Ca3Sc2N4 is Hausmannite-derived structured and crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing ScN4 tetrahedra. In the second Sc site, Sc(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing ScN4 trigonal pyramids. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Sc(1), and one Sc(2) atom to form distorted NCa4Sc2 octahedra that share corners with three equivalent N(1)Ca4Sc2 octahedra, corners with six equivalent N(2)Ca2Sc2 trigonal pyramids, edges with two equivalent N(1)Ca4Sc2 octahedra,  an edgeedge with one N(2)Ca2Sc2 trigonal pyramid, and  a faceface with one N(1)Ca4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 33-78°. In the second N site, N(2) is bonded to two equivalent Ca(1), one Sc(1), and one Sc(2) atom to form distorted NCa2Sc2 trigonal pyramids that share corners with six equivalent N(1)Ca4Sc2 octahedra, corners with four equivalent N(2)Ca2Sc2 trigonal pyramids, and  an edgeedge with one N(1)Ca4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 51-78°.
Ca3Sc2N4 is Hausmannite-derived structured and crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. There is one shorter (2.68 Å) and one longer (2.69 Å) Ca(1)-N(1) bond length. There is one shorter (2.31 Å) and one longer (2.34 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. There are two shorter (2.45 Å) and two longer (2.76 Å) Ca(2)-N(1) bond lengths. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing ScN4 tetrahedra. Both Sc(1)-N(1) bond lengths are 2.12 Å. Both Sc(1)-N(2) bond lengths are 2.10 Å. In the second Sc site, Sc(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing ScN4 trigonal pyramids. Both Sc(2)-N(1) bond lengths are 2.19 Å. Both Sc(2)-N(2) bond lengths are 2.06 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Sc(1), and one Sc(2) atom to form distorted NCa4Sc2 octahedra that share corners with three equivalent N(1)Ca4Sc2 octahedra, corners with six equivalent N(2)Ca2Sc2 trigonal pyramids, edges with two equivalent N(1)Ca4Sc2 octahedra,  an edgeedge with one N(2)Ca2Sc2 trigonal pyramid, and  a faceface with one N(1)Ca4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 33-78°. In the second N site, N(2) is bonded to two equivalent Ca(1), one Sc(1), and one Sc(2) atom to form distorted NCa2Sc2 trigonal pyramids that share corners with six equivalent N(1)Ca4Sc2 octahedra, corners with four equivalent N(2)Ca2Sc2 trigonal pyramids, and  an edgeedge with one N(1)Ca4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 51-78°.