Ca5(VN3)2 crystallizes in the monoclinic Pm space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), and two equivalent N(6) atoms to form CaN4 trigonal pyramids that share corners with two equivalent Ca(2)N5 square pyramids, corners with two equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(4)N5 square pyramid, and edges with two equivalent Ca(3)N5 trigonal bipyramids. In the second Ca site, Ca(2) is bonded to one N(2), one N(4), one N(6), and two equivalent N(5) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(2)N5 square pyramids,  a cornercorner with one Ca(3)N5 trigonal bipyramid, corners with two equivalent Ca(1)N4 trigonal pyramids, edges with two equivalent Ca(4)N5 square pyramids, and  an edgeedge with one Ca(3)N5 trigonal bipyramid. In the third Ca site, Ca(3) is bonded to one N(2), one N(4), one N(6), and two equivalent N(3) atoms to form distorted CaN5 trigonal bipyramids that share  a cornercorner with one Ca(2)N5 square pyramid, corners with two equivalent Ca(3)N5 trigonal bipyramids,  an edgeedge with one Ca(2)N5 square pyramid, edges with two equivalent Ca(4)N5 square pyramids, and edges with two equivalent Ca(1)N4 trigonal pyramids. In the fourth Ca site, Ca(4) is bonded to one N(1), one N(3), one N(5), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(4)N5 square pyramids, edges with two equivalent Ca(2)N5 square pyramids, edges with two equivalent Ca(3)N5 trigonal bipyramids, and  an edgeedge with one Ca(1)N4 trigonal pyramid. In the fifth Ca site, Ca(5) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(5), and two equivalent N(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a trigonal planar geometry to one N(2), one N(4), and one N(6) atom. In the second V site, V(2) is bonded in a trigonal planar geometry to one N(1), one N(3), and one N(5) atom. There are six inequivalent N sites. In the first N site, N(1) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Ca(4), one Ca(5), and one V(2) atom. In the second N site, N(2) is bonded to one Ca(2), one Ca(3), two equivalent Ca(5), and one V(1) atom to form distorted NCa4V square pyramids that share  a cornercorner with one N(4)Ca4V square pyramid, corners with two equivalent N(2)Ca4V square pyramids, corners with three equivalent N(6)Ca4V trigonal bipyramids, edges with two equivalent N(3)Ca5V octahedra, and  an edgeedge with one N(4)Ca4V square pyramid. In the third N site, N(3) is bonded to one Ca(1), one Ca(4), one Ca(5), two equivalent Ca(3), and one V(2) atom to form NCa5V octahedra that share corners with two equivalent N(3)Ca5V octahedra, edges with two equivalent N(2)Ca4V square pyramids, edges with two equivalent N(4)Ca4V square pyramids, and edges with two equivalent N(6)Ca4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 13°. In the fourth N site, N(4) is bonded to one Ca(2), one Ca(3), two equivalent Ca(4), and one V(1) atom to form NCa4V square pyramids that share  a cornercorner with one N(2)Ca4V square pyramid, corners with two equivalent N(4)Ca4V square pyramids,  a cornercorner with one N(6)Ca4V trigonal bipyramid, edges with two equivalent N(3)Ca5V octahedra,  an edgeedge with one N(2)Ca4V square pyramid, and  an edgeedge with one N(6)Ca4V trigonal bipyramid. In the fifth N site, N(5) is bonded in a 5-coordinate geometry to one Ca(4), one Ca(5), two equivalent Ca(2), and one V(2) atom. In the sixth N site, N(6) is bonded to one Ca(2), one Ca(3), two equivalent Ca(1), and one V(1) atom to form distorted NCa4V trigonal bipyramids that share  a cornercorner with one N(4)Ca4V square pyramid, corners with three equivalent N(2)Ca4V square pyramids, corners with two equivalent N(6)Ca4V trigonal bipyramids, edges with two equivalent N(3)Ca5V octahedra, and  an edgeedge with one N(4)Ca4V square pyramid.
