Ba9(NbN6)2 crystallizes in the triclinic P-1 space group. There are nine inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one N(1), one N(11), one N(12), one N(2), one N(5), and two equivalent N(7) atoms. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one N(2), one N(4), one N(6), one N(7), one N(9), and two equivalent N(8) atoms. In the third Ba site, Ba(3) is bonded in a 8-coordinate geometry to one N(1), one N(11), one N(12), one N(2), one N(3), one N(5), and two equivalent N(10) atoms. In the fourth Ba site, Ba(4) is bonded to one N(3), one N(4), one N(6), and two equivalent N(9) atoms to form distorted BaN5 trigonal bipyramids that share  a cornercorner with one Ba(8)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra,  a cornercorner with one Nb(2)N4 tetrahedra,  a cornercorner with one Ba(5)N5 trigonal bipyramid, corners with three equivalent Ba(9)N5 trigonal bipyramids,  an edgeedge with one Ba(8)N6 octahedra, edges with two equivalent Ba(6)N6 octahedra,  an edgeedge with one Nb(1)N4 tetrahedra, and  an edgeedge with one Ba(4)N5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 77°. In the fifth Ba site, Ba(5) is bonded to one N(2), one N(4), one N(7), and two equivalent N(5) atoms to form distorted BaN5 trigonal bipyramids that share  a cornercorner with one Ba(8)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra, corners with three equivalent Nb(2)N4 tetrahedra,  a cornercorner with one Ba(4)N5 trigonal bipyramid,  an edgeedge with one Ba(6)N6 octahedra, and  an edgeedge with one Ba(5)N5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 100°. In the sixth Ba site, Ba(6) is bonded to one N(10), one N(11), one N(4), one N(6), one N(7), and one N(9) atom to form distorted BaN6 octahedra that share corners with two equivalent Ba(8)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra,  an edgeedge with one Nb(2)N4 tetrahedra,  an edgeedge with one Ba(5)N5 trigonal bipyramid,  an edgeedge with one Ba(9)N5 trigonal bipyramid, and edges with two equivalent Ba(4)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-19°. In the seventh Ba site, Ba(7) is bonded in a 6-coordinate geometry to one N(10), one N(11), one N(3), one N(4), one N(5), and one N(6) atom. In the eighth Ba site, Ba(8) is bonded to one N(1), one N(3), one N(4), one N(6), and two equivalent N(8) atoms to form distorted BaN6 octahedra that share corners with two equivalent Ba(6)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra,  a cornercorner with one Ba(4)N5 trigonal bipyramid,  a cornercorner with one Ba(5)N5 trigonal bipyramid,  an edgeedge with one Ba(8)N6 octahedra,  an edgeedge with one Nb(1)N4 tetrahedra,  an edgeedge with one Nb(2)N4 tetrahedra,  an edgeedge with one Ba(4)N5 trigonal bipyramid, and edges with two equivalent Ba(9)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-19°. In the ninth Ba site, Ba(9) is bonded to one N(1), one N(11), one N(3), one N(8), and one N(9) atom to form distorted BaN5 trigonal bipyramids that share  a cornercorner with one Nb(2)N4 tetrahedra, corners with three equivalent Nb(1)N4 tetrahedra, corners with three equivalent Ba(4)N5 trigonal bipyramids,  an edgeedge with one Ba(6)N6 octahedra, and edges with two equivalent Ba(8)N6 octahedra. