Ba4ZrN4 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(1), one N(3), one N(4), and two equivalent N(2) atoms. In the second Ba site, Ba(2) is bonded to two equivalent N(2) and two equivalent N(3) atoms to form distorted BaN4 trigonal pyramids that share corners with two equivalent Ba(4)N5 square pyramids, corners with four equivalent Zr(1)N4 tetrahedra, corners with two equivalent Ba(3)N5 trigonal bipyramids, and edges with two equivalent Ba(2)N4 trigonal pyramids. In the third Ba site, Ba(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted BaN5 trigonal bipyramids that share corners with three equivalent Ba(4)N5 square pyramids, corners with three equivalent Zr(1)N4 tetrahedra, corners with two equivalent Ba(2)N4 trigonal pyramids, edges with three equivalent Ba(4)N5 square pyramids,  an edgeedge with one Zr(1)N4 tetrahedra, and edges with two equivalent Ba(3)N5 trigonal bipyramids. In the fourth Ba site, Ba(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted BaN5 square pyramids that share  a cornercorner with one Zr(1)N4 tetrahedra, corners with three equivalent Ba(3)N5 trigonal bipyramids, corners with two equivalent Ba(2)N4 trigonal pyramids, edges with two equivalent Ba(4)N5 square pyramids, edges with two equivalent Zr(1)N4 tetrahedra, and edges with three equivalent Ba(3)N5 trigonal bipyramids. Zr(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form ZrN4 tetrahedra that share  a cornercorner with one Ba(4)N5 square pyramid, corners with three equivalent Ba(3)N5 trigonal bipyramids, corners with four equivalent Ba(2)N4 trigonal pyramids, edges with two equivalent Ba(4)N5 square pyramids, and  an edgeedge with one Ba(3)N5 trigonal bipyramid. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ba(1), two equivalent Ba(3), two equivalent Ba(4), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing NBa5Zr octahedra. The corner-sharing octahedral tilt angles range from 12-27°. In the second N site, N(2) is bonded in a 5-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and one Zr(1) atom. In the third N site, N(3) is bonded to one Ba(1), one Ba(3), one Ba(4), two equivalent Ba(2), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing NBa5Zr octahedra. The corner-sharing octahedral tilt angles range from 19-22°. In the fourth N site, N(4) is bonded to one Ba(1), two equivalent Ba(3), two equivalent Ba(4), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing NBa5Zr octahedra. The corner-sharing octahedral tilt angles range from 12-27°.
Ba4ZrN4 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(1), one N(3), one N(4), and two equivalent N(2) atoms. The Ba(1)-N(1) bond length is 2.79 Å. The Ba(1)-N(3) bond length is 3.04 Å. The Ba(1)-N(4) bond length is 3.17 Å. There is one shorter (2.70 Å) and one longer (3.05 Å) Ba(1)-N(2) bond length. In the second Ba site, Ba(2) is bonded to two equivalent N(2) and two equivalent N(3) atoms to form distorted BaN4 trigonal pyramids that share corners with two equivalent Ba(4)N5 square pyramids, corners with four equivalent Zr(1)N4 tetrahedra, corners with two equivalent Ba(3)N5 trigonal bipyramids, and edges with two equivalent Ba(2)N4 trigonal pyramids. There is one shorter (2.76 Å) and one longer (2.81 Å) Ba(2)-N(2) bond length. There is one shorter (2.69 Å) and one longer (2.84 Å) Ba(2)-N(3) bond length. In the third Ba site, Ba(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted BaN5 trigonal bipyramids that share corners with three equivalent Ba(4)N5 square pyramids, corners with three equivalent Zr(1)N4 tetrahedra, corners with two equivalent Ba(2)N4 trigonal pyramids, edges with three equivalent Ba(4)N5 square pyramids,  an edgeedge with one Zr(1)N4 tetrahedra, and edges with two equivalent Ba(3)N5 trigonal bipyramids. The Ba(3)-N(3) 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. There is one shorter (2.80 Å) and one longer (2.90 Å) Ba(3)-N(4) bond length. In the fourth Ba site, Ba(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted BaN5 square pyramids that share  a cornercorner with one Zr(1)N4 tetrahedra, corners with three equivalent Ba(3)N5 trigonal bipyramids, corners with two equivalent Ba(2)N4 trigonal pyramids, edges with two equivalent Ba(4)N5 square pyramids, edges with two equivalent Zr(1)N4 tetrahedra, and edges with three equivalent Ba(3)N5 trigonal bipyramids. The Ba(4)-N(3) bond length is 2.85 Å. There is one shorter (2.87 Å) and one longer (3.17 Å) Ba(4)-N(1) bond length. There is one shorter (2.86 Å) and one longer (3.06 Å) Ba(4)-N(4) bond length. Zr(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form ZrN4 tetrahedra that share  a cornercorner with one Ba(4)N5 square pyramid, corners with three equivalent Ba(3)N5 trigonal bipyramids, corners with four equivalent Ba(2)N4 trigonal pyramids, edges with two equivalent Ba(4)N5 square pyramids, and  an edgeedge with one Ba(3)N5 trigonal bipyramid. The Zr(1)-N(1) bond length is 2.10 Å. The Zr(1)-N(2) bond length is 2.14 Å. The Zr(1)-N(3) bond length is 2.12 Å. The Zr(1)-N(4) bond length is 2.14 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ba(1), two equivalent Ba(3), two equivalent Ba(4), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing NBa5Zr octahedra. The corner-sharing octahedral tilt angles range from 12-27°. In the second N site, N(2) is bonded in a 5-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and one Zr(1) atom. In the third N site, N(3) is bonded to one Ba(1), one Ba(3), one Ba(4), two equivalent Ba(2), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing NBa5Zr octahedra. The corner-sharing octahedral tilt angles range from 19-22°. In the fourth N site, N(4) is bonded to one Ba(1), two equivalent Ba(3), two equivalent Ba(4), and one Zr(1) atom to form a mixture of distorted corner and edge-sharing NBa5Zr octahedra. The corner-sharing octahedral tilt angles range from 12-27°.