Ba4VN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 5-coordinate geometry to one N(4), two equivalent N(2), and two equivalent N(3) atoms. In the second Ba site, Ba(2) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(4) atoms to form distorted BaN6 pentagonal pyramids that share corners with two equivalent V(1)N4 tetrahedra, edges with three equivalent Ba(2)N6 pentagonal pyramids, and edges with two equivalent V(1)N4 tetrahedra. In the third Ba site, Ba(3) is bonded in a rectangular see-saw-like geometry to one N(3), one N(4), and two equivalent N(1) atoms. In the fourth Ba site, Ba(4) is bonded in a 4-coordinate geometry to one N(2), one N(4), and two equivalent N(1) atoms. V(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form VN4 tetrahedra that share corners with two equivalent Ba(2)N6 pentagonal pyramids and edges with two equivalent Ba(2)N6 pentagonal pyramids. There are four inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Ba(3), two equivalent Ba(4), and one V(1) atom to form distorted edge-sharing NBa4V trigonal bipyramids. In the second N site, N(2) is bonded in a distorted single-bond geometry to one Ba(4), two equivalent Ba(1), two equivalent Ba(2), and one V(1) atom. In the third N site, N(3) is bonded in a 6-coordinate geometry to one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one V(1) atom. In the fourth N site, N(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(3), one Ba(4), two equivalent Ba(2), and one V(1) atom.
Ba4VN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 5-coordinate geometry to one N(4), two equivalent N(2), and two equivalent N(3) atoms. The Ba(1)-N(4) bond length is 2.94 Å. There is one shorter (2.98 Å) and one longer (3.15 Å) Ba(1)-N(2) bond length. There is one shorter (2.74 Å) and one longer (3.05 Å) Ba(1)-N(3) bond length. In the second Ba site, Ba(2) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(4) atoms to form distorted BaN6 pentagonal pyramids that share corners with two equivalent V(1)N4 tetrahedra, edges with three equivalent Ba(2)N6 pentagonal pyramids, and edges with two equivalent V(1)N4 tetrahedra. There is one shorter (2.90 Å) and one longer (2.96 Å) Ba(2)-N(2) bond length. There is one shorter (2.83 Å) and one longer (2.89 Å) Ba(2)-N(3) bond length. There is one shorter (2.86 Å) and one longer (3.01 Å) Ba(2)-N(4) bond length. In the third Ba site, Ba(3) is bonded in a rectangular see-saw-like geometry to one N(3), one N(4), and two equivalent N(1) atoms. The Ba(3)-N(3) bond length is 2.77 Å. The Ba(3)-N(4) bond length is 2.98 Å. There is one shorter (2.76 Å) and one longer (2.77 Å) Ba(3)-N(1) bond length. In the fourth Ba site, Ba(4) is bonded in a 4-coordinate geometry to one N(2), one N(4), and two equivalent N(1) atoms. The Ba(4)-N(2) bond length is 2.84 Å. The Ba(4)-N(4) bond length is 3.15 Å. There is one shorter (2.65 Å) and one longer (2.68 Å) Ba(4)-N(1) bond length. V(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form VN4 tetrahedra that share corners with two equivalent Ba(2)N6 pentagonal pyramids and edges with two equivalent Ba(2)N6 pentagonal pyramids. The V(1)-N(1) bond length is 1.86 Å. The V(1)-N(2) bond length is 1.84 Å. The V(1)-N(3) bond length is 1.85 Å. The V(1)-N(4) bond length is 1.83 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Ba(3), two equivalent Ba(4), and one V(1) atom to form distorted edge-sharing NBa4V trigonal bipyramids. In the second N site, N(2) is bonded in a distorted single-bond geometry to one Ba(4), two equivalent Ba(1), two equivalent Ba(2), and one V(1) atom. In the third N site, N(3) is bonded in a 6-coordinate geometry to one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one V(1) atom. In the fourth N site, N(4) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(3), one Ba(4), two equivalent Ba(2), and one V(1) atom.