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one N(2), one N(3), one N(8), and one N(9) atom to form NbN4 tetrahedra that share  a cornercorner with one Ba(6)N6 octahedra,  a cornercorner with one Ba(8)N6 octahedra,  a cornercorner with one Ba(4)N5 trigonal bipyramid,  a cornercorner with one Ba(5)N5 trigonal bipyramid, corners with three equivalent Ba(9)N5 trigonal bipyramids,  an edgeedge with one Ba(8)N6 octahedra, and  an edgeedge with one Ba(4)N5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 71-85°. In the second Nb site, Nb(2) is bonded to one N(1), one N(5), one N(6), and one N(7) atom to form NbN4 tetrahedra that share  a cornercorner with one Ba(4)N5 trigonal bipyramid,  a cornercorner with one Ba(9)N5 trigonal bipyramid, corners with three equivalent Ba(5)N5 trigonal bipyramids,  an edgeedge with one Ba(6)N6 octahedra, and  an edgeedge with one Ba(8)N6 octahedra. There are twelve inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), one Ba(8), one Ba(9), and one Nb(2) atom. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(5), and one Nb(1) atom. In the third N site, N(3) is bonded in a 6-coordinate geometry to one Ba(3), one Ba(4), one Ba(7), one Ba(8), one Ba(9), and one Nb(1) atom. In the fourth N site, N(4) is bonded to one Ba(2), one Ba(4), one Ba(5), one Ba(6), one Ba(7), and one Ba(8) atom to form a mixture of corner and edge-sharing NBa6 octahedra. The corner-sharing octahedral tilt angles range from 20-24°. In the fifth N site, N(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), one Ba(7), two equivalent Ba(5), and one Nb(2) atom. In the sixth N site, N(6) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(4), one Ba(6), one Ba(7), one Ba(8), and one Nb(2) atom. In the seventh N site, N(7) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(5), one Ba(6), two equivalent Ba(1), and one Nb(2) atom. In the eighth N site, N(8) is bonded to one Ba(9), two equivalent Ba(2), two equivalent Ba(8), and one Nb(1) atom to form distorted NBa5Nb octahedra that share corners with two equivalent N(4)Ba6 octahedra,  an edgeedge with one N(4)Ba6 octahedra, and edges with two equivalent N(8)Ba5Nb octahedra. The corner-sharing octahedral tilt angles range from 20-24°. In the ninth N site, N(9) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(6), one Ba(9), two equivalent Ba(4), and one Nb(1) atom. In the tenth N site, N(10) is bonded in a 4-coordinate geometry to one Ba(6), one Ba(7), two equivalent Ba(3), and one N(12) atom. In the eleventh N site, N(11) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), one Ba(6), one Ba(7), one Ba(9), and one N(12) atom. In the twelfth N site, N(12) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one N(10), and one N(11) atom.
Ba9(NbN6)2 crystallizes in the triclinic P-1 space group. There are nine inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one N(1), one N(11), one N(12), one N(2), one N(5), and two equivalent N(7) atoms. The Ba(1)-N(1) bond length is 2.94 Å. The Ba(1)-N(11) bond length is 3.04 Å. The Ba(1)-N(12) bond length is 3.29 Å. The Ba(1)-N(2) bond length is 2.76 Å. The Ba(1)-N(5) bond length is 3.19 Å. There is one shorter (2.70 Å) and one longer (2.83 Å) Ba(1)-N(7) bond length. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one N(2), one N(4), one N(6), one N(7), one N(9), and two equivalent N(8) atoms. The Ba(2)-N(2) bond length is 2.98 Å. The Ba(2)-N(4) bond length is 2.83 Å. The Ba(2)-N(6) bond length is 3.31 Å. The Ba(2)-N(7) bond length is 3.35 Å. The Ba(2)-N(9) bond length is 3.07 Å. There is one shorter (2.90 Å) and one longer (3.02 Å) Ba(2)-N(8) bond length. In the third Ba site, Ba(3) is bonded in a 8-coordinate geometry to one N(1), one N(11), one N(12), one N(2), one N(3), one N(5), and two equivalent N(10) atoms. The Ba(3)-N(1) bond length is 2.74 Å. The Ba(3)-N(11) bond length is 3.34 Å. The Ba(3)-N(12) bond length is 3.15 Å. The Ba(3)-N(2) bond length is 2.62 Å. The Ba(3)-N(3) bond length is 3.34 Å. The Ba(3)-N(5) bond length