Ca5ZnN4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two 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 distorted CaN4 trigonal pyramids that share corners with two equivalent Ca(2)N4 tetrahedra, corners with two equivalent Zn(1)N4 tetrahedra, corners with eight equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(2)N4 tetrahedra,  an edgeedge with one Zn(1)N4 tetrahedra, and edges with two equivalent Ca(1)N4 trigonal pyramids. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form CaN4 tetrahedra that share corners with four equivalent Zn(1)N4 tetrahedra, corners with eight equivalent Ca(1)N4 trigonal pyramids, and edges with four equivalent Ca(1)N4 trigonal pyramids. Zn(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form ZnN4 tetrahedra that share corners with four equivalent Ca(2)N4 tetrahedra, corners with eight equivalent Ca(1)N4 trigonal pyramids, and edges with four equivalent Ca(1)N4 trigonal pyramids. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Ca(2), four equivalent Ca(1), and one Zn(1) atom. In the second N site, N(2) is bonded to one Ca(2), four equivalent Ca(1), and one Zn(1) atom to form a mixture of distorted edge and corner-sharing NCa5Zn octahedra. The corner-sharing octahedral tilt angles range from 62-64°.
Ca5ZnN4 is Ilmenite-like structured and crystallizes in the orthorhombic Pmmn space group. There are two 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 distorted CaN4 trigonal pyramids that share corners with two equivalent Ca(2)N4 tetrahedra, corners with two equivalent Zn(1)N4 tetrahedra, corners with eight equivalent Ca(1)N4 trigonal pyramids,  an edgeedge with one Ca(2)N4 tetrahedra,  an edgeedge with one Zn(1)N4 tetrahedra, and edges with two equivalent Ca(1)N4 trigonal pyramids. There is one shorter (2.48 Å) and one longer (2.52 Å) Ca(1)-N(1) bond length. There is one shorter (2.38 Å) and one longer (2.50 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form CaN4 tetrahedra that share corners with four equivalent Zn(1)N4 tetrahedra, corners with eight equivalent Ca(1)N4 trigonal pyramids, and edges with four equivalent Ca(1)N4 trigonal pyramids. Both Ca(2)-N(1) bond lengths are 2.36 Å. Both Ca(2)-N(2) bond lengths are 2.36 Å. Zn(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form ZnN4 tetrahedra that share corners with four equivalent Ca(2)N4 tetrahedra, corners with eight equivalent Ca(1)N4 trigonal pyramids, and edges with four equivalent Ca(1)N4 trigonal pyramids. Both Zn(1)-N(1) bond lengths are 2.20 Å. Both Zn(1)-N(2) bond lengths are 2.23 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Ca(2), four equivalent Ca(1), and one Zn(1) atom. In the second N site, N(2) is bonded to one Ca(2), four equivalent Ca(1), and one Zn(1) atom to form a mixture of distorted edge and corner-sharing NCa5Zn octahedra. The corner-sharing octahedral tilt angles range from 62-64°.