Ca5(VN3)2 crystallizes in the monoclinic Pm space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), and two equivalent N(6) atoms to form CaN4 trigonal pyramids that share corners with two equivalent Ca(2)N5 square pyramids, corners with two equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(4)N5 square pyramid, and edges with two equivalent Ca(3)N5 trigonal bipyramids. The Ca(1)-N(1) bond length is 2.38 Å. The Ca(1)-N(3) bond length is 2.44 Å. Both Ca(1)-N(6) bond lengths are 2.59 Å. In the second Ca site, Ca(2) is bonded to one N(2), one N(4), one N(6), and two equivalent N(5) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(2)N5 square pyramids,  a cornercorner with one Ca(3)N5 trigonal bipyramid, corners with two equivalent Ca(1)N4 trigonal pyramids, edges with two equivalent Ca(4)N5 square pyramids, and  an edgeedge with one Ca(3)N5 trigonal bipyramid. The Ca(2)-N(2) bond length is 2.41 Å. The Ca(2)-N(4) bond length is 2.42 Å. The Ca(2)-N(6) bond length is 2.64 Å. Both Ca(2)-N(5) bond lengths are 2.50 Å. In the third Ca site, Ca(3) is bonded to one N(2), one N(4), one N(6), and two equivalent N(3) atoms to form distorted CaN5 trigonal bipyramids that share  a cornercorner with one Ca(2)N5 square pyramid, corners with two equivalent Ca(3)N5 trigonal bipyramids,  an edgeedge with one Ca(2)N5 square pyramid, edges with two equivalent Ca(4)N5 square pyramids, and edges with two equivalent Ca(1)N4 trigonal pyramids. The Ca(3)-N(2) bond length is 2.70 Å. The Ca(3)-N(4) bond length is 2.41 Å. The Ca(3)-N(6) bond length is 2.56 Å. Both Ca(3)-N(3) bond lengths are 2.50 Å. In the fourth Ca site, Ca(4) is bonded to one N(1), one N(3), one N(5), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(4)N5 square pyramids, edges with two equivalent Ca(2)N5 square pyramids, edges with two equivalent Ca(3)N5 trigonal bipyramids, and  an edgeedge with one Ca(1)N4 trigonal pyramid. The Ca(4)-N(1) bond length is 2.33 Å. The Ca(4)-N(3) bond length is 2.47 Å. The Ca(4)-N(5) bond length is 2.99 Å. Both Ca(4)-N(4) bond lengths are 2.51 Å. In the fifth Ca site, Ca(5) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(5), and two equivalent N(2) atoms. The Ca(5)-N(1) bond length is 2.91 Å. The Ca(5)-N(3) bond length is 2.39 Å. The Ca(5)-N(5) bond length is 2.49 Å. Both Ca(5)-N(2) bond lengths are 2.50 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a trigonal planar geometry to one N(2), one N(4), and one N(6) atom. The V(1)-N(2) bond length is 1.81 Å. The V(1)-N(4) bond length is 1.79 Å. The V(1)-N(6) bond length is 1.79 Å. In the second V site, V(2) is bonded in a trigonal planar geometry to one N(1), one N(3), and one N(5) atom. The V(2)-N(1) bond length is 1.72 Å. The V(2)-N(3) bond length is 1.88 Å. The V(2)-N(5) bond length is 1.80 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Ca(4), one Ca(5), and one V(2) atom. In the second N site, N(2) is bonded to one Ca(2), one Ca(3), two equivalent Ca(5), and one V(1) atom to form distorted NCa4V square pyramids that share  a cornercorner with one N(4)Ca4V square pyramid, corners with two equivalent N(2)Ca4V square pyramids, corners with three equivalent N(6)Ca4V trigonal bipyramids, edges with two equivalent N(3)Ca5V octahedra, and  an edgeedge with one N(4)Ca4V square pyramid. In the third N site, N(3) is bonded to one Ca(1), one Ca(4), one Ca(5), two equivalent Ca(3), and one V(2) atom to form NCa5V octahedra that share corners with two equivalent N(3)Ca5V octahedra, edges with two equivalent N(2)Ca4V square pyramids, edges with two equivalent N(4)Ca4V square pyramids, and edges with two equivalent N(6)Ca4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 13°. In the fourth N site, N(4) is bonded to one Ca(2), one Ca(3), two equivalent Ca(4), and one V(1) atom to form NCa4V square pyramids that share  a cornercorner with one N(2)Ca4V square pyramid, corners with two equivalent N(4)Ca4V square pyramids,  a cornercorner with one N(6)Ca4V trigonal bipyramid, edges with two equivalent N(3)Ca5V octahedra,  an edgeedge with one N(2)Ca4V square pyramid, and  an edgeedge with one N(6)Ca4V trigonal bipyramid. In the fifth N site, N(5) is bonded in a 5-coordinate geometry to one Ca(4), one Ca(5), two equivalent Ca(2), and one V(2) atom. In the sixth N site, N(6) is bonded to one Ca(2), one Ca(3), two equivalent Ca(1), and one V(1) atom to form distorted NCa4V trigonal bipyramids that share  a cornercorner with one N(4)Ca4V square pyramid, corners with three equivalent N(2)Ca4V square pyramids, corners with two equivalent N(6)Ca4V trigonal bipyramids, edges with two equivalent N(3)Ca5V octahedra, and  an edgeedge with one N(4)Ca4V square pyramid.