Ca3(VN2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form distorted CaN6 octahedra that share corners with four equivalent V(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and edges with four equivalent V(1)N4 tetrahedra. V(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form VN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with two equivalent V(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and  an edgeedge with one V(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-54°. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to one Ca(2), four equivalent Ca(1), and two equivalent V(1) atoms. In the second N site, N(2) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and two equivalent V(1) atoms.
Ca3(VN2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. There is one shorter (2.54 Å) and one longer (2.58 Å) Ca(1)-N(2) bond length. There are a spread of Ca(1)-N(1) bond distances ranging from 2.53-2.82 Å. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and four equivalent N(2) atoms to form distorted CaN6 octahedra that share corners with four equivalent V(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and edges with four equivalent V(1)N4 tetrahedra. Both Ca(2)-N(1) bond lengths are 2.61 Å. There are two shorter (2.48 Å) and two longer (2.52 Å) Ca(2)-N(2) bond lengths. V(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form VN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with two equivalent V(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and  an edgeedge with one V(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-54°. There is one shorter (1.97 Å) and one longer (2.01 Å) V(1)-N(1) bond length. There is one shorter (1.89 Å) and one longer (1.92 Å) V(1)-N(2) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to one Ca(2), four equivalent Ca(1), and two equivalent V(1) atoms. In the second N site, N(2) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), and two equivalent V(1) atoms.