is 2.69 Å. There is one shorter (3.16 Å) and one longer (3.35 Å) Ba(3)-N(10) bond length. In the fourth Ba site, Ba(4) is bonded to one N(3), one N(4), one N(6), and two equivalent N(9) atoms to form distorted BaN5 trigonal bipyramids that share  a cornercorner with one Ba(8)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra,  a cornercorner with one Nb(2)N4 tetrahedra,  a cornercorner with one Ba(5)N5 trigonal bipyramid, corners with three equivalent Ba(9)N5 trigonal bipyramids,  an edgeedge with one Ba(8)N6 octahedra, edges with two equivalent Ba(6)N6 octahedra,  an edgeedge with one Nb(1)N4 tetrahedra, and  an edgeedge with one Ba(4)N5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 77°. The Ba(4)-N(3) bond length is 3.01 Å. The Ba(4)-N(4) bond length is 2.71 Å. The Ba(4)-N(6) bond length is 2.93 Å. There is one shorter (2.72 Å) and one longer (3.29 Å) Ba(4)-N(9) bond length. In the fifth Ba site, Ba(5) is bonded to one N(2), one N(4), one N(7), and two equivalent N(5) atoms to form distorted BaN5 trigonal bipyramids that share  a cornercorner with one Ba(8)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra, corners with three equivalent Nb(2)N4 tetrahedra,  a cornercorner with one Ba(4)N5 trigonal bipyramid,  an edgeedge with one Ba(6)N6 octahedra, and  an edgeedge with one Ba(5)N5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 100°. The Ba(5)-N(2) bond length is 3.03 Å. The Ba(5)-N(4) bond length is 2.98 Å. The Ba(5)-N(7) bond length is 2.71 Å. There is one shorter (2.86 Å) and one longer (2.95 Å) Ba(5)-N(5) bond length. In the sixth Ba site, Ba(6) is bonded to one N(10), one N(11), one N(4), one N(6), one N(7), and one N(9) atom to form distorted BaN6 octahedra that share corners with two equivalent Ba(8)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra,  an edgeedge with one Nb(2)N4 tetrahedra,  an edgeedge with one Ba(5)N5 trigonal bipyramid,  an edgeedge with one Ba(9)N5 trigonal bipyramid, and edges with two equivalent Ba(4)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-19°. The Ba(6)-N(10) bond length is 3.01 Å. The Ba(6)-N(11) bond length is 3.13 Å. The Ba(6)-N(4) bond length is 2.74 Å. The Ba(6)-N(6) bond length is 2.80 Å. The Ba(6)-N(7) bond length is 2.92 Å. The Ba(6)-N(9) bond length is 2.95 Å. In the seventh Ba site, Ba(7) is bonded in a 6-coordinate geometry to one N(10), one N(11), one N(3), one N(4), one N(5), and one N(6) atom. The Ba(7)-N(10) bond length is 3.10 Å. The Ba(7)-N(11) bond length is 3.25 Å. The Ba(7)-N(3) bond length is 2.86 Å. The Ba(7)-N(4) bond length is 2.57 Å. The Ba(7)-N(5) bond length is 3.23 Å. The Ba(7)-N(6) bond length is 2.63 Å. In the eighth Ba site, Ba(8) is bonded to one N(1), one N(3), one N(4), one N(6), and two equivalent N(8) atoms to form distorted BaN6 octahedra that share corners with two equivalent Ba(6)N6 octahedra,  a cornercorner with one Nb(1)N4 tetrahedra,  a cornercorner with one Ba(4)N5 trigonal bipyramid,  a cornercorner with one Ba(5)N5 trigonal bipyramid,  an edgeedge with one Ba(8)N6 octahedra,  an edgeedge with one Nb(1)N4 tetrahedra,  an edgeedge with one Nb(2)N4 tetrahedra,  an edgeedge with one Ba(4)N5 trigonal bipyramid, and edges with two equivalent Ba(9)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-19°. The Ba(8)-N(1) bond length is 2.99 Å. The Ba(8)-N(3) bond length is 3.17 Å. The Ba(8)-N(4) bond length is 2.98 Å. The Ba(8)-N(6) bond length is 2.95 Å. There is one shorter (2.87 Å) and one longer (3.06 Å) Ba(8)-N(8) bond length. In the ninth Ba site, Ba(9) is bonded to one N(1), one N(11), one N(3), one N(8), and one N(9) atom to form distorted