Ca4VN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(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 Ca site, Ca(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. In the third Ca site, Ca(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Ca(4)N5 square pyramids, corners with three equivalent V(1)N4 tetrahedra, edges with two equivalent Ca(3)N5 square pyramids, edges with three equivalent Ca(4)N5 square pyramids, and  an edgeedge with one V(1)N4 tetrahedra. In the fourth Ca site, Ca(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Ca(3)N5 square pyramids,  a cornercorner with one V(1)N4 tetrahedra, edges with two equivalent Ca(4)N5 square pyramids, edges with three equivalent Ca(3)N5 square pyramids, and edges with two equivalent V(1)N4 tetrahedra. 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  a cornercorner with one Ca(4)N5 square pyramid, corners with three equivalent Ca(3)N5 square pyramids,  an edgeedge with one Ca(3)N5 square pyramid, and edges with two equivalent Ca(4)N5 square pyramids. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one V(1) atom to form a mixture of corner and edge-sharing NCa5V octahedra. The corner-sharing octahedral tilt angles range from 15-16°. In the second N site, N(2) is bonded in a 5-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and one V(1) atom. In the third N site, N(3) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing NCa5V octahedra. The corner-sharing octahedral tilt angles range from 15-16°. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one V(1) atom.
Ca4VN4 crystallizes in the triclinic P-1 space group. There are four inequivalent Ca sites. In the first Ca site, Ca(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 Ca(1)-N(1) bond length is 2.45 Å. The Ca(1)-N(3) bond length is 2.61 Å. The Ca(1)-N(4) bond length is 2.60 Å. There is one shorter (2.39 Å) and one longer (2.72 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. There is one shorter (2.40 Å) and one longer (2.49 Å) Ca(2)-N(2) bond length. There is one shorter (2.45 Å) and one longer (2.55 Å) Ca(2)-N(3) bond length. In the third Ca site, Ca(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Ca(4)N5 square pyramids, corners with three equivalent V(1)N4 tetrahedra, edges with two equivalent Ca(3)N5 square pyramids, edges with three equivalent Ca(4)N5 square pyramids, and  an edgeedge with one V(1)N4 tetrahedra. The Ca(3)-N(3) bond length is 2.44 Å. There is one shorter (2.43 Å) and one longer (2.45 Å) Ca(3)-N(1) bond length. There is one shorter (2.49 Å) and one longer (2.67 Å) Ca(3)-N(4) bond length. In the fourth Ca site, Ca(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form distorted CaN5 square pyramids that share corners with three equivalent Ca(3)N5 square pyramids,  a cornercorner with one V(1)N4 tetrahedra, edges with two equivalent Ca(4)N5 square pyramids, edges with three equivalent Ca(3)N5 square pyramids, and edges with two equivalent V(1)N4 tetrahedra. The Ca(4)-N(3) bond length is 2.47 Å. There is one shorter (2.42 Å) and one longer (2.55 Å) Ca(4)-N(1) bond length. There is one shorter (2.62 Å) and one longer (2.67 Å) Ca(4)-N(4) 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  a cornercorner with one Ca(4)N5 square pyramid, corners with three equivalent Ca(3)N5 square pyramids,  an edgeedge with one Ca(3)N5 square pyramid, and edges with two equivalent Ca(4)N5 square pyramids. The V(1)-N(1) bond length is 1.83 Å. The V(1)-N(2) bond length is 1.84 Å. The V(1)-N(3) bond length is 1.89 Å. The V(1)-N(4) bond length is 1.87 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one V(1) atom to form a mixture of corner and edge-sharing NCa5V octahedra. The corner-sharing octahedral tilt angles range from 15-16°. In the second N site, N(2) is bonded in a 5-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and one V(1) atom. In the third N site, N(3) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing NCa5V octahedra. The corner-sharing octahedral tilt angles range from 15-16°. In the fourth N site, N(4) is bonded in a 6-coordinate geometry to one Ca(1), two equivalent Ca(3), two equivalent Ca(4), and one V(1) atom.