Ca2VN3 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form distorted CaN4 trigonal pyramids that share corners with three equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(3)N5 square pyramid, and edges with two equivalent Ca(2)N5 square pyramids. In the second Ca site, Ca(2) is bonded to one N(4), two equivalent N(2), and two equivalent N(3) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(2)N5 square pyramids, edges with two equivalent Ca(3)N5 square pyramids, and edges with four equivalent Ca(1)N4 trigonal pyramids. 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 CaN5 square pyramids that share corners with two equivalent Ca(3)N5 square pyramids, edges with two equivalent Ca(2)N5 square pyramids, and edges with two equivalent Ca(1)N4 trigonal pyramids. There are two inequivalent V sites. In the first V site, V(1) is bonded in a trigonal planar geometry to one N(4) and two equivalent N(2) atoms. In the second V site, V(2) is bonded in a trigonal planar geometry to one N(3) and two equivalent N(1) atoms. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(3), and one V(2) atom. In the second N site, N(2) is bonded in a distorted square co-planar geometry to one Ca(2), two equivalent Ca(1), and one V(1) atom. In the third N site, N(3) is bonded to one Ca(3), two equivalent Ca(1), two equivalent Ca(2), and one V(2) atom to form distorted corner-sharing NCa5V octahedra. The corner-sharing octahedral tilt angles are 18°. In the fourth N site, N(4) is bonded in a square co-planar geometry to one Ca(2), two equivalent Ca(3), and one V(1) atom.
Ca2VN3 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form distorted CaN4 trigonal pyramids that share corners with three equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(3)N5 square pyramid, and edges with two equivalent Ca(2)N5 square pyramids. The Ca(1)-N(1) bond length is 2.36 Å. The Ca(1)-N(3) bond length is 2.35 Å. Both Ca(1)-N(2) bond lengths are 2.54 Å. In the second Ca site, Ca(2) is bonded to one N(4), two equivalent N(2), and two equivalent N(3) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(2)N5 square pyramids, edges with two equivalent Ca(3)N5 square pyramids, and edges with four equivalent Ca(1)N4 trigonal pyramids. The Ca(2)-N(4) bond length is 2.38 Å. Both Ca(2)-N(2) bond lengths are 2.49 Å. Both Ca(2)-N(3) bond lengths are 2.54 Å. 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 CaN5 square pyramids that share corners with two equivalent Ca(3)N5 square pyramids, edges with two equivalent Ca(2)N5 square pyramids, and edges with two equivalent Ca(1)N4 trigonal pyramids. The Ca(3)-N(3) bond length is 2.60 Å. Both Ca(3)-N(1) bond lengths are 2.51 Å. Both Ca(3)-N(4) bond lengths are 2.51 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a trigonal planar geometry to one N(4) and two equivalent N(2) atoms. The V(1)-N(4) bond length is 1.77 Å. Both V(1)-N(2) bond lengths are 1.78 Å. In the second V site, V(2) is bonded in a trigonal planar geometry to one N(3) and two equivalent N(1) atoms. The V(2)-N(3) bond length is 1.92 Å. Both V(2)-N(1) bond lengths are 1.72 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(3), and one V(2) atom. In the second N site, N(2) is bonded in a distorted square co-planar geometry to one Ca(2), two equivalent Ca(1), and one V(1) atom. In the third N site, N(3) is bonded to one Ca(3), two equivalent Ca(1), two equivalent Ca(2), and one V(2) atom to form distorted corner-sharing NCa5V octahedra. The corner-sharing octahedral tilt angles are 18°. In the fourth N site, N(4) is bonded in a square co-planar geometry to one Ca(2), two equivalent Ca(3), and one V(1) atom.