Ca7TiN6 crystallizes in the orthorhombic Ibam space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form CaN4 tetrahedra that share corners with two equivalent Ti(1)N4 tetrahedra and  an edgeedge with one Ca(1)N4 tetrahedra. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to two equivalent N(2) and three equivalent N(1) atoms. In the third Ca site, Ca(3) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. Ti(1) is bonded to four equivalent N(1) atoms to form TiN4 tetrahedra that share corners with four equivalent Ca(1)N4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), one Ca(3), three equivalent Ca(2), and one Ti(1) atom to form distorted NCa5Ti octahedra that share corners with six equivalent N(1)Ca5Ti octahedra, corners with four equivalent N(2)Ca6 pentagonal pyramids, edges with two equivalent N(1)Ca5Ti octahedra, edges with two equivalent N(2)Ca6 pentagonal pyramids, and  a faceface with one N(1)Ca5Ti octahedra. The corner-sharing octahedral tilt angles range from 40-58°. In the second N site, N(2) is bonded to two equivalent Ca(1) and four equivalent Ca(2) atoms to form distorted NCa6 pentagonal pyramids that share corners with eight equivalent N(1)Ca5Ti octahedra, edges with four equivalent N(1)Ca5Ti octahedra, and edges with three equivalent N(2)Ca6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 30-70°.
Ca7TiN6 crystallizes in the orthorhombic Ibam space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form CaN4 tetrahedra that share corners with two equivalent Ti(1)N4 tetrahedra and  an edgeedge with one Ca(1)N4 tetrahedra. Both Ca(1)-N(1) bond lengths are 2.43 Å. There is one shorter (2.43 Å) and one longer (2.47 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to two equivalent N(2) and three equivalent N(1) atoms. There is one shorter (2.43 Å) and one longer (2.61 Å) Ca(2)-N(2) bond length. There are a spread of Ca(2)-N(1) bond distances ranging from 2.39-2.90 Å. In the third Ca site, Ca(3) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. All Ca(3)-N(1) bond lengths are 2.50 Å. Ti(1) is bonded to four equivalent N(1) atoms to form TiN4 tetrahedra that share corners with four equivalent Ca(1)N4 tetrahedra. All Ti(1)-N(1) bond lengths are 1.95 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), one Ca(3), three equivalent Ca(2), and one Ti(1) atom to form distorted NCa5Ti octahedra that share corners with six equivalent N(1)Ca5Ti octahedra, corners with four equivalent N(2)Ca6 pentagonal pyramids, edges with two equivalent N(1)Ca5Ti octahedra, edges with two equivalent N(2)Ca6 pentagonal pyramids, and  a faceface with one N(1)Ca5Ti octahedra. The corner-sharing octahedral tilt angles range from 40-58°. In the second N site, N(2) is bonded to two equivalent Ca(1) and four equivalent Ca(2) atoms to form distorted NCa6 pentagonal pyramids that share corners with eight equivalent N(1)Ca5Ti octahedra, edges with four equivalent N(1)Ca5Ti octahedra, and edges with three equivalent N(2)Ca6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 30-70°.