BaN5 trigonal bipyramids that share  a cornercorner with one Nb(2)N4 tetrahedra, corners with three equivalent Nb(1)N4 tetrahedra, corners with three equivalent Ba(4)N5 trigonal bipyramids,  an edgeedge with one Ba(6)N6 octahedra, and edges with two equivalent Ba(8)N6 octahedra. The Ba(9)-N(1) bond length is 2.86 Å. The Ba(9)-N(11) bond length is 3.28 Å. The Ba(9)-N(3) bond length is 2.82 Å. The Ba(9)-N(8) bond length is 2.65 Å. The Ba(9)-N(9) bond length is 2.86 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one N(2), one N(3), one N(8), and one N(9) atom to form NbN4 tetrahedra that share  a cornercorner with one Ba(6)N6 octahedra,  a cornercorner with one Ba(8)N6 octahedra,  a cornercorner with one Ba(4)N5 trigonal bipyramid,  a cornercorner with one Ba(5)N5 trigonal bipyramid, corners with three equivalent Ba(9)N5 trigonal bipyramids,  an edgeedge with one Ba(8)N6 octahedra, and  an edgeedge with one Ba(4)N5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 71-85°. The Nb(1)-N(2) bond length is 2.00 Å. The Nb(1)-N(3) bond length is 1.99 Å. The Nb(1)-N(8) bond length is 1.97 Å. The Nb(1)-N(9) bond length is 2.03 Å. In the second Nb site, Nb(2) is bonded to one N(1), one N(5), one N(6), and one N(7) atom to form NbN4 tetrahedra that share  a cornercorner with one Ba(4)N5 trigonal bipyramid,  a cornercorner with one Ba(9)N5 trigonal bipyramid, corners with three equivalent Ba(5)N5 trigonal bipyramids,  an edgeedge with one Ba(6)N6 octahedra, and  an edgeedge with one Ba(8)N6 octahedra. The Nb(2)-N(1) bond length is 2.01 Å. The Nb(2)-N(5) bond length is 1.99 Å. The Nb(2)-N(6) bond length is 1.99 Å. The Nb(2)-N(7) bond length is 1.96 Å. There are twelve inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), one Ba(8), one Ba(9), and one Nb(2) atom. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), one Ba(3), one Ba(5), and one Nb(1) atom. In the third N site, N(3) is bonded in a 6-coordinate geometry to one Ba(3), one Ba(4), one Ba(7), one Ba(8), one Ba(9), and one Nb(1) atom. In the fourth N site, N(4) is bonded to one Ba(2), one Ba(4), one Ba(5), one Ba(6), one Ba(7), and one Ba(8) atom to form a mixture of corner and edge-sharing NBa6 octahedra. The corner-sharing octahedral tilt angles range from 20-24°. In the fifth N site, N(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), one Ba(7), two equivalent Ba(5), and one Nb(2) atom. In the sixth N site, N(6) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(4), one Ba(6), one Ba(7), one Ba(8), and one Nb(2) atom. In the seventh N site, N(7) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(5), one Ba(6), two equivalent Ba(1), and one Nb(2) atom. In the eighth N site, N(8) is bonded to one Ba(9), two equivalent Ba(2), two equivalent Ba(8), and one Nb(1) atom to form distorted NBa5Nb octahedra that share corners with two equivalent N(4)Ba6 octahedra,  an edgeedge with one N(4)Ba6 octahedra, and edges with two equivalent N(8)Ba5Nb octahedra. The corner-sharing octahedral tilt angles range from 20-24°. In the ninth N site, N(9) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(6), one Ba(9), two equivalent Ba(4), and one Nb(1) atom. In the tenth N site, N(10) is bonded in a 4-coordinate geometry to one Ba(6), one Ba(7), two equivalent Ba(3), and one N(12) atom. The N(10)-N(12) bond length is 1.19 Å. In the eleventh N site, N(11) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(3), one Ba(6), one Ba(7), one Ba(9), and one N(12) atom. The N(11)-N(12) bond length is 1.19 Å. In the twelfth N site, N(12) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(3), one N(10), and one N(11) atom.