Ca3(VN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing VN4 tetrahedra. In the second V site, V(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing VN4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one V(1), and one V(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), one V(1), and one V(2) atom.
Ca3(VN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. The Ca(1)-N(1) bond length is 2.44 Å. There are a spread of Ca(1)-N(2) bond distances ranging from 2.41-2.59 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. Both Ca(2)-N(2) bond lengths are 2.77 Å. There are two shorter (2.58 Å) and two longer (2.64 Å) Ca(2)-N(1) bond lengths. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing VN4 tetrahedra. Both V(1)-N(1) bond lengths are 1.90 Å. Both V(1)-N(2) bond lengths are 1.89 Å. In the second V site, V(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing VN4 tetrahedra. Both V(2)-N(1) bond lengths are 1.95 Å. Both V(2)-N(2) bond lengths are 1.99 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one V(1), and one V(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), one V(1), and one V(2) atom.