Ca3(TiN2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted CaN6 octahedra that share corners with two equivalent Ca(1)N6 octahedra, corners with five equivalent Ca(2)N6 octahedra, corners with six equivalent Ti(1)N4 tetrahedra, edges with six equivalent Ca(1)N6 octahedra, edges with three equivalent Ti(1)N4 tetrahedra, and  a faceface with one Ca(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 15-62°. 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 ten equivalent Ca(1)N6 octahedra, corners with four equivalent Ti(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, edges with four equivalent Ti(1)N4 tetrahedra, and faces with two equivalent Ca(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 31-62°. Ti(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form TiN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with six equivalent Ca(1)N6 octahedra, corners with two equivalent Ti(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, edges with three equivalent Ca(1)N6 octahedra, and  an edgeedge with one Ti(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-82°. 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 Ti(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 Ti(1) atoms.
Ca3(TiN2)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted CaN6 octahedra that share corners with two equivalent Ca(1)N6 octahedra, corners with five equivalent Ca(2)N6 octahedra, corners with six equivalent Ti(1)N4 tetrahedra, edges with six equivalent Ca(1)N6 octahedra, edges with three equivalent Ti(1)N4 tetrahedra, and  a faceface with one Ca(2)N6 octahedra. The corner-sharing octahedral tilt angles range from 15-62°. There is one shorter (2.53 Å) and one longer (2.68 Å) Ca(1)-N(2) bond length. There are a spread of Ca(1)-N(1) bond distances ranging from 2.57-2.82 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 ten equivalent Ca(1)N6 octahedra, corners with four equivalent Ti(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, edges with four equivalent Ti(1)N4 tetrahedra, and faces with two equivalent Ca(1)N6 octahedra. The corner-sharing octahedral tilt angles range from 31-62°. Both Ca(2)-N(1) bond lengths are 2.63 Å. There are two shorter (2.48 Å) and two longer (2.58 Å) Ca(2)-N(2) bond lengths. Ti(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form TiN4 tetrahedra that share corners with two equivalent Ca(2)N6 octahedra, corners with six equivalent Ca(1)N6 octahedra, corners with two equivalent Ti(1)N4 tetrahedra, edges with two equivalent Ca(2)N6 octahedra, edges with three equivalent Ca(1)N6 octahedra, and  an edgeedge with one Ti(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-82°. There is one shorter (2.01 Å) and one longer (2.11 Å) Ti(1)-N(1) bond length. Both Ti(1)-N(2) bond lengths are 1.95 Å. 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 Ti(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 Ti(1) atoms.