonal bipyramids that share corners with four equivalent Ba(1)N7 pentagonal bipyramids,  a cornercorner with one V(1)N4 tetrahedra, edges with three equivalent Ba(1)N7 pentagonal bipyramids, and edges with four equivalent V(1)N4 tetrahedra. Both Ba(1)-N(1) bond lengths are 2.86 Å. There is one shorter (2.82 Å) and one longer (2.85 Å) Ba(1)-N(2) bond length. There is one shorter (2.86 Å) and two longer (2.98 Å) Ba(1)-N(3) bond lengths. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to two equivalent N(3) and three equivalent N(2) atoms. There is one shorter (2.84 Å) and one longer (2.95 Å) Ba(2)-N(3) bond length. There is one shorter (2.92 Å) and two longer (2.99 Å) Ba(2)-N(2) bond lengths. V(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form VN4 tetrahedra that share  a cornercorner with one Ba(1)N7 pentagonal bipyramid, corners with two equivalent V(1)N4 tetrahedra, and edges with four equivalent Ba(1)N7 pentagonal bipyramids. The V(1)-N(2) bond length is 1.79 Å. The V(1)-N(3) bond length is 1.77 Å. Both V(1)-N(1) bond lengths are 1.86 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Ba(1) and two equivalent V(1) atoms. In the second N site, N(2) is bonded to two equivalent Ba(1), three equivalent Ba(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing NBa5V octahedra. The corner-sharing octahedral tilt angles are 18°. In the third N site, N(3) is bonded in a distorted single-bond geometry to two equivalent Ba(2), three equivalent Ba(1), and one V(1) atom.