Ca3(RuN2)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 Ru(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and edges with four equivalent Ru(1)N4 tetrahedra. Ru(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted RuN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with two equivalent Ru(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and  an edgeedge with one Ru(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-56°. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), four equivalent Ca(1), and two equivalent Ru(1) atoms to form a mixture of distorted corner, edge, and face-sharing NCa5Ru2 pentagonal bipyramids. 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 Ru(1) atoms.
Ca3(RuN2)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 (2.46 Å) and one longer (2.64 Å) Ca(1)-N(2) bond length. There are a spread of Ca(1)-N(1) bond distances ranging from 2.54-2.79 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 Ru(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and edges with four equivalent Ru(1)N4 tetrahedra. Both Ca(2)-N(1) bond lengths are 2.61 Å. There are two shorter (2.41 Å) and two longer (2.50 Å) Ca(2)-N(2) bond lengths. Ru(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted RuN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with two equivalent Ru(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, and  an edgeedge with one Ru(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-56°. There is one shorter (2.02 Å) and one longer (2.17 Å) Ru(1)-N(1) bond length. There is one shorter (1.96 Å) and one longer (1.99 Å) Ru(1)-N(2) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), four equivalent Ca(1), and two equivalent Ru(1) atoms to form a mixture of distorted corner, edge, and face-sharing NCa5Ru2 pentagonal bipyramids. 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 Ru(1) atoms.