Na2Ca5N4 crystallizes in the tetragonal P4/ncc space group. Na(1) is bonded in a linear geometry to two equivalent N(1) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a square co-planar geometry to four equivalent N(1) atoms. In the second Ca site, Ca(2) is bonded in a distorted see-saw-like geometry to four equivalent N(1) atoms. N(1) is bonded to one Na(1), one Ca(1), and four equivalent Ca(2) atoms to form a mixture of corner and edge-sharing NNaCa5 octahedra. The corner-sharing octahedral tilt angles range from 0-20°.
Na2Ca5N4 crystallizes in the tetragonal P4/ncc space group. Na(1) is bonded in a linear geometry to two equivalent N(1) atoms. Both Na(1)-N(1) bond lengths are 2.41 Å. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a square co-planar geometry to four equivalent N(1) atoms. All Ca(1)-N(1) bond lengths are 2.58 Å. In the second Ca site, Ca(2) is bonded in a distorted see-saw-like geometry to four equivalent N(1) atoms. There are a spread of Ca(2)-N(1) bond distances ranging from 2.38-2.53 Å. N(1) is bonded to one Na(1), one Ca(1), and four equivalent Ca(2) atoms to form a mixture of corner and edge-sharing NNaCa5 octahedra. The corner-sharing octahedral tilt angles range from 0-20°.